1. The Changing Landscape of Human Chemistry, Wright State University, Dayton, OH, 2 Performance – The Impact of Nanosciences United States; Department of Mechanical and and Biochemistry Materials Engineering, Wright State University, Dayton, OH, United States; 3Department of Physics, Morley O. Stone. 711th Human Performance Wing, Wright State University, Dayton, OH, United States. Air Force Research Laboratory, Wright-Patterson AFB, OH, United States. The potential application of silicene as a hydrogen storage material is studied by computational In all human endeavors, there is a desire to push the modeling using both first principles calculations and limits of human performance – operations within the classical grand canonical Monte Carlo simulations. Air Force are no exception. From aviation to ground The energetics of the adsorption of hydrogen atoms operations, traditional stressors such as fatigue are on silicene are investigated by DFT calculations. In being compounded by the need to process ever- addition, classical simulations were carried out to increasing amounts of information. This deluge of study the physisorption of molecular hydrogen in a information caused by sensor and bandwidth slit-pore model, constructed using two silicene layers, proliferation makes human-intensive operations, such and whose slit-pore size is varied by changing the as decision making, increasingly complicated. interlayer separation. Traditional approaches to alleviate this problem have relied upon increases in manpower (the 4. Interfacial Friction and Sliding in “brainpower”) to sift, prioritize, and act upon this Amorphous Carbon/Nanotube mountain of information. Increasingly, the Nanocomposites Department of Defense and the Air Force are realizing that this solution is untenable. Within the Zhenhai Xia, Jianbing Niu. Department of Human Performance Wing, we realize that advances Mechanical Engineering, The University of Akron, in the biosciences, e.g., neuroscience, and Akron, OH, United States. nanoscience and engineering, e.g., nanoparticle Amorphous carbon matrix nanocomposites assays, are keys to pushing human capacity past reinforced with nanoscale reinforcement such as traditionally accepted limitations. This talk will carbon nanotubes (CNTs) and nano-particles are examine this frontier and outline efforts to reach promising as next generation super-tough and wear novel, multi-disciplinary approaches to redefine resistant coatings. The strength and toughness human performance. properties of these composites are determined by the interface between reinforcement and amorphous- 2. Computational Research for Aerospace phases. Here, interfacial sliding and friction in Materials Development CNT/amorphous carbon composites are analyzed Barry L. Farmer. Materials and Manufacturing using molecular dynamics simulations. We Directorate, Air Force Research Laboratory, Wright- investigate pullout in a nanoscale composite using a Patterson AFB, OH, United States. unit cell composed of one carbon nanotube or a nanofiber and surrounding amorphous carbon matrix The AFRL Materials and Manufacturing Directorate with a certain degree of sp2/sp3 interfacial bonding. utilizes a broad spectrum of computational tools to The nanotubes full of amorphous carbon as discover, develop, understand, and predict the nanofibers were compared with the tube properties and behavior of a wide range of materials configurations. The results show that the interfacial of interest for aerospace applications. These include bonding break and formation play a key role in both hard and soft materials for structural, sensing, interfacial friction. In the case of no chemical optical, thermal, and other applications. An overview bonding formation at the interface, the nanoscale of the types of computational tools that are being roughness determines interfacial friction and it is used and the types of computational chemistry and found that the frictional behavior can be described by materials research that is being conducted will be a molecular friction law. provided through brief summaries of recent and current research projects. 5. Aspects of Multi-Scale Modeling: Calculations of Optical Properties at the 3. Hydrogen Sorption in a Slit-Pore Model of Nano-Scale Silicon Nanosheets Paul N. Day, Kiet A. Nguyen, Jinsong Duan, Ruth Rachel S. Aga,1 Kristy Wickman,1 Amir A. Pachter. Materials & Manufacturing Directorate, Air Farajian,2 Lok C. Lew Yan Voon.3 1Department of

Force Research Laboratory, Wright-Patterson Air developments in the simulation and informatics Force Base, Ohio, United States. methodologies that make the implementation of such approaches a practical reality in both academic and The need for multi-scale modeling is evident in the industrial contexts. prediction of optical properties unique to materials at the nano-scale, which are used in a multitude of applications. In our continuing interest in calculating 7. Probing the Conformational Transition multi-photon absorption for molecular and potentially Mechanism of ClpY by Using Molecular nanomaterials, including nanoclusters and hybrid Dynamics Simulations nanomaterials, we outline limitations from quantum- Huan Wang, Manori Jayasinghe, George Stan. to-continuum modeling, which can be addressed by Department of Chemistry, University of Cincinnati, sequential, combined, and concurrent methods. As an Cincinnati, Oh, United States. example, calculation of spectra of gold nanoclusters will be described, while for nanomaterials at a Clp ATPases are bacterial AAA+ motors which use relatively larger nano-scale, effects of various ATP-dependent conformational transitions to effect parameters on the optical properties of a molecular substrate protein (SP) degradation and emitter nearby gold nanorods will be reported. In this disaggregation. context, multi-scale issues encountered in modeling Structurally, Clp ATPases are ring-shaped homo- weak interactions at a molecule—plasmonic hexamers with a dynamic central channel. nanostructure interface will be discussed. Diaphragm-forming loops, located in the central channel, are suggested to promote the unfoldase and 6. The Role of Simulation and Informatics in translocase actions through repetitive pulling of the the Electronic Laboratory Environment SP. We use molecular dynamics simulations to elucidate the collaboration between subunits and Michael J. Doyle, George Fitzgerald. Accelrys Inc., between the central channel loops during the San Diego, CA, United States. sequential allosteric motions. Our focus is on ClpY, For many years, virtual chemistry and simulation has the best structurally characterized Clp ATPase. been a key decission making step in the design of Conformational transitions between open and close news systems, from catalysts through polymers to states of ClpY are modeled by using the Targeted advanced composites and nanofibers. With the advent Molecular Dynamics (TMD) simulation method, in of modern high performance ciomputing this which a holonomic constraint is employed to reduce capability has become more ubiquitious, and now the RMSD from the target by a preset value at each stands poised to deliver on the vision of pattern based molecular dynamics step. The trajectory of the decission making in materials design and selection. transition was simulated by using langevin dynamics The data source agnostic perspective of modern high and implicit solvent model (EEF1). We find that throughput materials development and informatics, single-subunit conformational transitions elicit a considers simulation and experimental data as both strong response within the adjacent subunit nearest to valid feeds of information into this decission matrix. the active ATP binding site.Channel loops associated with these coupled subunits also interact strongly, which suggests the chiral handing of the SP within the pore. These results are in accord with experiments that indicate ordered sequential allostery of the Clp ATPase ring.

8. Applied Metamaterials Augustine M. Urbas, Katie Thorp. Materials and Manufacturing Directorate, Air Force Resaerch Lab, Dayton, OH, United States. Metamaterials redefine the fundamental properties of systems by creating artificial, meso-scale meta-atoms which dictate the system response to external fields. These meta-atoms and their mutual interactions can yield property sets that natural materials are not The talk will cover recent reductions to proof of these capable of and tailor materials properties to specific concepts as well as discuss new algoriuthmic needs. The Air Force Research Lab has launched a

coherent effort to identify the range of properties transfer cascade among the energy level of the donor accessible by metamaterials systems in an effort to and acceptors, leading to the generation of high spin map out the application potential of the emerging and states. Ability of amphiphilic C60-(antenna) to dynamic research area. As examples, researchers undergo molecular self-assembly forming bilayer have proposed that materials with negative effective vesicle structures may also facilitate our control in refractive indices that are closely matched to free the alignment of fullerene cage molecules. space and materials with values of epsilon or mu near Preliminary investigation on intrinsic and zero could be built with suitably engineered meta- photoinduced magnetic effects of EF-6MCn and its systems. The utility of these composite materials in complex derivatives using the measurements of dc ultra-compact antennas and signal coupling and ac magnetic susceptibilities in the temperature applications will ultimately be determined by range of 1.8–400 K with the magnetization versus secondary considerations based on the application applied magnetic field from –9 to +9 Tesla provides environment and performance gain against insight on the basic magnetic nature of these –• conventional approaches. Similar modification of materials. Detection of stable (EF-6MCn) spin, via electromagnetic response at optical frequencies has EPR measurements, with new absorption bands at been applied to high performance absorbers. Acoustic 1350-1550 nm indicates clearly its electron accepting metamaterials are beginning to be explored for tuned characteristics. Facile triplet spin state formation of mechanical responses and related structured systems EF-6MCn may allow us to explore the possibility of for thermal transport control are being investigated. certain magnetic ordering under saturation We will explore example applications of these magnetization. materials systems and requirements for relevant environments. Research and development thrusts that 10. Tuning Permittivity and Permeability are of interest for pushing the application of Responses by Using Radical Pairs towards metamaterials forward will be described. Development of Molecular MetaMaterials 9. Synthesis and Photoinduced Bin Hu. Department of Materials Science and Pharacteristics of Emerald Green Fullerene Engineering, University of Tennessee, Knoxville, Tennessee, United States. and C60-(Antenna) Nanostructures as Molecular Basis of Metamaterials This presentation will report the recent research progress in tuning permittivity and permeability by Long Chiang,1 Arthur Epstein,2 Loon-Seng Tan,3 3 1 using photoinduced radical pairs in organic Augustine Urbas. Department of Chemistry, semiconducting materials. We found that University of Massachusetts Lowell, Lowell, MA, 2 photoinduced radical pairs can exhibit tunable United States; Department of Physics, The Ohio intrinsic electric and magnetic dipoles which are State University, Columbus, OH, United States; 3 sensitive to applied electromagnetic field. In AFRL/RX, Air Force Research Laboratory, Dayton, particular, the photoinduced radical pairs can modify OH, United States. the permittivity and permeability and consequently The new concept of molecular metamaterials is changes the refractive index in organic materials. based on the ability of molecular organics to undergo Furthermore, we observed that changing dielectric ultrafast responses upon light irradiation associated and magnetic background can affect the permittivity with the generation of unnatural or exceptional and permeability responses in radical-pair systems. effects on electric polarization and magnetic local Therefore, radical pairs form a new pathway to field. Emerald Green Fullerene, EF-6MCn, possesses generate permittivity and permeability responses unique [18π]-trannulene belt orbital at the HOMO– towards the development of molecular metamaterials. LUMO transition level. Negatively charged EF-6MCn This presentation will discuss the fundamental upon irradiation in reversibility is proposed to serve processes involved in the permittivity and as a key component in the design of molecular permeability responses in radical-pair systems. metamaterials. Synthetic challenge to attach six addends on one C60 cage in the highest possible 11. Production of High Aspect Ratio symmetrical manner led to the discovery of low Magnetic Oxide Nanoparticles Via Novel excitation energy band-gap of EF-6MCn in NIR Synthetic Techniques region. Its combination with ultrafast Matthew J. O’Malley,1 Thomas F. Ekiert,1 Kelsey photoresponsive C60-(antenna)x (x = 1, or 2) Miles,2 Angela Griner,2 Cory Flynn,2 Brandon nanostructure in femtosecond region may allow both 2 2 3 1 the intramolecular and intermolecular excited energy- Yocum, Kevin Davis, Max Alexander. Universal Technology Corporation (UTC), United States;

2Southwestern Council for Higher Education Richard A. Vaia. Air Force Research Laboratory, (SOCHE), United States; 3Wright Patterson Air Force Wright-Patterson Air Force Base, Dayton, Ohio, Base (WPAFB), United States. United States. The overall objective of this research is to develop The coupling of optical excitation to the plasmon new hybrid metal/polymer nanocomposite resonances of well-defined proto-assemblies of metamaterials with low electrical losses (tan δ < noble-metal nanoparticles, such as parallel rods, U- 0.001) and independently modifiable permittivity and or H- configurations, provide exciting opportunities permeability (µ = ε ∼ 3-5) in the 800 MHz to 10 GHz to tailor local field intensities or generate an artificial frequency range. These material properties are key to permeability. In numerous applications, large-area, enabling improved conformal antenna gain, reduction three-dimensional organization of these proto- in antenna aperture size, and improved bandwidth assemblies is desired. As an alternative to top-down control. Our approach to achieving independently lithographic techniques and their inherent challenges engineered permittivity and permeability while limiting these goals, bottom-up approaches to maintaining low electronic loss is to produce high fabricate the proto-assemblies provide a possible aspect ratio magnetic oxide core/shell nanoparticles alternative commensurate with large-scale composed of both hard and soft magnetic materials. manufacturing. In this context, the different side and The results presented here build on our previous end chemistry of gold nanorods was utilized to work involving core/shell nanoparticles as well as our control the orientation dependence of the particle-pair more recent work using novel microwave assisted potential. By taking advantage of the tuned solvent and solvothermal synthetic techniques in order to chemistry governed by the functionality of these produce high aspect ratio magnetic oxide tailored molecules, control assembly of these rods as nanoparticles with a spinel structure (Fe3O4, a parallel pair was achieved. For instance, good CoFe2O4, and etc. ). The resulting structural and solvent for CTAB such as ethanol destabilizes the magnetic properties of these size and shape tailored CTAB bilayer on the side of the nanorods. This systems will be presented. Methods of instantaneously reduces the electrostatic repulsion characterization include scanning and transmission between the rods dominating the van der Waals electron microscopy, X-ray Diffraction as well as attraction, resulting in side by side pair formation of SQUID magnetometry. the rods. The plasmon coupling of these pairs was characterized by extinction spectroscopy and dark 12. Organo-Soluble Functionalized Gold field scattering. The intensity and energy of the Nanorods: Opportunity and Challenge plasmon resonances depended on rod spacing and local arrangement, and were consistent with the 1 1 2 2 Quan Li, Yannian Li, Dingshan Yu, Liming Dai, plasmon hybridization model and electrodynamic 3 1 Augustine Urbas. Liquid Crystal Institute, Kent calculations. State University, Kent, Ohio, United States; 2 Department of Chemical Engineering, Case Western 14. Doping Carbon Nanotube Using Spark Reserve University, Cleveland, Ohio, United States; Plasma Sintering 3Materials and Manufacturing Directorate, Air Force Research Laboratory, Dayton, Ohio, United States. Keqin Yang, Jian He, H. Dale, Pooja Puneet, Z. Su, Malcolm J. Skove, Terry M. Tritt, Apparao M. Rao. Owing to their unusual behaviour compared with Department of Physics and Astronomy, Clemson spherical gold nanoparticles as well as corresponding University, Clemson, SC, United States. bulk materials, gold nanorods provide tremendous opportunities as well as challenges for insights in Here we show that carbon nanotube (CNT) can be fundamental science that opens the door to doped with boron atoms the using spark plasma applications such as optics, sensors, biological sintering (SPS) method. Raman spectra were used to imaging, and anticancer agents. In this talk, I will characterize boron doped carbon nanotubes. A present our recent progress on organo-soluble plateau appears in the temperature dependent functionalized gold nanorods. resistivity data ρ(T) ∼40 K, and is accompanied with a phonon drag feature in the same temperature range 13. Bottom-Up Approach towards Optical in the thermoelectric power data. These features Metamaterials: Proto-Assembly of Gold changes systematically with different doping Nanorods for Tunable Plasmon Coupling concentration. Specifically, ρ(T) of 7.5 at. % boron doped CNT sample show a current dependent Dhriti Nepal, Kyoungweon Park, Christopher Tabor, behavior at low temperature, which is explained in Jinsong Duan, Ruth Pachter, Michael Durstock, term of Fermi surface nesting. Magnetic

susceptibility measurements showed reduction effects of ligands/solvent on the structure, stability, around 20 K which may be associated with and spectra were also examined for selected clusters. superconducting transition in boron doped CNTs. 17. Nano Scale Physical Property 15. Modeling and Simulations of Carbon Measurement of Carbon Fibers and Polymers Nanotubes, Graphene and Their Nanopapers with Electron Emission Loss Spectroscopy for Technological Application (EELS) Alper Buldum. Department of Physics, Department Sabyasachi Ganguli,1,2 Ajit K. Roy,2 Robert of Chemistry, The University of Akron, Akron, OH, Wheeler.3 1UDRI, University of Dayton, Dayton, United States. OH, United States; 2AFRL/RXBT, Materials and Manufacturing Directorate, Dayton, OH, United Nanoscale materials such as carbon nanotubes and 3 graphene are promising candidates for fabrication of States; MCF, UES, Dayton, OH, United States. nanoscale devices such as transistors, switches, Measurement of the physical properties of materials computer memories, chemical sensors and flat panel with nano-constituents is usually associated with displays. By performing theoretical research, we aim making multiple large form factor specimens. at understanding and controlling the novel Practically this is not a viable option as the primary mechanical, electronic and transport properties of objective of the addition of nano-constituents is to nanoscale materials, and evaluating their potential achieve improved synergistic properties compared applications. In this respect, a wide variety of with the pure material by tailoring the interface phenomena related with nanoscale materials is between the nano-constituent and the bulk material. investigated. Here, we will present our theoretical Predicting the physical properties of the nano- investigations on carbon nanotubes, graphene and engineered composite from EELS as established in their nanopapers for potential applications such as this study is an enabling technique that can lead to touch sensors, adhesives, vibrational suppression rapid prototyping of the different interface tailoring systems and thermal management materials. of the nano-constituent and predicting the final properties. Plasmon energy originates due to the 16. Toward Understanding Structural and excitation of valence electrons in a material. Since Optical Properties of Nanoscale Zinc and the availability of valence electrons in carbon fibers Cadmium Chalcogenide Magic-Size is different from that in thermoplastics, the plasmon Quantum Dots: Insight from Computational model should be different between the two. This is Prediction evident from our study. 1,2 3 1 1 Kiet A. Nguyen, Paul N. Day, Ruth Pachter. Air 18. Development of a Metal Decorated Force Research Laboratory, Wright-Patterson Air 2 Carbon Nanotubes-Supported Catalyst for a Force Base, OH, United States; UES, Inc., Dayton, Microchannel Methanation Reactor OH, United States; 3General Dynamics Information 1 1 Technology, Dayton, OH, United States. Chung-Hsuan Huang, Jane H. Fujiyama-Novak, Susana Carranza,2 Randy L. Vander Wal.1 1Energy Structure and properties of small quantum dots are of and Mineral Engineering & EMS Energy Institute, fundamental and practical interest due to a broad PENNSYLVANIA STATE UNIVERSITY, range of applications that exploit their optical University Park, PENNSYLVANIA, United States; tunability. However, these materials have not been 2 Makel Engineering, Inc., Chico, California, United systematically characterized, except for very small States. clusters (n = 1,16). In this work, the structure of (AB)n (A = Cd, Zn; B = S, Se; up to n = 54) clusters For anticipated In Situ Resource Utilization (ISRU) was studied using a combination of structure methane is used in a carbothermal process to generate enumeration, Monte Carlo search, and local oxygen from the oxygen-rich lunar regolith. In this optimization. DFT binding energy (En and relative study, for the conversion of CO (a carbothermal binding energy, ∆En = n(En+1 - En), per AB unit) byproduct) back to methane, multi-walled carbon calculations were carried out to identify the magic nanontubes (MWNT) were used as ruthenium (Ru) size (MS, ∆En > 0) quantum dots. In addition, catalyst support. The Ru/MWNT and Ru/MWNT- TDDFT calculations of one-photon absorption Al2O3 systems were prepared by metal cation spectra for MS clusters were carried out to compare activation and surface adsorption of anionic with experimental spectra in order to provide insight surfactant impregnation. Concentrated nitric acid into cluster formation during early growth. The treatment increased the carboxylic and hydroxyl

functionalities on the MWNTs, which resulted in a solution of 0.5 M H2SO4 is similar to classic curve of higher amount of metal decoration. The catalytic other Pt nanostructure. The mass activity of the Pt nucleating center (nickel) formed a uniform nanostructure can reach 400 A/g at a scan rate of 20 monolayer of Ru nanoparticles on the CNT surface. mV/s and in a solution of 1 M CH3OH/0.5 M H2SO4. All prepared Ru-based catalysts showed high Furthermore, a programmed pulse potential with nanoparticle dispersion with 2 nm diameter and a recovery time at 0 V nearly eliminated the effects of narrow particle size distribution. As reducing agent in carbon monoxide poisoning. The mass activity of Pt both processes, the ethylene glycol completely for methanol oxidation can be maintained at 300 A/g converted Ru2+ to Ru0 as confirmed by EDS analysis for more than 3000 s, which is 19 times of that under of TEM. The supported catalysts deposited within an a constant potential of 0.7 V (vs Ag/AgCl). open cell–porous foam substrate was housed in a microreactor. The foam carrier improves heat and 20. Ferric Iron Nanoparticle Formation mass transfer and maintains a low-pressure drop. Mediated by Negatively Charged Among the prepared catalysts, Ru/MWNT-Al2O3 Polypeptides prepared by Ni2+ activation showed the best performance for the hydrogenation reaction. We Vamsi Krishna Aluru, Robin S. Farmer. believe the Al2O3-MWNT hybrid support created a Department of chemical Engineering, West Virginia higher Ru nanoparticle dispersion. University, Morgantown, west virginia, United States. 19. Catalytic Activity of Ultrathin Pt Film The creation of magnetite particles by magnetotactic Coated on an Aligned CNT Substrate bacteria has been of great interest for a number of Xin Su, Ji Wu, Bruce J. Hinds. Department of years. Previous studies have shown that magnetite Chemical and Materials Engineering, University of nanocrystals have been synthesized in the presence of Kentucky, Lexington, Kentucky, United States. recombinant Mms6 protein that is thought to be involved in the biomineralization of bacterial Due to increasing energy demands and the possibility magnetite nanocrystals. The objective of this research of significant methanol production via biomass is to determine the effect of functional group type on conversion, there is active research focused on direct size and shape of magnetic nanoparticles formed by methanol fuel cells for electricity generation. The biomineralization. Control over the size of thermodynamic oxidation potential for methanol is, nanoparticles is paramount. Use of nanoparticles as only 0.02 V (vs NHE), which is close that for contrast agents in MRI is advantageous, as they are hydrogen oxidation. Furthermore the theoretical small enough to be localized in desired region by energy density of methanol fuel cell can reach 6.1 applying local magnetic fields. Sequences VA1, kWh/kg, which is 10 times higher than that of Li VA2, VA3, and VA4 were designed with battery. However, the methanol reaction rate is modifications in the functional groups Mms6 several orders of magnitude lower than that of sequence. Magnetite synthesis is performed in a hydrogen oxidation. Methanol fuel cell fabrication polymeric gel to make sure that conditions at which thus requires catalytic Pt loading onto the surfaces of magnetite nanocrystals formed in magnetotactic electrodes to have useful methanol oxidation rates. bacteria are better mimicked. Solutions of peptide Aligned array CNTs substrates for chemically stable were mixed with ferric and ferro salts and allowed to methanol fuel cell anodes have been fabricated by interact under inert atmosphere. 2 ‘flip trick’, which have high active area (785 cm The nanoparticles formed are examined under SEM 2 active surface area per 1 cm substrate area). and TEM and compared for differences. Use of Electrochemical treatment of the CNTs by peptides with different functional groups may diazoniumbenzoic acid was applied to introduce the provide a unique route to produce uniform magnetite uniform carboxyl functional groups on the surface. Pt nanocrystals with definite control of morphology. was deposited on CNTs with/ without surface modification under the same conditions. SEM, EDS, 21. Controlling the Formation of Bacterial TEM were used to characterize the structure and Films on Engineered Structured Surfaces composite of Pt deposited the aligned CNTs 1,2 1,2 with/without the treatment. The results demonstrated Joanna Aizenberg, Allon Hochbaum, Benjamin 1,2 1,2 1 that surface modification of the CNTs prevent the Hatton, Alexander Epstein. School of large Pt crystallites forming and allow to ultrathin Pt Engineering and Applied Sciences, Harvard 2 film coated on them. The Cyclic voltamograms curve University, United States; Wyss Institute for of the ultrathin Pt film coated on CNTs with surface Biologically Inspired Engineering, Harvard modification at a scan rate of 100mV/s and in a University, United States.

In nature, bacteria organize themselves into behavior. Utilizing a self-assembly process, we are communities, called biofilms, with complex able to produce three types of arrayed nanopatterns, structural and phenotypic diversity. These self- including islands, connected islands, and pits. These organized populations are responsible for a variety of features are created by sputtering a thin film of problems ranging from medical infections to dental gadolinium-doped ceria (GDC) onto a flat yttria- plaque and interfering with industrial processes. stabilized zirconia (YSZ) substrate, followed by Bacterial adhesion is a well-studied field, but many annealing between 1100 °C and 1300 °C to basic questions remain concerning the fundamental spontaneously produce the low-cost, efficiently steps connecting individual cell adsorption to manufactured substrates. This process can be scaled surfaces to mature biofilm growth. Among those is to areas as large as a uniform temperature zone can the role of surface topography in the interactions be maintained and, unlike self-assembly methods between bacteria and surfaces. Though surface such as polymer demixing, provides semi-ordered chemistry provides a transient path to antimicrobial features aligned to the underlying substrate. materials, surface structures may be more permanent Additionally, this method is more expedient than features to prevent bacterial adhesion. Substrate direct-write technologies such as dip-pen or e-beam topography has been shown to have pronounced lithography. effects on mammalian cells, and some studies suggest that bacteria cells may have analogous sensors for We validated these substrates by studying the effect surface interactions. This talk will discuss recent of nanotopography on the morphology and adhesion work in my lab investigating the role of periodic of SK-N-SH neural cells. SK-N-SH neuroblastoma surface structures on the behavior of adsorbed cells are sensitive to their environment, changing bacteria. Specifically, we have found dimensions and morphology in response to surrounding conditions. periodicities of features to which bacteria are To quantify changes in cell function due to sensitive and which direct their adhesion, assembly, nanotopography, we examined cell morphology, and behavior on surfaces. By understanding the spreading, and the expression of cytoskeletal proteins biological mechanisms of these interactions, it may such as actin, vinculin, and vitronectin, which are be possible to engineer materials to affect the vital to cell adhesion. Changes in cell morphology on adhesion of bacteria and alter the development of differing feature morphologies indicate an immediate biofilms on arbitrary surfaces. change in cell function due to the nanoscale environment. By labeling focal contacts formed from 22. Innovative, Inexpensive Surfaces To these proteins, we will gain a deeper understanding of Investigate the Effect of Nanotopography on cell reaction to the nanoscale features produced by Cells our method, and an improved overall understanding of the effects of nanotopography on cell behavior. Kunal S. Parikh,1 Shreyas Rao,1 L. Burr Zimmerman,1 Haris Ansari,2 L. J. Lee,1 Sheikh A. 2 1,3 1 23. Exploring Bio-Inspired Strategies for the Akbar, Jessica O. Winter. William G. Lowrie Production of Nobel Metal Nanocatalysts Department of Chemical and Biomolecular Engineering, The Ohio State University, Columbus, Marc R. Knecht,1 Ryan Coppage,1 Dennis B. OH, United States; 2Department of Materials Science Pacardo,1 Joseph M. Slocik,2 Rajesh R. Naik.2 and Engineering, The Ohio State University, 1Department of Chemistry, University of Kentucky, 2 Columbus, OH, United States; 3Department of Lexington, KY, United States; Nanostructured and Biomedical Engineering, The Ohio State University, Biological Materials Branch, Air Force Research Columbus, OH, United States. Laboratory, Wright-Patterson Air Force Base, OH, United States. Nanotopography is a key aspect of cell response to biomaterials, and through advances in the electronics With the threat of the exhaustion of fossil fuels and industry, numerous methods have been developed to the deteriorating environment, new catalytic synthesize nano-features. materials are required that are both energy and However, nanofabrication techniques such as photo- environmentally friendly. To that end, materials that and electron beam lithography are expensive and are functional in water, at room temperature, and at time consuming, making controlled exploration of low concentrations are desirable; however, attaining this field difficult. all three characteristics from one species remains challenging. In contrast to traditional materials We have developed a simple, inexpensive method to approaches, bio-inspired methods have been gaining examine the effects of nanotopography on cell strength as alternative techniques to produce functional materials that operate under biological

conditions. Phage display has been used to isolate Development of selective liquid state sensors benefits peptide sequences that can nucleate and grow greatly from biologically based recognition elements. nanomaterials of technologically interesting One such element is a DNA oligomer (aptamer) compositions. In this talk, our recent efforts to which can bind a target molecule and change control the production of Pd nanocatalysts using conformations. In this work, the DNA aptamer which peptides will be presented. Based upon the peptide’s binds the biological marker riboflavin was covalently surface structure, nanomaterials are achieved that are attached to a zinc oxide semiconductor in a field functional for C-coupling reactions in water at room effect transistor (FET) structure. When riboflavin is temperature. The materials are active at Pd loadings introduced to the biofunctionalized FET, the aptamer ≥0.001 mol% for quantitative reaction yields. binds the small molecule, adopting a more compact structure which causes the negative charges on the 24. Peptide Based Molecular Recognition DNA aptamer to come into contact with the Elements for Binding 2,4,6-Trinitrotoluene semiconductor. The conformational change is transduced into an electrical signal as a decrease in Avram W. Siegel, Robin S. Farmer. Department of current (‘off-state’) for the n-type zinc oxide Chemical Engineering, West Virginia University, semiconductor. This FET ‘off-state’ structure shows Morgantown, WV, United States. selective sensing of riboflavin down to the pM range. Methods for detection and quantification of Additionally, an ‘on-state’ sensing structure was explosives are needed for both public safety and developed for riboflavin where a redox molecule environmental monitoring. Trinitrotoluene (TNT) is a (ferrocene) was attached to the 5’ terminus of the known toxin and mutagen which has detrimental riboflavin DNA aptamer. As riboflavin binds to the affects to both marine and mammalian wildlife. In the aptamer, the 5’ end is brought to the surface of the present study, three TNT binding peptides, AS2p, zinc oxide where it donates and injects electrons into AS3p and AS6p, have been designed. The main the semiconductor. This scheme transduces the purpose of this research is to test the contribution of aptamer conformational change into an increase in the secondary structure to the overall binding of the current through the FET showing pM selective peptide to the TNT. AS6p is a dimer based on a 12 detection of riboflavin. amino acid phage display peptide reported by Goldman et al and 3 amino acids (histidine, arginine 26. Design of Cell-Based Sensors by and tryptophan) are thought to be critical for binding Employing a Synthetic Riboswitch to TNT. AS2p and AS3p were designed to contain Svetlana V. Harbaugh, Molly E. Davidson, Jorge L. these amino acids; however secondary structures Chavez, Latha Narayanan, Nancy Kelley-Loughnane, were modified. AS2p contains amino acids with a Morley O. Stone. 711th Human Performance Wing, high propensity to form beta sheet and AS3p contains Human Effectiveness Directorate, Air Force amino acids with a high propensity for forming an Research Laboratory, Wright-Patterson Air Force alpha helix. Structural characterization has been Base, Dayton, Ohio, United States. performed using circular dichroic spectroscopy. Binding studies have been carried out via enzyme Cell-based biosensors are advantageous due to their linked immunosobent assay (ELISA ) and specificity, selectivity, internal signal amplification, demonstrate binding of sequences to trinitrobenzene and portability. We have developed a cell-based conjugated albumin by showing an increase in signal detection system by coupling a sensing element, with increasing peptide concentration. theophylline synthetic riboswitch1, to a reporter gene encoding a new green fluorescent protein from 2 25. DNA Aptamer Functionalized Zinc Oxide Amphioxus (GFPa1) . Theophylline riboswitch is a Field Effect Transistors for Liquid State regulatory RNA that activates translation of Selective Sensing of Small Molecules downstream genes upon analyte binding. Thus, addition of theophylline to E. coli cells harboring the Joshua A. Hagen,1,2 Sang Nyon-Kim,2 Nancy riboswitch construct led to an increase in Kelley-Loughnane,1 Rajesh R. Naik,2 Morley O. fluorescence intensity due to GFPa1 expression. In Stone.1 1711th Human Performance Wing RHCB, Air order to increase the resistance of cells to the Force Research Laboratory, Wright Patterson Air environment, we have encapsulated E. coli cells Force Base, OH, United States; 2Materials and using two techniques: layer-by-layer assembly and Manufacturing Directorate RXBN, Air Force sol-gel encapsulation. Cell viability and fluorescence Research Laboratory, Wright Patterson Air Force studies confirmed that encapsulated cells remained Base, OH, United States. viable and were able to express GFPa1 in the presence of theophylline. Encapsulation of living

cells harboring riboswitch is a promising approach to reactions to occur without solvents. Reducing the create stable and controllable cell-based biosensors. amount of solvents used in reactions will greatly reduce chemical waste and improve the well-being of 1S. A. Lynch and J. P. Gallivan (2009) A flow our environment. cytometry-based screen for synthetic riboswitches. Nucleic Acids Res. 37(1):184-92. We are using high speed ball milling to develop a high performing, safe, and environmentally benign 2E. K. Bomati, G. Manning, D. D. Deheyn (2009) method for making dialkyl carbonates. Dialkyl Amphioxus encodes the largest known family of carbonates have been used for a variety of purposes green fluorescent proteins, which have diversified such as fuel additives and drugs for treatment of into distinct functional classes. BMC Evol. Biol. lipidemia and depression. However, the current 9:77. methods available to make them either perform inadequately or use unsafe reaction conditions and 27. Surface Interactions between create solvent waste. Under high speed ball milling Biomolecules and Au Nanoparticles conditions, we have synthesized dialkyl carbonates by reacting metal carbonates along with various types Manish Sethi, Marc R. Knecht. Chemistry, of electrophiles. University of Kentucky, Lexington, Kentucky, United States. 29. Computational Modeling of Rhodium- The binding capabilities of biomolecules with Based Catalytic Dendrimers nanostructures need to be explored in more detail as Daniel A. Turner, Christopher M. Hadad. the applications of these bio-based materials becomes Department of Chemistry, The Ohio State University, more prevalent. Peptides are able to bind to material Columbus, Ohio, United States. surfaces and control their growth and activities based upon their amino acid sequence and geometrical Dendrimers are repeatedly branched molecules linked arrangement. We have developed a sensitive through covalent bonds, often adopting a spherical spectroscopic/microscopic method to investigate this (globular) shape. The macromolecular structure and process employing Au nanoparticles. For this study, folding of dendrimers often imitates the structure of citrate-capped Au nanoparticles are employed where enzymes, suggesting the use of dendrimers as partial displacement of the surface ligands with catalytic molecules. Parquette and coworkers have arginine results in a charged, segregated ligand developed folded dendrons based on a 2,6- network on the material’s surface. From this, an pyridinedicarboxamide repeat unit, preorganized electronic dipole is generated, which results in the based on their syn-syn conformational preference. assembly of linear chains. These results are important Additionally, these dendrons adopt a P or M helical as they lend information to the understanding of the chirality based upon the chirality of the terminal biotic/abiotic interface and methods to analyze such group. The dendrons were attached at the 3 and 3’ binding events. positions of a 2,2’-bis(diphenylphosphinoxy)biphenyl scaffold and complexed with rhodium to be used as a 28. Making Dialkyl Carbonates under High catalyst for the asymmetric hydrogenation of methyl Speed Ball Milling Conditions a-acetamidocinnamate. Using an oxazoline- terminated dendron, enantioselectivities of up to 91% Daniel C. Waddell, Ashley Bunger, James Mack. were achieved. After additional experiments, it was Department of Chemistry, University of Cincinnati, hypothesized that helical bias of the dendron (P/M) is Cincinnati, OH, United States. transferred to the core (P/M), and then transferred to The field of green chemistry was created in order to the catalytic center (S/R product). develop more environmentally benign chemistry. Within our group, we use high speed ball milling in order to conduct more environmentally friendly organic reactions. In this approach, the chemical reactants are placed inside a custom made ½” x 2” screw-capped stainless steel vial along with a stainless steel ball bearing. Shaking this vial in the ball mill causes collisions and creates good mixing of the reactants so that a chemical reaction can occur. The high speed mixing of our approach allows

Jeffrey D. Fogle, William A. Feld. Department of Chemistry, Wright State University, Dayton, Ohio, United States. Biphenyls and terphenyls exhibit rotational barriers associated with bulky substituents in ortho-positions. In most cases, this substituent has been a methyl group which gives rise to two distinct peaks in the 1H NMR spectrum due to the prescence of a mixture of cis and trans diastereomers. Diethyl 2,3-bis(2- fluorophenyl)terephthalate, synthesized by way of the corresponding cyclopentadienone, exhibits a rotational barrier due to fluorine as seen in the 1H, 13 19 Figure 1. Asymmetric hydrogenation of methyl α- C, and F NMR spectra. Chemical shifts of the acetamidocinnamate using an oxazoline-terminated aromatic hydrogens on the terephthalate ring indicate dendrimer. what appears to be a long-range, through-space effect of the o-fluorophenyl substituents. Related Computational studies were performed to strengthen derivatives, the bis(hydroxy methyl)terephthalate and the proposed hypothesis. Using density functional the bis(chloromethyl)-terephthalate, show a similar theory (DFT), specifically RI-BP86/TZVP, we phenomena. calculated the ester- and oxazoline-terminated dendrons studied in the hydrogenation reaction and 31. Palladium-Catalyzed Borostannylative confirmed the helical bias observed experimentally. Cyclization of 1,n-Diynes. Synthesis and However, calculating the full dendrimer was more Properties of Atropisomeric 1,3-Dienes difficult, due to the size and conformational flexibility. Our approach was to generate a diverse set Amanda M. Kutney, T. V. RajanBabu. Department of structures of the core using a Monte of Chemistry, The Ohio State University, Columbus, Carlo/Molecular Mechanics (MC/MM) approach and Ohio, United States. then optimize the resulting core structures using Under Pd-catalysis, borostannane reagents undergo DFT. We then appended the dendrons to the core and highly regio- and stereoselective additions to α,γ- used the same protocol and level of theory used for diynes resulting in the formation of highly the core optimization. We found that the helical bias functionalized (Z,Z)-1,3-bisalkylidenecycloalkane of the dendron was transferred to the core, as products. Sensitive functional groups such as silyl- predicted by experiment. As a further validation of ethers, ketals, and β-lactams are tolerated under the our results, we computed the circular dichroism (CD) cyclization reaction lending to the potential utility as spectrum of the dendrimers, which compared precursors for pharmaceutically relevant compounds favorably to the experimental spectrum. (e.g. carbapenems and other similar bicyclic compounds).

The resulting 1,3-diene adopts a non-planar, helically chiral configuration due to the steric demands of the B- and Sn –substituents. In monocyclic systems these Figure 2. Optimized DFT (RI-BP86/TZVP for Rh, 1,3- dienes exhibit a low activation barrier for the SV(P)) structure of the oxazoline-terminated helical isomerization. However, if the dendrimer. atropisomerization can be frozen, as in several bicyclic systems, we can study how resident central 30. Restricted Rotation in Ortho-Fluorine or axial chirality affects the atropselectivity of diyne Substituted Terephthalates cyclization. The resulting heterobimetallic vinyl- metal compounds can also be further derivatized via the difference of intrinsic reactivities of the

individual carbon-metal bonds leading to highly using bismuth triflate (10 mol %) in tetrahydrofuran complex natural products. as solvent. Similar attempts employing acrylonitrile or ethyl acrylate failed to produce appreciable 32. Investigating the Ullman Reaction under alkylation. Solvent-Free High spped Ball Millng Teresa L. Cook, James Mack. Chemistry, University of Cincinnati, Cincinnati, Ohio, United States. This project will investigate a novel approach to making carbon-carbon bonds. Traditionally, many carbon-carbon bonds are synthesized using metal catalyst and an alkene based halide. Our research 35. Insights into the Molecular Mechanism of focuses on the copper catalyzed Ullman reaction in Conformational Transition between which substituted biphenyls are synthesized under Functional States of Archaeal Chaperonin high speed ball milling (HSBM). HSBM is a solvent Thermosome by Using Normal Mode free technique in which reactants are placed inside Analysis and Elastic Network Model screw capped vial along with a ball bearing and react as a result of the mechanical force. By eliminating Manori I. Jayasinghe,1 Pooja Shrestha,1 George solvents we are conducting greener syntheses and Stan,1 X. Wu.2 1Department of Chemistry, University there is no need for catalyst recovery. With this of Cincinnati, Cinciinati, Ohio, United States; unique approach to carbon-carbon bond formation we 2NHLBI, National Institutes of Health, Laboratory of hope to explore other metal catalyzed reactions. Biophysical Chemistry, Bethesda, MD, United States. Chaperonins are bio-molecular machines, which play 33. Microwave Synthesis of 1,4-Disubstituted a crucial role such as protein folding assistance in the 1,2,3-Triazoles from Organic Azides cell. Structurally, chaperonins are barrel shaped Peter Norris. Chemistry, Youngstown State double-ring constructs, enclosing a central chamber, University, Youngstown, OH, United States. where the protein folding takes place. Functionally, these machines convert the chemical energy, derived Organic azides, particularly those of low molecular from ATPase, to mechanical energy, which is used to weight, are notorious for being difficult to handle and transform the system from one functional state to for their tendancy to detonate upon heating, for another via dramatic large-scale conformational example during distillation. Forming these changes. These changes allow chaperonins to bind compounds in solution, and then converting them misfolded proteins, encapsulate them into expanded directly to useful products, avoids this issue. Reaction cavities and release them back into the cellular progress is conveniently monitored by IR environment. spectroscopy in order to follow azide formation and We present the mechanism of conformational consumption. transition between functional states of archaeal chaperonin thermosome by computing the normal 34. Microwave-Assisted Michael Additions of modes of an Elastic Network Model (ENM) based on N-(arylsulfonyl)pyrroles and -Indoles the crystal structure. Our results show that the thermosome transition is facilitated by several Kelsey C. Miles, Benjamin K. Southerland, Daniel different eigenmodes and the lowest frequency M. Ketcha. Department of Chemistry, Wright State eigenmodes do not contribute significantly in the ring University, Dayton, OH, United States. based arrangement. By contrast, conformational The Michael type addition of methyl vinyl ketone transitions of the bacterial chaperonin GroEL are (MVK) to pyrroles bearing strongly electron dominated by a single lowest frequency eigenmode. withdrawing N-protecting groups (e.g., arylsulfonyl) We proposed the differences between these have yet to be reported. We find that such alkylative mechanisms originate in the sequential allostery in processes can be effected in moderate yields using Thermosome compared to the concerted motions in metal triflate catalysts in conjunction with microwave GroEL. irradiation. Optimization of reaction conditions Key words: Chaperonin, thermosome, allosteric indicates that of the catalysts examined (rare earth conformational change, Normal Mode Analysis, triflate and chlorides) and solvents (nitromethane, Elastic Network Model. acetonitile, dichloroethane, ethanol, etc.) highest yields of mono-alkylated derivatives are obtained

36. Substrate Protein Unfolding and specific mechanism that involve either universal Translocation by the p97 Nanomachine hydrophobic or electrostatic interactions. We used structural and bioinformatic analyses to predict SP Sam Tonddast-Navaei, Manori Jayasinghe, George binding sites of group II chaperonins. Based on large Stan. Department of Chemistry, University of changes in accessible surface area and strong Cincinnati, Cincinnati, Ohio, United States. conservation of amino acids, we propose SP binding The p97 nanomachine, a member of the family of the sites to be a helical protrusion and two helices located ATPases Associated with various cellular Activities at the cavity opening. The conservation of (AAA+), P97 is a homo-hexameric ring with two hydrophobic and charged amino acids at these sites nucleotide binding domains, D1 and D2, per subunit. indicates the universal and specific aspects of the ATP hydrolysis within D2 subunit results in a substrate recognition mechanisms. We further paddling motion of loops located at the entrance of elucidate subunit specific mechanisms by identifying D2 pore. Trp551 and Phe552 are strongly conserved conservation of negative or positive character of the residues of these loops. Additionally, Arg586 and charged amino acid within the subset of eukaryotic Arg599, located near the loops, assist the unfolding subunits. action. The p97 mutant is able to unfold tagged substrate proteins using its described paddling 38. Negative and Infinite Microcanonical, motion. By docking the Ssra peptide tag inside D2 “Continuous” Canonical, and “Discrete” pore and mutating the two arginines we reveal how Canonical Temperature States in Two-Level these arginines are important in making a binding site Magnetic Spin Lattices inside D2 pore.We use coarse-grained molecular 1 2 dynamics simulations to investigate the unfolding Mark B. Masthay, Ross E. Jones, Robert N. Karingithi,2 Philip A. Miller,2 Ramakanth Ananthoji,2 mechanism of a four helix bundle protein (HBP) 2 1 coupled with ATP-driven conformational changes in Harry B. Fannin. Department of Chemistry, University of Dayton, Dayton, Ohio, United States; the D2 domain of p97. Our simulations show that full 2 unfolding and translocation is due to the Department of Chemistry, Murray State University, collaboration between the arginine residues and the Murray, KY, United States. critical residues at the paddling D2 loop. The The concept of microcanonical temperature Tµ = substrate is restrained by the arginine residues of -1 (∂U/∂S)V = k (∂U/∂Ω[N,V,U])V is being increasingly adjacent subunits and the force exerted by Trp551 employed because of its applicability to large systems and Phe552 pulls the substrate through the central away from equilibrium, to small “pseudo-isolated” pore of p97. systems (e.g., individual polyatomic molecules, molecular clusters, atomic nuclei, etc.), and because 37. Structural and Bioinformatic Analyses of the constant energy conditions which apply to the the Substrate Binding Mechanism of microcanonical partition function Ω(N,V,U) are Archaeal and Eukaryotic Chaperonins assumed in molecular dynamics and Monte Carlo Pooja Shrestha,2 Manori Jayasinghe,1 Xiongwu simulations. In earlier work, we applied the concept Wu,3 George Stan.1 1Department of Chemistry, of microcanonical temperature to two-level magnetic University of Cincinnati, Cincinnati, OH, United spin lattices (M.B. Masthay and H.B. Fannin, J. States; 2Department of Physics, University of Chem. Educ. 82[6], 867-873, 2005). In the current Cincinnati, Cincinnati, OH, United States; 3National presentation, we compare the effects of system size Institutes of Health (NIH), United States. and magnetic field strength on Tµ, on the conventional, “continuous” canonical temperature Tc Chaperonins are large ring assemblies that assist = (∂U/∂S)V and on a novel “discrete” canonical folding of substrate proteins (SPs) under non- temperature Tdc = (∆U/∆S)V in two-level spin lattices permissive conditions. Spectacular ATP driven with large (high field) and small (low field) energetic conformational changes take place within each splittings ∆U = U↓ – U↑= ε between spin-up and spin- chaperonin ring to effect the transition between the down states. We have characterized our expressions open to the closed ring. Group I chaperonins, which to spin lattices containing having are found in bacteria, have identical subunits and utilize universal substrate recognition mechanism via 10 ≤ N ≤ 6 × 1023 lattice sites, giving special attention exposed hydrophobic amino acids. By contrast, group to the unusual negative temperature (N↓> N/2) and II chaperonins, found in archaeal and eukaryotic infinite (N↓ = N↑ = N/2) temperature states accessible organisms, have non-identical monomer sequences in two-level systems. suggesting substrate recognition through subunit

We find that Tµ, Tc, and Tdc are non-intensive for mineral crystals and carbonate content, b) degree of finite lattices, but become normally intensive in the mineralization of the collagen matrix and possible thermodynamic (large N) limit. Because the ratio of losses in the organic/inorganic bone components, and two extensive thermodynamic functions are c) mineral crystallinity. Additional tissue samples intensive, and because the microstate energies U = were chemically digested and examined by FAAS to N↓ε are inherently extensive, this size dependence determine the average calcium content. X-ray originates from the microcanonical and canonical fluorescence meausrements were performed to show entropies Sµ and Sc, which are non-extensive for the calcium distribution along the inner and outer small lattices but become normally extensive at large cross-sections of tibiotarsi. All three techniques show corroborating results that the PGMs exposures led to N. We also find that Tµ correlates more closely to Tdc a premature aging process of bone tissue and than to Tc and that Tµ and Tdc more accurately reflect the thermodynamic properties of small spin lattices heterogenous calcium inclusions. than Tc. We discuss the accuracies of temperature measurements in previously reported experimental 40. Interfacial Structure of Bilayer studies of paramagnetic and nuclear spin lattices in Compensation Films Prepared by Sequential light of our findings. In addition, we detail the Solution Process temperature dependence of the microcanonical (based Wumin Yu, Mark D. Foster. Department of Polymer on Tµ) and canonical microstate population Science, The University of Akron, Akron, OH, distributions (based on T ), as these distributions c United States. appear to violate normal Gibbs-Boltzmann population statistics at small N. Highly anisotropic polymer films formed by rigid-rod like aromatic polyimides (PIs) show uniaxial 39. Toxicity of Platinum Group Metals in negative birefringence and have been used as Chick Embryo Tibiotarsi compensation films to widen the viewing angles of liquid crystal display system (LCD). Fluorinated Jennifer Monahan,1 Jessica Dagher,1 Tai Lam,1 1 1 pendent groups have been introduced into the PIs in Marjorie Markopoulos, Allie Meyerhoefer, Kent order to attain solubility in common organic solvents Weaver,1 Britney NeJame,2 Jacob Cowley,2 Robert 3 3 2 without substantially decreasing the rigidity of their Slaughter, Larry Burggraf, Zofia Gagnon, Ioana backbones. A new procedure for incorporating the Pavel.1 1Department of Chemistry, Wright State 2 polyimide compensation film in the multilayer LCD University, Dayton, OH, United States; Department assembly by directly coating the PI film on a of Environmental Science and Policy, Marist substrate film, e.g. triacetate cellulose (TAC), is College, Poughkeepsie, NY, United States; 3 preferred in industry for its simplicity and cost- Department of Engineering Physics, Air Force effectiveness. To obtain high quality multilayer films Institute of Technology, Wright Patterson, OH, with excellent durability, sufficient adhesion strength United States. is needed. This adhesion directly correlates with the Platinum group metals (PGMs) have been shown to structure of the interface between the PI layer and the accumulate in various tissues of organisms, but their TAC substrate. It is also important that the TAC toxicity is not well-known. A chick embryo model bottom layer should not be damaged during the direct was chosen for qualitative and quantitative analysis coating process. of the changes in the chemical composition of Sequential solution processes such as sequential spin tibiotarsi caused by PGMs exposure. The following coating and spin coating followed by solution casting spectroscopic techniques were employed to address have been used to create model bilayer structures for these aspects: micro-Raman, flame atomic so that X-ray reflectivity (XR) can be used to probe absorption, and X-ray fluorescence. PGMs were the interface of PI and TAC bilayer films. High injected into chick embryos as Pt (IV), Rh (III), and Pd resolution x-ray reflectivity measurements revealed (II) salt solutions or PGMs mixtures at 0.1, 1.0, 5.0, or that with one potential solvent the interfacial width of the bilayer is only several nanometers. The interface 10.0 ppm. The LD100 was established at 10 ppm. Micro-Raman maps were recorded on the paraffin structure has also been studied in the case that a embedded tibiotarsus cross-sections. Anomolous solvent which tends to swell TAC is added to the PI calcium inclusions were detected at PGM solution to determine the swelling agent’s effect on concentrations as low as 1 ppm, which is sufficient to the interfacial structure. The insights gained will have impede circulation within the cartilage matrix and to broader applicability to the practically important, but cause bone deformities. The following bone theoretically challenging, area of interfaces formed properties were analyzed and quantified: a) age of under nonequilibrium conditions.

41. High-Level Quantum Mechanical Studies We have calculated canonical (qc) and of Bromocarbenes microcanonical (qµ) Tsallis indices for two-level spin “superlattices” comprised of two equally sized Jean M. Standard, Rebecca J. Steidl, Matthew C. “sublattices” containing n = n = N /2 ≤128 non- Beecher, Robert W. Quandt. Department of A B A+B interacting spins. While Sµ and S are both Chemistry, Illinois State University, Normal, IL, c superextensive for most microstates of small (N United States. A+B ≤50) superlattices, both entropies become normally Bromine-containing hydrocarbons may serve as extensive and qµ → qc →1 for all microstates as NA+B replacement compounds for chlorofluorocarbons in becomes large, indicating that the microstate many applications. These compounds have garnered populations of large (small) spin lattices obey recent attention as a result of their greater than (violate) Gibbs-Boltzmann statistics. This result expected ozone depletion potentials. applies regardless of whether the population statistics Photodissociation of bromocarbons such as are governed by the conventional “canonical” bromoform may follow two different routes temperature (Tc ) or by non-conventional depending upon the excitation wavelength: microcanonical (Tµ) or “discrete canonical” (Tdc) dissociation into atomic bromine and a substituted temperatures, the latter of which applies to systems methyl radical or dissociation into molecular bromine with population statistics intermediate between those and a singlet carbene. In this work, we report the of canonical and microcanonical ensembles. qc = qdc results of high-level CASPT2 and MRCI calculations for all microstates, and generally converges to 1 more of the lowest singlet and triplet states, as well as the rapidly with increasing lattice size than qµ, indicating first excited singlet state, for a series of that normal Gibbs-Boltzmann thermostatistics are bromocarbenes: CHBr, CFBr, CClBr, CBr2, and approached more rapidly with increasing lattice size CBrI. The singlet states of these compounds are the in the canonical than in the microcanonical ensemble. expected photoproducts from one channel in the The convergence is particularly rapid for dissociation of various bromocarbons. The results superlattices comprised of identical spin-0 (i.e., nA↑ = presented include equilibrium geometries and nA↓ = nB↑ = nB↓) sublattices, for which a global harmonic vibrational frequencies of each of the canonical thermal equilibrium condition (TcA = TcB = electronic states, along with singlet-triplet gaps and TcA+B = ∞) prevails. Accordingly, qc = qdc = 1 adiabatic transition energies. regardless of lattice size for this unique case, though qµ approaches 1 only in the thermodynamic limit 42. Nonextensive Entropies and Non- because TµA = TµB → TµA+B → ∞ only as NA+B Boltzmann (Tsallis) Thermostatistics in Two- becomes large. We justify our use of Tµ and Tdc and Level Magnetic Spin Lattices in the Absence detail differences in the dependence of qµ and qc = qdc of Long-Range Interactions on lattice size, microstate, temperature, and proximity Mark B. Masthay,1 Ross E. Jones,2 Robert N. to global thermal equilibrium. We also discuss Karingithi,2 Philip A. Miller,2 Ramakanth Ananthoji,2 potential differences in the population distributions of Harry B. Fannin.2 1Department of Chemistry, lattices comprised of non-interacting spins and University of Dayton, Dayton, OH, United States; lattices with long-range spin-spin interactions, since 2Department of Chemistry, Murray State University, long-range interactions give rise to non-Gibbs- Murray, KY, United States. Boltzmann (i.e., Tsallis) statistics. The Tsallis q index quantifies the extent to which (i) 43. Drug Discovery: Ingenuity or the entropy S of a supersystem A+B comprised of Serendipity? two subsystems A and B is thermodynamically extensive and (ii) the population statistics of the Richard B. Silverman. Department of Chemistry, supersystem microstates violate the normal Gibbs- Northwestern University, Evanston, IL, United Boltzmann distribution. The entropy is “extensive” States. (i.e., additive, with S = S + S ) when q=1, is A+B A B In this lecture I will briefly describe the drug “superextensive” (i.e., S > S + S ) when q<1, and A+B A B discovery process, look at the mechanisms for how is “subextensive” (i.e., S < S + S ) when q>1) A+B A B several classes of drugs work, and attempt to answer according to the question of whether drug discovery is a logical,

rational process or one that depends on fate and luck. q = 1 + k (S - [S + S ]/S S ). A+B A B A B At the end I will describe our discovery of LyricaTM,

a drug for the treatment of epilepsy, neuropathic pain, and generalized anxiety.

44. Interactions of Peptides and Ionic Liquids similar to those found in other elastomeric proteins. with Silica Surfaces In our study we use molecular dynamics to elucidate 1 1 1 the effect of amino-acid sequence variation on the R. J. Berry, L. B. Hill, Y. H. Ngo, Vikas mechanical properties of resilin-like peptides. In Varshney,1 M. L. Jespersen,1 P. A. Mirau,1 Hendrik 2 2 1 particular, we address the role of disorder in the Heinz, F. S. Emami. RXB, Air Force Research relaxed state and the amount of conformational Laboratory, WPAFB, OH, United States; 2 entropy lost upon extension. We simulate model Department of Polymer Engineering, University of systems comprising multiple identical repeats from Akron, Akron, OH, United States. single elastic units observed in fruit fly and mosquito Molecular dynamics (MD) simulations were resilin gene products. The entropic nature of the conducted to study the adsorption of peptides to silica restoring force in resilin-like peptides is estimated surfaces in an aqueous environment. Variations in the from molecular dynamics simulations. We find a computed binding energies as a function of peptide high level of disorder and lack of stable secondary sequence, concentration, surface structure, sodium structure in well solvated relaxed state in all ion distribution and pH will be discussed and simulated peptides; consistent with the conclusion compared with results of NMR studies and from circular dichroism spectra of resilin-like biochemical binding assays. peptides. We conclude that the restoring force is primarily of entropic origin and largely insensitive to Nanoscale ionic materials (NIMs) with a negatively- amino-acid composition of resilin-like elastic repeats. charged corona and positively-charged ionic liquid canopy were also investigated using MD simulations. 46. Molecular Simulations of Actin Flexibility The canopy consists of ethylene and propylene oxide Jiyoung Lee, Ruxandra Dima. Department of block copolymer chains terminated by an amine Chemistry, University of Cincinnati, Cincinnati, group. Neutral chains were modeled to predict Ohio, United States. behavior in a dry environment while ionized chains with OH- counter-ions were representative of moist Muscle contraction results from the interaction of conditions. Thermal properties were attained by filamentous actin (F-actin) with the molecular motor examining cooling curves obtained from NPT myosin. F-actin results from the polymerization of dynamics. Transport properties such as diffusion globular actin (G-actin). To probe the basis of the coefficients and viscosity were obtained from NVT mechanical behavior of actin that leads to muscle dynamics. The core and corona were modeled by contraction, we studied the response of G-actin and sulfonate terminated chains covalently bound to a F-actin to an applied tension. Our extensive silica surface. The effect of canopy chain length, molecular simulations are based on a self-organized block copolymer ratio and ionization on the polymer model (SOP) [1] of the actin molecule. We computed thermal and transport properties will be found that the experimentally measured stiffness for discussed and compared with NMR results. F-actin [2] is mostly due to the stiffness of its basic unit, i.e., G-actin. Furthermore, our simulations also 45. Molecular Dynamics Study of Entropic show that the actin-myosin interaction surface Force in Resilin-Like Peptides responds faster to force than the actin-actin interaction surface, which correlates very well with 1 3,4 Roman Petrenko, Matthew B. Dickerson, Rajesh the known experimental data on the rigidity of each 4 4,5 1 R. Naik, Soumya S. Patnaik, Thomas L. Beck, G-actin subdomain [3]. 2 1 Jaroslaw Meller. Department of Physics, University of Cincinnati, Cincinnati, OH, United States; [1] Hyeon C, Dima RI, Thirumalai D (2006) 2 Department of Environmental Health, University of Structure 14:1633-1645. 3 Cincinnati, Cincinnati, OH, United States; Research [2] Liu X, Pollack GH (2002) Biophys J 83:2705- Associateship Program, National Research Council, 2715. 4 Washington, DC, United States; Materials and [3] Page R, Lindberg U, Schutt CE (1998) J Mol Biol Manufacturing Directorate, Air Force Research Lab, 280:463-474. WPAFB, Dayton, OH, United States; 5Modeling Solutions, Inc, West Chester, OH, United States. 47. Interaction of Protein Building Blocks Resilin is an elastomeric protein characterized by and Surfactants with Shaped Surfaces of Au, rubber-like elasticity, very high resilience and high Pd, and Silica in Aqueous Solution fatigue lifetime. These outstanding material properties are conferred by multiple elastic repeats,

Hendrik Heinz. Department of Polymer with a narrow axial pore serving as a translocation Engineering, University of Akron, Akron, Ohio, channel into the peptidase subunit, ClpQ. ATP-driven United States. conformational changes of ClpY subunits are coupled with mechanical unfolding and translocation of SP’s The binding strength of peptides to surfaces of fcc via motions of flexible loops within the ClpY pore. It metals is mostly determined by molecular epitaxy, as was proposed that these ClpY subunit transitions are identified by molecular dynamics simulation and sequential, but not necessarily ordered within the experimental data. The time-averaged fit of ring. We use coarse grained molecular dynamics polarizable groups of amino acids and peptides to simulations of ordered and random transitions to characteristic epitaxial lattice spacing on the metal probe the effects of ClpY conformational changes of surface determines the strength of adsorption and was ClpY on a four helix bundle protein. We predict that computed in a near-quantitative way using accurate ordered sequential transitions are the most efficient potentials and advanced sampling techniques. We for unfolding and translocation of the SP. We identify explain the selectivity of adsorption of peptides in a major pathway for unfolding, which is initiated by aqueous solution to {111}, {100}, and other metal pulling onto the C-terminal helix by the axial loops. surfaces, the competition with solvent molecules, and Our results are in accord with experimental findings the influence of curvature. A fundamental and that indicate the unraveling of the protein from the powerful indicator to design molecules of specific tagged C-terminus. Translocation occurs by a power binding ability is the surface potential. Simulation stroke mechanism, utilizing the loops for binding and results are consistent with numerous observations, pulling SP’s through the channel. e.g., sequences of binding peptides derived from phage display, binding constants, QCM data, relation between sequence and growth of metal 49. Assessment of Varied Gridcenter nanostructures, affinity to spherical vs even surfaces. Searching Algorithm in Ligand-Protein Docking Adsorption of peptides onto much less attractive Q3 Zhifeng Kuang, Rajesh R. Naik, Barry L. Farmer. and Q2 silica surfaces in solution is associated with Materials and Manufactoring Directorate, Air Force superficial cation-exchange and interactions of a Research Laboratories, Wright-Patterson AFB, OH, range of hydrogen-bonded residues with the surface. United States. N-terminal ammonium groups, Lys, and, to a lesser extent, Arg, participate in ion exchange reactions Docking methods are routinely used to predict while Ser, His, and Asp residues in particular support ligand-protein binding modes in structure-based drug hydrogen bonds and polar interactions with silica design. Much effort has been put into improving the surfaces. Visual analysis, Ramachandran plots, and prediction accuracy of those methods. We have computed changes in NMR spectral shifts upon developed a novel procedure to more accurately adsorption from solution to the surface indicate a predict the native binding sites and modes of ligands pattern of subtle changes in conformation which have to proteins based on a varied gridcenter searching a substantial effect on binding energies. Further, algorithm. Using this procedure, we are able to sequence-dependent changes in adsorption energies reproduce four native binding modes out of five were recorded experimentally and excellent tested complexes for which current popular docking correlation with simulation results is seen, enabling programs failed. reliable molecular-level monitoring of the specific adsorption processes. 50. Layered Metamaterials for Optical Filtering 48. Computational Modeling of Protein Rachel Jakubiak. Materials & Manufacturing Unfolding and Translocation by the ClpY Directorate, AFRL, WPAFB, OH, United States. Biological Nanomachine This talk will provide an overview of multilayer Andrea N. Kravats, Manori Jayasinghe, George metal/dielectric and mixed dielectric optical coatings Stan. Department of Chemistry, University of designed to achieve a specific spectral performance Cincinnati, Cincinnati, Ohio, United States. (i.e. transmission and reflection) with the mixture of AAA+ ATPases are molecular machines which assist materials that have a complex index of refraction not in the unfolding, remodeling, and degradation of found in nature and not found in the bulk tagged substrate proteins (SPs). Our focus is ClpY, a constituents. Special emphasis will be placed on bacterial homolog of the chaperone component of the silver-dielectric multilayers used to reject infrared proteosome. ClpY assembles into a hexameric ring and ultraviolet wavelengths while maintaining high

transmission in the visible (induced transmission directly demonstrate the first practically lossless and filters). active NIM. The original loss-limited negative refractive index and the figure of merit (FOM) of the 51. Loss-Free and Active Optical Negative- device have been dramatically improved with loss Index Metamaterials compensation in the visible wavelength range. At a wavelength of 731 nm, the negative refractive index Shumin Xiao, Vladimir P. Drachev, Alexander V. improves from -2.48 to -3.19, and the FOM increases Kildishev, Xingjie Ni, Uday K. Chettiar, Hsiao-Kuan from 1.9 to 1.8x103. This study demonstrates Yuan, Vladimir M. Shalaev. School of Electrical and conclusively and for the first time an optical Computer Engineering and Birck Nanotechnology metamaterial that is not limited by the inherent loss Center, Purdue University, west lafayette, IN, United of its metal constituent. We anticipate a significant States. impact from this breakthrough in the fields of Optical NIMs are artificially tailored composites metamaterials and transformation optics, which where a counterintuitive negative refractive index would enable a family of new applications for optical arises from the nanoscale “meta-atoms” designed into metamaterials. the material. These optical NIM building blocks typically require a plasmonic material such as silver 52. Structural Changes in Plasma or gold in addition to dielectric constituents. Losses Polymerized Films Derived from Titanium inherent in these noble metals at optical frequencies (IV) Isoproxide plague the entire field of metamaterials and are one 1,2 1,2 1,3 of the major restrictions preventing metamaterials Lirong Sun, Hao Jiang, John T. Grant, 1 1 1 & from leaving the domain of academic research and Timothy J. Bunning, Rachel Jakubiak. Materials entering industrial applications. Recently, Manufacturing Directorate, AFRL, WPAFB, OH, United States; 2General Dynamics Information incorporating an active material has been suggested 3 as a viable and effective method to minimize or Technology, Dayton, OH, United States; University eliminate loss in NIMs. This method has been of Dayton Research Institute, Dayton, OH, United theoretically discussed with a variety of gain models, States. resulting in dramatic predictions for performance Transition metal oxynitrides combine the favorable improvements. However, the high levels of gain optical and dielectric properties of metal oxides with required for this method were previously considered the strength and durability of metal nitrides. Using impossible to obtain in experiments. The impairment plasma-enhanced chemical vapor deposition of low gain levels can be overcome by using a thick (PECVD), highly cross-linked, amorphous plasma active host layer, as was shown in the recent polymerized (PP-) films of TiOxCyNz formed from demonstration of the spaser. However, in a NIM- the room temperature gas phase reaction of titanium based device the thickness of the active material must (IV) isopropoxide and nitrogen-rich ionizing plasma. be kept necessarily small in order to preserve the Changing the relative concentration of nitrogen in the negative refractive index. Therefore, the carrier gas varied the stoichiometry of the TiOxCyNz incorporation of gain in an optical NIM design is thin films. Counter intuitively, the atomic weight mired in difficulty, even though such an achievement concentration of nitrogen in the films scaled inversely would produce low- or no-loss optical NIMs for use with nitrogen concentration in the reactive plasma. in a large number of breakthrough applications. We Possible reasons include saturation of atomic have overcome this limitation by an approach in nitrogen production and ablation of low molecular which the active medium within the NIM gives rise weight species from the film’s surface during ion to an effective gain much higher than its bulk bombardment. From XPS and FTIR studies, the counterpart. The large value of gain is achieved due amorphous, 3-D crosslinking network of carbon-rich to the local-field enhancement inherent to the domains and TixOy moieties were linked together plasmonic response of NIMs, providing a new only through C-O-Ti bonds. Substitution of nitrogen direction for the compensation of losses in NIMs. In with oxygen in the carrier gas created multi-phase our experiments, the transmission through the optical films with granular morphologies. NIM sample is amplified by pumping the active medium incorporated within the sample, and the 53. Fabrication of a 2-D Square Hole Array structure is carefully designed to make the active by Attenuated Holographic-Lithography for medium experience the highest local field while Plasmonics simultaneously preserving the negative index property of the metamaterial. Our experimental Michael J. Birnkrant,1 Lalgudi V. Natarajan,1,2 results, along with our numerical simulations, Vincent P. Tondiglia,1,2 Richard L. Sutherland,1,2

Augustine M. Urbas,1 Timothy J. Bunning.1 between 4.6 and 6.0 nm Au NP’s and flat {111} Au 1Materials & Manufacturing Directorate, Air Force facet. This suggests the existence of a critical Au NP Research Laboratory, Wright-Patterson Air Force size beyond which the strong binding of peptide Base, Ohio, United States; 2Science Applications protects the Au NP from aggregation or further International Corporation, Dayton, Ohio, United growth. These results may help understand the role of States. A3 in Au NP formation and develop Au NP with controlled sizes. Holographic-Lithography (HL) is an easy method for fabricating 1-, 2- and 3-dimensional structures in References: photoresist materials for photonic applications. The 1.Slocik, J. M.; Stone, M. O.; Naik, R. R. Small 2005, morphological control of HL patterned structures is 1, 1048. important for masking techniques. In this 2.Heinz, H.; Farmer, B. L.; Pandey, R. B.; Slocik, J. presentation, the morphology of a periodic 2-D M.; Patnaik, S. S.; Pachter, R.; Naik, R. R. J. Am. square array of holes is investigated when the HL Chem. Soc. 2009, 131, 9704. writing intensity is attenuated through the photoresist. 3.Stanley, S. K.; Becker, M. L.; Lin, E. K.; Wu, W. The addition of a dye to the photoresist attenuates the Langmuir 2009, 25, 10886. laser intensity through the SU-8 film. This resulted in a hole array displaying a truncated cone morphology observed using scanning electron microscopy. The 2- 55. Wiring Gold Monolayer Protected D square array in SU-8 was shadowed, which Clusters resulted in a metal film containing a periodic array of Brian N. Turner, David E. Cliffel. Department of holes. In addition there was a complimentary array of Chemistry, Vanderbilt University, Nashville, TN, metal dots. The period of the SU-8 hole array United States. corresponds with the wave vector of the surface plasmon for the metal films and the diameter of the 1-phenylacetyl-4-mercaptobenzene (PAMB) was holes/disks. The effect of this resonance could be synthesized by a new synthetic route. Based on the observed in optical transmission and reflection structure of this molecule, it may act as a small measurements. molecule organic conductor. Alkanethiol monolayer protected clusters (MPCs) functionalized with PAMB 54. Stability Limited Growth Mechanism of will be studied using the scanning electrochemical microscope (SECM). The kinetics of electron transfer Peptide-Mediated Au Nanoparticle Synthesis between an ultramicroelectrode (UME) and the Using Molecular Dynamics Simulations PAMB MPCs will be compared to those of Jing Yu, Matthew L. Becker, Gustavo A. Carri. unfunctionalized MPCs to determine whether Department of Polymer Science, University of transferred electrons tunnel between the UME and Akron, Akron, Ohio, United States. the MPC gold core or if they are conducted through the PAMB. Previous studies suggest that electron The synthesis of peptide-based of Au nanoparticles transfer kinetics are limited by the rate of tunneling (NP) with controlled sizes and morphologies has through the insulating alkanethiol monolayer. In the attracted a lot of attention from the scientific case where the electrons are conducted through the community due to its potential in bio-imaging as well PAMB, the kinetics should, theoretically, be limited as many other applications. The specific affinity of by mass transfer and not tunneling. the peptide AYSSGAPPMPPF (A3) to gold has been 1 studied both in phage display experiments. and 56. Effective Material for Reproducible SERS molecular dynamics simulations (MD).2 We have previously reported that the kinetics of the Au NP “Blinking” formation was dependent on peptide, HEPES buffer Andrey V. Malkovskiy, Alexei P. Sokolov, Mark D. and HAuCl4 concentrations.3 In this work, we have Foster. Department of Polymer Science, The studied the effect of NP size to the size-controlling University of Akron, Akron, Ohio, United States. mechanism of peptide in the formation of Au NP’s using MD simulations. The adsorption free energies Surface-enhanced Raman spectroscopy (SERS) is a and equilibrium structures were compared to show very promising technique for sensing, detection and that all Au NP’s were capable of forming strong analysis of single molecules and nano-structures. It is bindings with the peptide; the stability of A3 was based on gigantic enhancement of an optical signal quantified with the average change of the dihedral by surface plasmons in metallic clusters. While the angles, which showed higher stabilities on larger Au phenomenon of SER was discovered a long time ago NP’s. Furthermore, there were no obvious differences [1], “intermittent” seemingly random enhancement of

various peaks, often termed “blinking”, was Niti Garg,1 Ashok Mohanty,2 Rongchao Jin.1 discovered only very recently [2,3] and is far from 1Chemistry, Carnegie Mellon University, Pittsburgh, being well understood. However, the notion that PA, United States; 2c, National Metallurgical “blinking” is a sign of extreme enhancement or, Laboratory, Jamshedpur, Jharkhand, India. possibly, even single-molecule detection, is generally Use of nanometer-size metal particles each coated by agreed upon. an organic monomolecular layer for the purpose of

chemiresitive sensor has been initiated in late The biggest problem that is hindering the study of nineteenth century. Since then, such systems have such extreme enhancement is its low reproducibility. become very popular subject of study within the Minor variations in sizes and shapes of individual research community mainly due of their intriguing metal clusters may shift the plasmon resonance. properties. Their response towards VOCs is very high Often there is also a need for freshly-prepared metal (compared to other existing system like polymers), particles, as their enhancing ability degrades over fast, reversible and selective. Unfortunately, such time. systems are associated with long term stability issues.

Particles tend to loose their sensitivity with time as We have employed a known procedure for metal they age and change their morphologies. We have particle preparation and obtained SERS substrates made an attempt to overcome the limitations providing reproducible “blinking” enhancement for associated with such system while keeping their other substrates prepared by simple drop casting. Electron superior characteristics intact. We have synthesized a Microscopy has shown the sizes and shapes of the new type of alkanethiol which contains three thiol particles as synthesized, while Atomic Force groups per molecule. Such thiols are used as ligand Microscopy and simple optical microscopy have during gold nanoparticles synthesis. The physical revealed the surface morphology of particles on properties of monothiol and trithiol coated polymer analyte surfaces. This “blinking” was nanoparticles are systematically compared and also correlated to the optical absorption peak of the SERS their response to volatile organic vapor adsorption. substrate and was not seen for a different wavelength We found that our new system is significantly more of illumination light. Instead, a simple increase of the sensitive towards all the different types of VOCs main peaks was observed. Such an increase was (polar, non-polar) and display very high stability generally stable over time. Surface Near-field Optical compared to its monothiol counterpart. The Microscopy helped to identify the positions and the mechanism by which our novel system work and the structure of “hot spots”. Light absorption spectra plausible reason behind their higher sensitivity and measured for particles in solution and on the surface stability has been explained in the report. of substrates agreed well with published data and were consistent with the enhancement behavior at different illumination wavelengths. We discuss the 58. Active Targeting PDT Drug Delivery possibility of carbon contamination of the substrates through Gold Nanoparticle for Brain Cancers and ways of distinguishing between “carbon” and Yu Cheng,1 Joseph D. Meyers,2 Ann-Marie real analyte blinking. Broome,2 Richard Agnes,2 Malcolm E. Kenney,1 James P. Basilion,2 Clemens Burda.1 1Department of References: Chemistry, Case Western Reserve University, Cleveland, Ohio, United States; 2Departments of [1] Fleischmann, M.; Hendra, P. J.; McQuillan, A. J. Biomedical Engineering and Radiology, Case Chem. Phys. Lett., 1974, 26(2), 163-166. Western Reserve University, Cleveland, Ohio, United States. [2] Nie, S.; Emory, S. R. Science, 1997, 275(5303), 1102-1106. A non-covalent targeted drug delivery using gold nanoparticles (Au NPs) has been explored as a novel [3] Kneipp, K.; Wang, Y.; Kneipp, H.; Perelman, L. approach for photodynamic therapy (PDT) of brain T.; Itzkan, I.; Dasari, R. R.; Feld, M. S. Phys. Rev. cancers. The PDT drug Pc 4 has been entrapped by Lett., 1997, 78(9), 1667-1670. the EGF peptide modified Au NPs. In vitro studies of the EGF Au NP-Pc 4 conjugates have shown 57. Super Robust Gold Nanoparticles excellent biocompatibility in the dark and better PDT Stabilized by Trithiols for Sensing of Volatile effect than the free Pc 4. The drug delivery process is concentration dependent and regulated by EGFR on Organic Compounds the cell surface. Pc 4 drugs on the NPs are internalized by receptor-mediated endocytosis and

mainly localize in early endosomes. In vivo studies of Zhen Li,1 E. Sahle-Demessie,2 Ashraf A. Hassan,1 the EGF Au NP-Pc 4 conjugates have shown the drug George A. Sorial.1 1Department of Civil and can be transported through the blood brain barrier Environmental Engineering, University of Cincinnati, and an improved targeting effect to the brain tumors Cincinnati, OH, United States; 2Office of Research has been observed. After PDT treatment, the brain and Development, 2U.S. Environmental Protection tumors have shown shrinkage and necrosis. Agency, cincinnati, OH, United States. The increased production and use of manufactured 59. Size Selection and Concentration of Silver nanoparticles (NPs) presents concerns for human and Nanoparticles by Tangential Flow Filtration environmental health. When NPs are released to the for SERS-Based Biosensors environment, their stability, transport properties and John C. Trefry,2 Jennifer L. Monahan,1 Kent M. interaction with other pollutants and natural organic Weaver,1 Allie J. Meyerhoefer,1 Marjorie M. matter play a key role in the risk analysis. CeO2 NPs Markopoulos,1 Zachary S. Arnold,1 Dawn P. are example of novel nanomaterials which is widely Wooley,2 Ioana E. Pavel.1 1Department of Chemistry, used as polishing materials, automobile exhaust Wright State University, Dayton, Ohio, United catalysts, fuel cell materials, and additives in States; 2Department of Neuroscience, Cell Biology glass/ceramic application. There has been limited and Physiology, Wright State University, Dayton, work on the stability, mobility, transport and Ohio, United States. deposition of CeO2 NPs in the ground, which determines their potential exposure and Silver nanoparticles (AgNPs) have received bioavailability. Hence the transport and fate of CeO2 tremendous attention for their properties as NPs is of particular interest to fill the knowledge gap. ultrasensitive surface-enhanced Raman spectroscopy We have conducted experimental studies and (SERS)-based biosensors. A challenge in SERS- theoretical analysis to better understand the kinetics based biosensing is fabricating AgNPs that are non- of CeO2 NPs transport in porous media and the toxic, reproducible, stable, and at low energy costs. deposition from a flowing suspension onto solid AgNP size and aggregation state are typically surfaces or collectors. Engineered CeO2 NPs were controlled by aggressive chemical agents which are purchased from vendor and well characterized by not biologically compatible. To determine a method quantifying the mean diameter, size distribution, zeta for overcoming these disadvantages, a modified potential and UV-vis absorbance. The influence of Creighton colloid was subjected to two methods of ionic strength and pH on the transport and deposition isolation: ultracentrifugation and tangential flow of CeO2 NPs in water-saturated porous media was filtration. The resulting colloids were examined by investigated in a series of column experiments, various spectroscopic techniques. Ultracentrifugation during which CeO2 NPs suspensions under various yielded a suspension containing AgNPs and AgNP- solution chemistry were injected to the columns, and aggregates, which were 2.5 fold larger in size with a the relative effluent concentration C/C0 was 2.0 fold greater size distribution than the monomers interpreted using clean-bed filtration theory. Non- in the filtration method. The UV-Vis absorption reactive tracer was used to predict the movement of spectra confirmed these differences. FAAS showed well dispersed NPs through a sand packed column, that the concentrations of AgNPs obtained by operating under upflow condition and the Peclet filtration and ultracentrifugation were 198.7 µg mL-1 numbers were determined to estimate hydrodynamic and 77.4 µg mL-1, respectively. The analytical dispersion coefficient. (8.1x107) and surface enhancement factors (7.9x104) corresponding to the final AgNP filtration were 61. Versatility of Droplet-Interface-Bilayer similar to those determined for AgNP (DIB) Lipid Membranes ultracentrifugation. Both methods had a 1,000 fold improvement in SERS-sensitivity as compared to the Srikoundinya Punnamaraju, Andrew J. Steckl. original colloid. However, the filtration method Electrical and Computer Engineering, University of provides size-specificity and minimal aggregation in Cincinnati, Cincinnati, OHIO, United States. a highly concentrated colloidal suspension of AgNPs. Artificial lipid bilayer formation is very useful in mimicking biological cell membrane. 60. Kinetics of Transport, Dispersion and Droplet-Interface-Bilayer (DIB) is a novel technique Deposition of Engineered Nanoparticles in to form artificial lipid bilayers. Porous Media Lipid monolayers are coated on the surface of an aqueous droplet when dispensed into a lipid- containing oil bath. When two such lipid monolayer

coated droplets are brought into contact, a DIB lipid 63. Vesicle Encapsulated Hemoglobin membrane is formed at their interface. Electrodes are Dispersions as Potential Oxygen Carriers inserted into each droplet and experiments are conducted with greater flexibility. DIBs are Shahid Rameez, Andre F. Palmer. Chemical and characterized optically, mechanically, and Biomolecular Engineering, The Ohio State electrically. DIB versatility is demonstrated by University, Columbus, OH, United States. volume control of DIB forming droplets, manual Vesicles, which include liposomes and control of DIB overlap, voltage control of DIB polymersomes (polymer vesicles), are being overlap, ease of reformation, and flexibility in investigated as red blood cell (RBC) substitutes. In forming networks of lipid bilayers. Ion channel this study, we investigated the cytotoxicity and studies are conducted with great flexibility. Alpha- biophysical properties of vesicle encapsulated Hemolysin single pore insertions in DIB were hemoglobin (Hb) dispersions. Polymersome recorded at different applied potentials. Ion currents encapsulated Hbs (PEHs) were self-assembled from at various Alpha-Hemolysin concentrations in biocompatible amphiphilic diblock copolymers droplets and at various voltages were recorded. Also, composed of poly(ethylene oxide) (PEO) and ion currents at various ionic concentrations of poly(butadiene) (PBD). In the PEO-PBD diblock, droplets were recorded at various voltages for a given PEO functions as the hydrophilic block while PBD Alpha-Hemolysin concentration in the droplets. The functions as the hydrophobic block. In addition, mechanism behind the voltage control of DIB liposome encapsulated Hbs (LEHs) of different sizes, dimensions is similar to that observed in containing poly(ethylene glycol)5000- ‘Electrowetting on Dielectric’. Comparison is done distearoylphosphatidylethanolamine (PEG5000- between voltage control of DIB dimensions and DSPE), distearoylphosphatidylcholine (DSPC) and Electrowetting. cholesterol were also prepared.

62. Detection of a Common Ion Effect by The size distribution, Hb encapsulation, oxygen Artificial Stomach/Duodenum (ASD) Model affinity, cooperativity coefficient, and methemoglobin level of the vesicle encapsulated Hbs Christopher S. Polster, David C. Sperry. Analytical (both LEHs and PEHs) are consistent with values Chemistry, Eli Lilly and Company, Indianapolis, IN, required for efficient oxygen delivery in the systemic United States. circulation. To evaluate the potential use of PEHs in Lilly Compound A (LCA) is a hydrochloride salt vivo, we assessed the in vitro cytotoxicity of PEH drug candidate currently in clinical trials. In two dispersions with a human endothelial cell line. PEH separate clinical trials, differences in cmax and tmax dispersions showed negligible cytotoxicity at 1.5 g/L were observed between a dose given as a solution and of Hb. Collectively, our results demonstrate that these a dose given as the hydrochloride salt in a capsule. vesicle dispersions show good potential as an For capsules relative to solution, there was a ∼20% artificial oxygen carrier. drop in cmax while tmax was seen to increase from 0.5 to 3 hours. It is hypothesized that the differences 64. Hemoglobin Regulates the Metabolic, observed in vivo are due to a common ion effect with Synthetic, Detoxification and the chloride in the gastric environment. An Artificial Biotransformation Functions of Hepatoma Stomach/Duodenum (ASD) Model was used to Cells Cultured in a Hollow Fiber Bioreactor explore this hypothesis. The ASD model was used to simulate different gastric environments with varying Guo Chen, Andre F. Palmer. Department of levels of chloride while holding pH constant. While Chemical and Biomolecular Engineering, The Ohio the chloride content of gastric fluid has no impact on State University, Columbus, OH, United States. the expected availability of the solution dose, there is Hepatic hollow fiber (HF) bioreactors constitute one a clear trend of LCA dissolution inhibition with type of extracorporeal bioartificial liver assist device increasing chloride levels. The ASD qualitatively (BLAD). Ideally, cultured hepatocytes in a BLAD confirms that the common ion effect is indeed should closely mimic the in vivo oxygenation capable of producing the effects seen in vivo. environment of the liver sinusoid in order to yield a Computational modeling is used to assess the device with optimal performance. However, most quantitative agreement between in vitro and in vivo BLADs, including hepatic HF bioreactors, suffer results. from O2 limited transport towards cultured hepatocytes which reduces their performance. We hypothesize that supplementation of hemoglobin-

based O2 carriers (HBOCs) into the circulating cell several integrative protocols will be discussed, culture media of hepatic HF bioreactors is a feasible including: and effective strategy to improve bioreactor oxygenation and performance. We examined the i) identification and use of peptides/proteins to effect of bovine hemoglobin (BvHb) supplementation synthesize thin, conformal non-biological inorganic (15 g/L) in the circulating cell culture media of coatings (e.g., TiO2, SnO2) on, and replicas of, hepatic HF bioreactors on hepatocyte proliferation, complex-shaped biological or synthetic templates, metabolism and varied liver functions including and biosynthesis, detoxification and biotransformation. It was observed that BvHb supplementation supported ii) use of synthetic wet chemical deposition and/or the maintenance of a higher cell mass in the gas/solid reactive conversion methods to generate extracapillary space, improved hepatocyte metabolic functional inorganic (e.g., BaTiO3, Fe3O4, Au) efficiency (i.e. hepatocytes consumed much less replicas of complex-shaped biological templates. glucose), improved hepatocyte capacity for drug metabolism and conserved both albumin synthesis 66. Electrospun and Natural Fibers and ammonia detoxification functions compared to Containing Biologically Active Components controls (no BvHb supplementation) under the same as Antibacterial Materials experimental conditions. Matthew B. Dickerson,1,2 Heather R. Luckarift,3,4 Maneesh K. Gupta,1 Lawrence F. Drummy,1,5 Glenn 65. Integrating Biological Self-Assembly with 3 1 1 Synthetic Chemistry R. Johnson, Rajesh R. Naik. Materials and Manufacturing Directorate, Air Force Research Yunnan Fang,1 Jonathan P. Vernon,1 Samuel Shian,1 Laboratory, Wright-Patterson AFB, OH, United 1 1 2 John D. Berrigan, Ye Cai, Nicole Poulsen, States; 2Research Associateship Program, National 3 2 Matthew B. Dickerson, Seth R. Marder, Rajesh R. Research Council, Washington, D.C., United States; 3 2 1 Naik, Nils Kroger, Kenneth H. Sandhage. 3Materials & Manufacturing Directorate, Air Force 1 School of Materials Science and Engineering, Research Laboratory, Tyndall AFB, FL, United Georgia Institute of Technology, Atlanta, GA, United States; 4Universal Technology Corporation, Dayton, 2 States; School of Chemistry and Biochemistry, OH, United States; 5UES, Inc., Dayton, OH, United Georgia Institute of Technology, Atlanta, GA, United States. States; 3Materials and Manufacturing Directorate, Air Force Research Laboratory, Dayton, OH, United Textile materials capable of mitigating pathogenic States. bacteria and other potentially harmful biological agents are highly desirable and are under active Biology provides spectacular examples of development for use in filtration, protective hierarchical (micro-to-nanoscale) self-assembly of equipment, high performance clothing, and wound intricate organic and inorganic structures. For dressings. We present results on the fabrication of example, complex chitin-based assemblies with antimicrobial fibers based on natural B. mori silk periodic micro-to-nanoscale 2-D and 3-D fiber and electrospun nanofiber architectures. The morphologies are formed by certain butterflies and hybrid fibers produced in this work contain silver beetles. Diatoms (unicellular algae) generate nanoparticles prepared through in situ synthesis microscopic silica-bearing cell walls (frustules) with techniques and were functionalized with antibacterial a wide variety of species-specific 3-D shapes and enzymes or peptides utilizing layer-by-layer patterned nanoscale features. While the degree of processing strategies. The influence of peptide or structural precision and reproducibility achieved by enzyme loading, presence of silver nanoparticles, such organisms under ambient conditions is polyelectrolyte material selection, and electrospun impressive vis-à-vis man-made assembly methods, fiber composition on the ability of these fibers to the inorganic chemistries utilized by these organisms neutralize several strains of bacteria will be are quite limited in variety and in complexity relative described. The efficacy of enzyme/peptide to those routinely synthesized (albeit at much higher stabilization through layer-by-layer polyelectrolyte temperatures) by materials scientists/engineers. processing and the persistent antimicrobial activity of the resultant fibers were assessed under challenging Materials fabrication protocols that integrate environmental conditions and will be discussed in the biological self-assembly with synthetic chemical context of the electrospun and B. mori fiber systems. processing have the potential to take advantage of the The SEM and TEM characterization of the strengths of both approaches. In this presentation, antibacterial fibers produced during the course of this

study will be presented and factors impacting future performance of the TEV protease cleavage of the textile development discussed. eGFP-REACh FRET protein system.

67. Analytic Sensing: A Comparison of Our overarching goal is to create a bioreporter system Riboswitches and Bio-Functionalized that is capable of aqueous effluent monitoring of Nanoparticles military relevant targets. Thus one strategy has included the use of a published TNT-specific aptamer Nancy Kelley-Loughnane, Svetlana V. Harbaugh, that was previously incorporated in a solid state fiber Molly Davidson, Jorge L. Chavez, Morley O. Stone. optic biosensor. We placed the TNT-aptamer 711 Human Performance Wing , Human upstream of the riboswitch 12.1 expression platform Effectiveness Directorate, Air Force Research sequence. We employed the reporter system (i.e., Laboratory, Wright Patterson Air Force Base, Ohio, TEV-protease cleavage of FRET eGFP-REACh pair) United States. as a screening assay in order to insure greater Riboswitches are a type of genetic control element sensitivity of this new riboswitch to DNT activation. that uses an untranslated sequence in mRNA to Although DNT possesses one less nitrogen group recognize and bind small molecules, and in turn, than TNT, we envision this technology as a monitor regulate expression of that gene. Riboswitches are of aqueous effluents detecting hydrolyzed byproducts conceptually divided into two parts: an aptamer and of explosive manufacture. an expression platform. The aptamer directly binds the small molecule, and the expression platform Alternatively, we will discuss the development of undergoes structural changes in response to the portable, colorimetric sensors with fast responses and conformational changes in the aptamer and regulates high specificities for analytes. These sensors couple gene expression. We have selected as our model a the specificity and sensitivity from biology with the theophylline-responsive riboswitch that was placed promising physical properties of nanomaterials. upstream of the gene encoding several optical Recognition elements based on functional reporter systems. We selected a previously reported oligonucleotides (aptamers) and peptides have been synthetic riboswitch activated by theophylline and implemented as sensing moieties for various coupled the riboswitch to a reporter assay based on applications. Solution- and solid-phase sensors that fluorescence resonance energy transfer (FRET) respond to specific analytes have been designed with between two genetically-coded fluorescent proteins, metal nanoparticles functionalized with recognition enhanced Green Fluorescent Protein (eGFP) and a elements. The attributes of these two platforms dark yellow fluorescent protein (YFP)-based (riboswitch based and bio-functionalized Resonance Energy-Accepting Chromoprotein nanoparticles) will be compared. (REACh) (eGFP-REACh). Specifically, the theophylline-sensitive riboswitch was placed 68. Enzyme Activity of Horseradish upstream of the Tobacco Etch Virus (TEV) protease Peroxidase Encapsulated by Self-Assembled coding sequence and a FRET-based construct, eGFP- Peptide Nanotubes REACh, was linked by a peptide encoding the Byung-Wook Park, Dong-Shik Kim. Department of recognition sequence for TEV protease. The Chemical and Environmental Engineering, University advantage of using an eGFP-REACh pair is the of Toledo, Toledo, OH, United States. elimination of acceptor fluorescence which leads to an improved signal to noise ratio and sensitivity. We The objective of this study is to demonstrate the also have compared this reporter with the direct applicability of the peptide nanotubes (PNTs) to a coupling of the riboswitch with two different biosensor system. Because biomolecular chromophores, eGFP and an endogenous green nanostructures such as self-assembled peptide fluorescent protein (GFPa1) from Amphioxus (given nanotubes can be effectively used to exploit the to us by collaborator Dimitri Deheyn). For these specificity of biological systems for enzymes, in this studies, we implemented a newly optimized study PNTs were synthesized and used for enzyme theophylline riboswitch designated as 12.1 to the encapsulation. Enzymes are versatile biocatalysts that GFPa1 gene which showed increased riboswitch efficiently catalyze biochemical reactions. To activation and a greater signal-to-noise ratio. The enhance the catalytic activity and stability of enzyme, direct activation of the riboswitch on the GFPa1 the enzymes were encapsulated by PNTs. The reporter showed a 10-fold signal increase over the encapsulated enzymes inside PNTs were expected to riboswitch “off” state, similar to the superior have higher enzyme activity, higher thermal, and long-term stabilities as compared to the free enzymes

in a solution because the nanostructure of PNT has useful systems has been rarely explored. Heavier large surface-to-volume ratio and excellent atoms may introduce new properties that currently biocompatibility. PNTs can possibly provide are not available with the lighter atom cousins. environments with functionalities for enzymes. The enzyme chosen for this study was horseradish High-level computational methods, complete active peroxidase (HRP). We examined the catalytic activity space ab initio methods with (CASPT2) and without of HRP encapsulated inside PNTs in terms of thermal (CASSCF) perturbation theory, have been used to and long-term stabilities. The thermal stability of study the E-Z isomerization of aryl-phosphaalkenes HRP inside PNTs and that of free HRP in a solution (Ar-P=C(H)-Ar). Both the thermal and photo-excited were compared at the temperature ranging from 25 processes (energies, geometries, and transitions) have °C to 85 °C. Also, the enzyme activities of been explored for three proposed isomerization encapsulated HRP and free HRP were examined for 2 pathways. The pathways examined include (1) months in terms of the long-term stability when rotation about the central double bond (C-P=C(H)-C), stored in pH 7.0, 10 mM PB solution at 4 °C. (2) in-the-plane inversion about the C=P-C bond Microscopic, electrochemical, spectrophotometric angle, and (3) dissociation of the phosphorus-carbon techniques were used to characterize the double bond. nanostructure of the PNTs and the enzyme activity of HRP. Furthermore, the screen-printed electrodes The competition between this various pathways on (SPEs) were used to measure the enzyme activities the low-lying electronic states will be discussed. using cyclic voltammetry (CV). The CV results were Importantly, phosphaalkenes seem to adopt stilbene’s used to demonstrate the electrochemical effect of the classic rotation photoisomerization pathway for PNTs on the enzymes. The possibility of enhancing isomerization on the ground and first excited states. the enzyme activity by PNTs was confirmed using The results provide valuable insight for synthetic UV-Vis spectrophotometry with ABTS method and chemists who are attempting to understand, design, amperometric measurement. It turned out to be and fabricate photoactive polymeric materials. advantageous to utilize PNTs as the enzyme encapsulating material proving that the PNT 70. 4-Thiothymidine: A Nucleoside Analogue encapsulation can protect enzymes from harsh of Thymidine Showing Sub-Picosecond environmental conditions. Intersystem Crossing This advantage shows great potential of the enzyme encapsulation technique in the development of more Christian Reichardt, Carlos E. Crespo-Hernández. stable biosensors without compromising the enzyme Department of Chemistry,Center for Chemical sensitivity. Dynamics, Case Western Reserve University, Cleveland, Ohio, United States. 69. Z-E Photoisomerization of Aryl- The excited-state dynamics of the 4-thiolated Phosphaalkenes: Phosphorus Really Is a ribosylthymidine analogue (4-thioThd) have been Carbon Copy investigated with femtosecond broadband transient 1 1 absorption spectroscopy in buffered aqueous John L. Payton, John D. Protasiewicz, M. Cather 2 1 solution. Excitation of 4-thioThd at 340 or 360 nm Simpson. Department of Chemistry, Case Western leads to population of the S state. The bulk of the Reserve University, Cleveland, Ohio, United States; 1 2 excited molecules undergoes ultrafast intersystem Chemistry and Physics Departments and The Photon crossing to the triplet state while a negligibly small Factory, The University of Auckland, Auckland, New fraction stays in the singlet manifold to eventually Zealand. decay radiatively to the ground state. A fraction of The past several decades have seen heightened the triplet state population returns nonradiatively to interest in molecular devices such as molecular the ground state by triplet-triplet annihilation. Steady- switches, organic light emitting diodes (OLEDs), state emission spectroscopy in the presence and molecular wires, and numerous other molecularly absence of molecular oxygen reveals that another engineered devices. Many of these devices are fraction of the triplet-state population decays via organic-based materials that exploit E-Z phosphorescence emission at room temperature. isomerization of carbon-carbon, nitrogen-nitrogen, Quantum chemical calculations that include explicit and/or carbon-nitrogen double bonds. As intriguing and implicit solvent effects show that the presence of as the current literature is on these compounds, the the sulphur atom in 4-thioThd modifies the relative possibility of substituting heavier main group energies of the excited states to account for enhanced elements such as phosphorus into these potentially spin-orbit coupling and increased participation of the

triplet state in the excited-state dynamics of this a specific vibrational mode υ4, which is a typical thymidine analogue. marker of the oxidation state of the Iron center in a single Hemin molecule. Based on the autocorrelation 71. Computational Study of Photochemical and crosscorrelation analysis of the Raman spectra Properties of Substituted Naphthalimides mean trajectory and combined with the single- molecule spectroelectochemistry control Shubham Vyas,1 Ksenija D. Glusac,2 Christopher M. 1 1 measurements, single-molecule redox reaction at the Hadad. Department of Chemistry, The Ohio State Hemin/Ag interface is indentified to be driven by the University, Columbus, OH, United States; 2 slow thermal fluctuation and perturbed by the fast Department of Chemistry, Bowling Green State thermal fluctuation. The fluctuation dynamics of the University, Bowling Green, OH, United States. single-molecule redox reaction is critical for the Naphthalimides (NI) have both low-lying (π,π*) and further understanding, design and manipulation of the (n,π*) states in their electronic excited state manifold charge transfer process at the molecule-metal and substitution considerably alters the positioning of interface or metal-molecule-metal junctions, which these excited states. Due to these different low-lying are typical structure units in single-molecule excited states, NI chromophores have found a variety electronics. Moreover, site-specific AFM-correlated of applications. Raman spectroscopy will also be presented. To explore the photochemistry of NI, we performed density functional theory calculations on the ground 73. Shooting and Swimming Azobenzene and excited states of unsubstituted NI and 4-chloro, Single Crystals in Triacrylate Solution 4-nitro, 4-dimethylamino and 4-thiomethyl NI. The Thomas M. Sutter,1 Namil Kim,1 Dmitry Golovaty,2 lowest singlet excited state was (n,π*) state for Thein Kyu.1 1Department of Polymer Engineering, unsubstituted NI, while the S2 state was (π,π*) in University of Akron, Akron, OH, United States; character. Reversal of the aforementioned electronic 2Department of Theoretical and Applied arrangement was found for the substituted NIs. Mathematics, University of Akron, United States. Inversion of electronic excited states was observed upon solvation, consistent with experimental results. Spatio-temporal growth of gigantic azobenzene single crystals in triacrylate monomer (TA) is Excited state optimizations located two degenerate investigated in relation to the solid-liquid phase minima on the (n,π*) excited state surface of NI, diagram. Upon thermal quenching from the isotropic whereas a small energy difference between the (n,π*) melt to the crystal + liquid gap, diamond-shaped minima was introduced upon substitution. For 4-nitro single crystals emerge. During crystal growth, TA and 4-dimethylamino substituted NI, significant solvent is rejected from the growing facet fronts, geometrical changes were observed at the substituent enriching the regions adjacent to the crystal-solution unit upon optimization of (π,π*) excited state. interface with TA. As a result of TA expulsion, a Computed excited state properties were found to be concentration gradient forms and and induces in excellent agreement with the excited state convective flows in the solution and generates a experiments. These computational results and spatial variability of surface tension usually insights into the photochemistry of NIs will be responsible for the Marangoni effect. Either or both discussed in detail. of these phenomena may contribute to the observed shooting, swimming, sinking, and floating of the ejected azobenzene single crystals. Early in the 72. Probing Single-Electron Self-Exchange process, a growing faceted crystal becomes unstable, across a Molecule-Metal Interface developing a needle-like jaggedness. Further solvent Yuanmin Wang, Papatya Ceylan Sevinc, Yufan He, rejection induces the oscillatory concentration H. Peter Lu. Department of Chemistry, Bowling gradient at some distances from the solid-liquid Green State University, Bowling Green, OH, United interface. When the local concentration exceeds a States. critical value, nucleation takes place at a small distance away from the tips of the jagged facet. Once Single-molecule redox reaction dynamics of Hemin they appear, these nuclei immediately begin moving (Chloride) adsorbed on Ag nanoparticle surfaces has away from the existing interface while continuing been probed by single-molecule surface-enhanced their growth. In this talk, we will demonstrate these Raman spectroscopy (SMSERS) combined with phenomena both experimentally and theoretically in single-molecule spectroelectrochemistry. Redox the context of the surface tension driven process and reaction at the molecule/Ag interface is evidenced by crystal growth. the prominent fluctuation of the Raman frequency of

74. Synthesis and Characterization of Novel effects substantiate the assignment of the Platinum Acetylide Oligomers experimental observations.

Thomas M. Cooper, Douglas M. Krein, Aaron R. 76. Solvent Effects on Emission Spectra of Burke, Daniel G. McLean, Joy E. Haley, Jonathan M. Carminic Acid and Determination of Its Slagle, Jennifer Monahan. Air Force Research Laboratory, United States. Ground and Excited State Dipole Moments To develop novel chromophores for optical materials, Sarika Jaggannagari Brahmananda, Patty K.-L. processing and device performance investigations, Fu. Department of Chemistry, Governors State we synthesized a series of transition metal-containing University, University Park, IL, United States. phenyl acetylide oligomers. Ligand structures Absorption and fluorescence emission spectra of explored include polycyclic aromatic hydrocarbons, Carminic acid were recorded in various solvents with variable conjugation and inclusion of electron different solvent parameters such as polarities, donating and withdrawing groups. Structure-property dielectric constant and refractive index. The solvents relationship data will be presented from a variety of used in the experiment were water, DMSO, techniques, including flash photolysis and acetonitrile, methanol, propanol and butanol. The luminescence spectroscopy. To assist in developing a atomic radius of the molecule was obtained using structure-property relationship, we will also present Hartree-Fock method in molecular modeling using computational chemistry results, including molecular Spartan software. The dipole moments of Carminic orbitals, ground and excited state geometry, and acid in the ground state and excited states were predictions of ground and excited state vibrational determined. Solvatochromic shift method was used to spectra. determine the excited state dipole moments. The linear progressions were made and the slopes were 75. Ultrafast Single-Triplet Population determined from absorbance and fluorescence band Dynamics in Nitro-Aromatic Compounds shifts. The conclusions on the spectral shifts were done based on the polarity function of the solvents R. Aaron Vogt, Christian Reichardt, Carlos Crespo- and the dipole moments in ground and excited states Hernandez. Department of Chemistry, Case Western of the molecule. Reserve University, United States. The electronic energy relaxation of 2- 77. Ortho-Metallated Acetophenone Imine nitronaphthalene (2NN), 1-nitronaphthalene (1NN) Derivatives as Ligands for Group I, II, XI and 2-methyl-1-nitronaphthalene (2M1NN) were and XII Metals studied in various solvents using broadband transient absorption spectroscopy with femtosecond time John F. Beck, Joseph A. R. Schmidt. Department of resolution. As we have recently shown for 1NN, Chemistry, The University of Toledo, Toledo, OH, excitation of the 2NN and 2M1NN compounds at 340 United States. nm populates the S1(ππ*) state, which bifurcates into Ortho-metallated imines are commonly used as two almost barrierless nonradiative decay channels. ligands in late transition metal complexes. The first channel connects the S1 state with a receiver Unfortunately, not all metals can undergo the Tn state that has strong nπ* character. Intersystem necessary oxidative addition reactions to form the crossing is followed by internal conversion to the desired ortho-metallated complexes. Therefore a lowest triplet state, which is populated with excess synthetic methodology allowing easy access to this vibrational energy. The ensuing vibrational cooling binding mode from simple metal halides via the use dynamics in the triplet manifold depends on both the of ortho-lithiated imine is desirable. The ortho- solvent and the nitronaphthalene compound studied. lithiation of benzyl amines and aryl ethers has been The second minor channel involves conformational well studied. Imines are poorly developed due to a relaxation of the S1state to populate a dissociative lack of regioselectivity during lithiation and side singlet state that has significant charge-transfer reactions including nucleophilic attack of the imine character and negligible oscillator strength. It is carbon by the alkyl lithium reagent. Inclusion of a shown that the relative yield of the two initial 3,4-methylenedioxy substitution on the phenyl group nonradiative decay channels depends on the of the aryl imine allows for clean ortho-lithiation of nitronaphthalene compound studied and correlates the imine and isolation of these lithium salts. The with the measured steady-state photochemistry. substituents on the imine nitrogen have been found Quantum chemical calculations including solvent affect the clustering of the lithium complexes dramatically.Lithiated alkyl (Cy, tBu) imines

clustered as tetramers, whereas the lithiated aryl Coefficients for One Component of Binary imines formed dimers that exhibited long range Solutions ordering in the solid state forming polymeric chains. The reaction of 2 eq of lithiated imine with 2 eq of Stanley A. Studniarz. Chemisty, Penn State ethyl magnesium bromide yielded the bis-ligated University, Sharon, PA, United States. magnesium complexes via a pseudo Schlenk C. G. Wilson derived the non-ideal free energy equilibrium favoring the formation of magnesium (excess free energy) from the intermolecular complexes with more sterically demanding ligands. interactions and this approach remains of interest The lithiated imines have subsequently been reacted today. In the final Wilson equations the Gibbs free with copper(I) and copper(II) halides to form energy is minimized by adjusting two energy complexes analogous to the group I and II species. parameters but the equations are, unfortunately, Bis-ligated zinc complexes were also synthesized transcendental and generally require a medium to exhibiting a tetrahedral geometry around the metal large computer to generate the numerical solutions. center. The organometallic reactivity of group I and There are several reports in the published literature XII complexes is being investigated. describing the mathematical procedures to do this. However, Appelblatt more recently described a 78. Reactions of Methylmercuric Compounds simpler method to solve the Wilson equation; but the with Aqueous Hexacyanoferrate(II) Ion excess free energy (activity coefficient) must be measured at least at one concentration. This reports John S. Thayer. Department of Chemistry, the application of Appelblatt’s procedure to the University of Cincinnati, Cincinnati, OH, United Wilson equation to calculate the activity coefficient States. over a wide range of concentrations of organic As part of an investigation into electron-transfer compounds. Excellent agreement is obtained in reactions of aqueous organometallic compounds, we comparing the calculated results to the examined interactions between hexacyanoferrate(II) experimentally measured activity coefficients for the ion and methylmercuric compounds. Two reactions solutions tested. In addition, two tests will be occurred: electron transfer and cyanide transfer. described to confirm the validity of the final answer and the original data. The scope of this is limited to At mercury/iron ratios below 0.10, only electron binary solutions of miscible liquids. transfer was observed. Hexacyanoferrate(III) ion formation was measured by growth of an absorption 80. Bio-Inspired Synthesis, Characterization, peak at 420 nm. This increased linearly with time and and Catalytic Application of Pd Nanoparticle followed pseudo-first order kinetics. The calculated Networks overall second-order rate constant was 0.083 L/mol•s. No blue/green coloration appeared in such systems, Rohit Bhandari, Anshuman Jakhmola, Marc R. even after six days’ standing. Knecht. Department of Chemistry, University of Kentucky, Lexington, Kentucky, United States. At higher mercury/iron ratios, green and/or blue Peptides are known to mediate the production of an colors appeared, indicating the formation of mixed- array of inorganic materials on the nanoscale; valence iron cyanides. Most of these systems formed however, the final materials are typically limited to a dark blue precipitate, probably iron (III) spherical nanoparticles ranging from 2 – 150 nm. hexacyanoferrate(II). No blue or green coloration Altering the shape of the nanostructure can appeared in mixtures of hexacyanoferrates (II) and fundamentally change both the physical and (III), even after long standing. electronic properties of the material to impart a higher level of functionality, especially for catalytic We propose that both reactions proceed through an purposes. Using environmentally friendly reaction inner-shell intermediate containing a Fe --- CN --- Hg conditions, we have been able to produce Pd bridge. Reaction rates decreased in the order acetate nanoparticle networks (NPNs) in the presence of the > chloride >> iodide. These observations will be R5 peptide, which is able to self-assemble and thus discussed in the context of the chemistry of act as a template for shaped nanomaterials synthesis. methylmercuric compounds. Pd2+ ions are able to bind to the lysines of the peptide, which sequester the metal ions within the 79. Wilson Coefficients from the Excess biological framework. Upon reduction with NaBH4, Gibbs Free Energy and the Activity production of the linearly branched Pd NWNs is achieved and directed by the sterics of the system.

The metallic materials were characterized by UV-vis 2Nanostructured and Biological Materials Branch, Air spectroscopy, high-resolution transmission electron Force Research Laboratory, Wright-Patterson Air microscopy, and diffraction methods. The NWNs Force Base, Ohio, United States. were exceedingly stable in the ambient environment Combinatorial methods have been used to isolate and did not precipitate even after two months. The Pd peptides that act as stabilizers of nanomaterials, NPNs demonstrated high degree of catalytic whose synthesis and application can employ eco- reactivity for C-coupling reactions via Stille friendly conditions. We have recently exploited coupling. Using ≤0.50 mol% Pd, quantitative product peptide-based methods to prepare highly reactive Pd yields were achieved in 24.0 h with a turnover catalysts for the Stille coupling reaction. These frequency of 437.1 ± 14.3 mol BPCA (mol Pd.h)-1. catalysts are used in environmentally-friendly and Such studies demonstrate the possible capabilities energy efficient reaction conditions with low catalyst achieved by using peptide-mediated materials loadings; however, the full range of use and synthesis where final functional products are mechanism of reactivity of these unique species is achieved that operate under bio and eco friendly not well understood. By simple changes to the conditions. reaction conditions, we have been able to optimize the materials reactivity and begin to understand the 81. Conformational Analysis of Four catalytic mechanism at play. From these studies, we Polyphenolic Inhibitors of PAI-1 have fully explored the effects of reaction Christopher Fairchild, Patrick Spoutz, Maria C. temperature, catalyst loading, and reagent identity, all Milletti. Department of Chemistry, Eastern Michigan of which demonstrate a large effect on the observed University, Ypsilanti, MI, United States. catalysis. Furthermore, these results suggest that an atom leaching mechanism is likely to control the Plasminogen Activator Inhibitor-1 (PAI-1) plays a catalyst reactivity, which could be exploited for key role in inhibition of fibronolysis, the process by specific applications. which blood clots are broken down. In many cases it becomes necessary to increase the rate of 83. Validation of an HPLC-MS/MS Test fibronolysis. One way that this can be accomplished Method To Quantify S-Benzylmercapturic is by inhibiting PAI-1. Acid and S-Phenylmercapturic Acid in Previous research has shown that polyphenolic compounds that contain two gallate groups can be Human Urine effective PAI-1 inhibitors. The structures of these Clayton Bhymer. BHAB, NIOSH, Cincinnait, Ohio, compounds vary greatly in terms of the length and United States. characteristics of the linker between gallate groups. In this work we use Density Functional theory to An accurate and precise test method was developed explore the relationship between the activity of to detect and quantify the level of S- several polyphenolic compounds and the distance benzylmercapturic acid (S-BMA) and S- between their gallate rings. phenylmercapturic acid (S-PMA) in human urine. S- Specifically, relaxed scan calculations at the BMA and S-PMA are metabolites and biomarkers for B3LYP/6-31G level of theory are used to sample low exposure to toluene and benzene, respectively, and energy conformations. In addition, we examine the both solvents are of interest for use in the patterns of relative pKa of phenol protons to determination of human exposure in the workplace. determine whether there is a correlation with activity. Sample preparation for this test method included Four inhibitors with linkers between one and eight solid-phase extraction of the target analytes from the bonds in length are examined. There is a possible urine. Quantification was by means of a high- correlation between activity and distance between performance liquid chromatography with tandem rings. mass spectrometric detection. Deuterated analogs of However, there does not appear to be a significant both analytes were used as procedural internal correlation between relative pKa’s and activity. standards for this test method. Accuracy and precision of the method were demonstrated by a 82. Exploring the Effects of Reaction series of recovery experiments. Recovery varied between 99 and 110% of theory for spiked urine Conditions on the Activity of Biomimetic Pd samples with relative standard deviations of 5.0% or Nanoparticle Catalysts less. Substitute urine was also evaluated using spiked Dennis B. Pacardo,1 Rajesh R. Naik,2 Marc R. levels by this method; the recovery experiments Knecht.1 1Department of Chemistry, University of demonstrated less accuracy with the substitute urine Kentucky, Lexington, KY, United States; versus human urine. The limit of detection (LOD) for

this method was determined to be approximately 0.2 Candice N. M. N. Kashat, Lance A. Gschwender, ng/mL for S-BMA and for S-PMA. These data, other Wei Pang, Mark A. Benvenuto. Department of figures of merit and factors of the development and Chemistry & Biochemistry, University of Detroit validation of this test procedure will be described. Mercy, Detroit, MI, United States. A series of ligands, all incorporaing 84. Synthesis of Branched Gold Nanoparticles diethylenetriamine, triethylenetetraamine, or Nancy Ortiz, Sara E. Skrabalak. Department of spermine, and utilizing two further Lewis base atoms Chemistry, Indiana University- Bloomington, provided by a group of functional aldehydes, have Bloomington, IN, United States. been synthesized. Each ligand is a multi-bidentate moiety containing a minimum of three nitrogen donor The unique optical properties exhibited by branch atoms and possibly two oxygen donor atoms. The metal nanoparticles may be exploited for intensity stability of these ligands as free molecules as enhancement in surface enhanced Raman opposed to hydrochloride salts will be presented. spectroscopy (SERS), as a platform for chemical Routine structural characterization has been by 1H sensing, and in nanodevices. However, understanding and 13C nuclear magnetic resonance spectroscopy. the nature of branched nanoparticle growth, a This, plus indications of their metal binding abilities valuable factor for structure manipulation, is a will be discussed. relatively unknown process. Here, branched gold (Au) nanoparticles are produced by reducing Au (I) 87. Synthesis and Characterization of Silver in the presence of oleylamine and Pt (II). By altering surfactant concentration, reduction technique, and Nanoparticles for SERS-Based Biosensing temperature, changes in nanoparticle morphology Allie Meyerhoefer, Kent Weaver, Zachary Arnold, were observed by transmission electron microscopy Jennifer Monahan, Marjorie Markopoulos, Ioana and provide insight into the mechanism for branched Pavel. Department of Chemistry, Wright State nanoparticle formation. University, Dayton, OH, United States.

85. Unconventional Precursors with Colloidal silver nanoparticles (AgNPs) were synthesized via reduction of silver nitrate with Ultrasonic Spray Pyrolysis: Synthesis of sodium borohydride using a slightly modified Shape-Controlled Bi2WO6 Particles Creighton method. AgNPs were then characterized Amanda K. Peterson, Sara E. Skrabalak. using absorption spectrophotometry, transmission Department of Chemistry, Indiana University- electron microscopy (TEM), flame atomic absorption Bloomington, Bloomington, IN, United States. spectroscopy (FAAS), fluorescence spectroscopy, Raman and surface-enhanced Raman spectroscopy. The need to develop materials with controlled The absorption spectra presented a sharp maximum at morphologies and shapes is central to the 400 nm indicating a minimal aggregation. The TEM development of improved materials for a wide range images and size histograms were prepared by of applications, including catalysis, coatings, and analyzing 400 AgNPs indicating that the AgNPs were semiconductors. Ultrasonic spray pyrolysis (USP) is spherical with an average diameter of about 10 nm an aerosol technique that can produce fine, non- and a narrow size distribution. FAAS data agglomerated powders through the nebulization of a demonstrated a high reaction yield and allowed for precursor solution, followed by thermal the quantification of the amount of AgNPs produced decomposition of the dissolved species. By using (i.e., 15.31 ppm). Raman spectra helped confirm the unconventional precursors that yield non-transient purity of the AgNPs. Surface-enhanced Raman byproducts during USP, shape-controlled Bi2WO6 spectroscopy measurements were performed using particles have been achieved. Insight into their the rhodamine 6G (R6G) dye at various mechanism of formation was assessed by systematic concentrations to evaluate the sensing efficiency of variation of experimental parameters (e.g., these colloidal AgNPs. The analytical (7.3 x 104) and temperature, precursor properties) and thermal surface-enhanced Raman enhancement factors (5.1 x analysis of the precursors. 101) were calculated based on the Raman, SERS, and fluorescence spectra at a R6G concentration of 10-6 86. Developments in the Syntheses of a Series M. In conclusion, the proposed synthesis method led of Podand Ligands Utilizing to the formation of colloidal AgNPs of highly Diethylenetriamine, Triethylenetetraamine, uniform size and shape, minimal aggregation and or Spermine SERS-based biosensing potential similar to other

colloidal nanoparticle systems described in the required to know certain chemical facts. In 1937 the literature. Scout had to carry out several simple experiments in addition to knowing other chemical information. The CHED - undergraduate poster session. present requirements require the Scout to know about safety equipment in the laboratory, what MSDS’s are, 88. Elucidation of Peptide Effects That and how various chemicals can cause pollution in Control the Activity of Nanoparticles addition to knowing certain different chemical facts and carrying out simple experiments demonstrating Ryan H. Coppage,1 Joseph M. Slocik,2 Rajesh R. 2 1 1 chemical and physical phenomena. In addition a Naik, Marc R. Knecht. Department of Chemistry, Scout is now more explicitly exposed to chemical University of Kentucky, Lexington, KY, United 2 occupations. Requirements in 1911 dealt almost States; Nanostructured and Biological Materials entirely with inorganic chemistry. More recent Branch, Airforce Research Institution, Wright- requirements involve slightly more of the other Patterson Air Force Base, OH, United States. branches of chemistry. As of 2001 more than 240,000 Peptides have been isolated with the ability to young men had earned Chemistry Merit Badge, and complex inorganic materials to generate nanoparticle- interest remains strong with 3000-4000 Scouts based systems; however, the binding specificity of earning it each year. these peptides with the nanostructures is still relatively unknown. By designing sequence-specific 90. First Example of Triphenylene-Fused peptides to their corresponding materials, Porphyrin nanoparticles could be designed that optimize both Lin Jiang, Hong Wang. Department of Chemistry size and surface availability for reaction catalysis or and Biochemistry, Miami University, Oxford, Ohio, other functions. Furthermore, such systems are United States. envisioned to operate under environmentally friendly and energy efficient conditions and may address In recent years, porphyrins with extended pi-system issues related to future energy concerns. To probe have attracted considerable attention due to their this effect, we have isolated the Pd4 peptide, which is wide applications such as in Dye-Sensitized-Solar- able to generate nearly monodisperse Pd nanocatalyst Cells (DSSCs)1. Benzoporphyrins are well-known pi- and have begun to explore its specific surface binding extended porphyrins with red-shift absorption bands capabilities. To explore this phenomenon, we have and attractive properties for DSSCs. However, they selectively altered the binding capability through have limited synthetic approaches and are very hard single residue changes in the peptide sequence. to be modified. A concise and versatile approach to Catalytic analysis of the generated nanoparticles the synthesis of functionalized benzoporphyrins has demonstrated a direct correlation between the been developed in our laboratory (Structure 1)2. In reactivity and the peptide surface, which suggests this work, novel triphenylene-fused porphyrins were that the biotic/abiotic interface plays a critical role in synthesized through the Heck reaction and oxidative the overall material’s functionality. This data is coupling reaction (Structure 2). The fused porphyrins significant as it begins to suggest mechanistic exhibit strongly red-shifted UV-vis absorption understandings of this interface and its possible spectra. exploitation.

89. Chemistry Merit Badge – 1911-2010 Wendell L. Dilling. Department of Chemistry, Central Michigan University, Mt. Pleasant, Michigan, United States. The Boy Scouts of America is celebrating its 100th anniversary in 2010. One of the earliest merit badges was Chemistry, which was established in 1911. Unlike many other early merit badges, which have been discontinued, Chemistry Merit Badge continues to the present. The requirements for earning this 91. Structural Elucidation of Atmospheric badge have changed significantly over the past 99 Water-Soluble Organic Nitrogen Compounds years, often reflecting changes in the field of with Ultra-High Resolution Mass chemistry itself. In 1911 the Boy Scout was only Spectrometry

Jeffrey P. LeClair, Lynn R. Mazzoleni. Department 1Materials & Manufacturing Directorate, AFRL, of Chemistry, Michigan Technological University, WPAFB, OH, United States; 2UES, Inc., Dayton, Houghton, MI, United States. OH, United States; 3General Dynamics Information Technology, Dayton, OH, United States; 4SAIC, Both the chemical and physical properties of Dayton, OH, United States. atmospheric aerosol govern its ability to interact directly and indirectly with incoming and outgoing Room temperature plasma enhanced chemical vapor radiation, thus affecting the Earth’s climate. deposition (PECVD) processes can impart substantial Although the physical properties of aerosol have been internal stress in the resulting thin films. After studied in detail, there remain large uncertainties on fabrication, the accumulated residual stresses in the the climate forcing estimation of aerosol1. These films can cause deformation of the substrates coated large uncertainties can be reduced by understanding with the plasma-polymerized (PP-) films, resulting in the chemical composition at the molecular level. In adhesive and mechanical failures and device defects. our research, we focus on the identification of water- A sensitive interferometric method was employed to soluble organic compounds. Fourier transform ion quantify the deformation of silicon substrates coated cyclotron resonance mass spectrometry (FT-ICR- with thin plasma-polymerized acrylonitrile films MS) was used to obtain mass spectra and tandem deposited at room temperature. The technique is mass spectra with ultra-high resolution and high mass sensitive enough to detect deformations resulting accuracy for isolated organic anions of fog water from films with thicknesses of just 62 nm. A linear samples. Of the 1300+ organic compounds present, relationship was identified between substrate nearly 500 of them contain nitrogen2. Tandem mass deformation and film thicknesses ranging from 62- analysis was conducted with various scan ranges 372 nm. With this technique, a macroscopic change between 100 and 400 u to structurally identify in the deformation of the substrate due to nitrogen containing organic compounds. The mass compressive forces exerted by the PECVD process spectra ranges varied in complexity from simple can be correlated to film structure relaxation and spectra, where nitrophenols were identified, to very interface effects on the microscale. complex spectra containing the CHNO compounds. However, due to isobaric interferences in this topic: general physical chemistry. complex region, the isolation of a nominal mass for fragmentation analysis results in the fragmentation of 93. Densification of Plasma Polymerized several precursor ions simultaneously. The accurate TiOxCyNz Films with Air Exposure mass data was used to match fragment ions to 1,2 1,2 1,3 precursor ions. Preliminary fragmentation data of Lirong Sun, Hao Jiang, John T. Grant, 1 1 1 larger compounds (e.g., m/z 277 and 291) has shown Timothy J. Bunning, Rachel Jakubiak. Materials & losses corresponding to nitrophenol and nitro- Manufacturing Directorate, AFRL, WPAFB, OH, 2 naphthol fragment ions. These molecules may arise United States; General Dynamics Information 3 from reactions in the aqueous phase with NOx and Technology, Dayton, OH, United States; University carbonaceous precursor emissions (biogenic or of Dayton Research Institute, Dayton, OH, United anthropogenic) producing nitrophenolic structures. States. We propose structures, based on the FT-ICR-MS data Owing to their outstanding dielectric and structural obtained. These and other nitrogen containing properties, titanium oxides and oxynitrides find use compounds will be presented. in applications ranging from structural hardening to waveguides in microelectronic devices[1]. A number 1. IPCC, Climate change 2007: Synthesis Report, of techniques including spray pyrolysis, magnetron IPCC, Geneva, Switzerland, 2007. sputtering, chemical vapor deposition (CVD) and plasma enhanced CVD (PECVD) are used to grow 2. L. R. Mazzoleni, Ehrman, B.M., Shen, X., semi-crystalline or crystalline thin films of these Marshall, A.G., Collett Jr, J.L., Environ. Sci. materials. High deposition temperatures required Technol., 2010, In Press. (>400oC) for crystalline structures limit film deposition to substrate materials that have strong 92. Measurement of the Deformation of thermal resistance. Amorphous titanium oxide films Silicon Substrates Coated with a Plasma- have relatively high index of refraction compared to Polymerized Acrylonitrile Film purely organic thin films, retain much of the 1 1,2 functionality of the crystalline forms and can be David Sisler, Jesse Enlow, Vincent P. 1,4 1,3 1 deposited at low temperature. With PECVD operated Tondiglia, Hao Jiang, Rachel Jakubiak. at room temperature and in a remote configuration,

amorphous titanium oxide and oxynitride films can 95. Nano-Particles Influence on the Partition be deposited on fragile substrates like electronic of Polyaromatic Hydrocabons in Aquatic devices and polymers that otherwise would not Systems survive high temperatures or harsh environments. After deposition and contact with air, plasma- Qiuming Amy Zhao. Department of Sustainable polymerized (PP-) TiOxCyNz films derived from Technology Division, US EPA, 26 W. Martin Luther titanium (IV) isopropoxide undergo a continual King Drive, OH, United States. decrease in film thickness and increased index of The partitioning of hydrophobic contaminants refraction that does not stabilize for several days after between nano-particles and water is an important deposition. After one hour in air, the thickness of the parameter for modeling the fate and transport of these films rapidly decreased by 14% and after three weeks contaminants in aquatic environment. The octanol- the thickness decreased 30% (128 – 90 nm). This was water partition coefficient is the ratio of the accompanied by an increase of the refractive index concentration of a chemical in octanol and in water at from n589 = 1.72 to 1.84. This has implications for equilibrium. Octanol is an organic solvent that is used calibrating deposition parameters necessary to as a surrogate for natural organic matter, and correlate PP-TiOxCyNz film thickness, optical partitioning of contaminants between the two phases constants and composition. help to determine the fate of contaminants in the environment, such as to predict the extent of 94. Plasma Polymerization for Bio-Assisted bioaccumulation of contaminants aquatic biomes Fabrication of Nanostructures animals. This study is focused on the influence of Rachel Jakubiak,1 Kyle D. Anderson,2 Joseph M. nano-particles on the octanol-water partitioning Slocik,1,3 Michael E. McConney,1,2 Jesse O. Enlow,1,3 pollutants. Sorbtion of hydrophobic organic Timothy J. Bunning,1 Rajesh R. Naik,1 Vladimir V. pollutants to nano-particles increased the 2 1 concentration of contaminants in the aqueous phase Tsukruk. Materials & Manufacturing Directorate, 2 as compared to the “true” partitioning due to the AFRL, WPAFB, OH, United States; School of octanol-water partitioning. The effects of nano- Materials Science and Engineering, Georgia Institute 3 materials on the mobility of pollutants that are of Technology, Atlanta, GA, United States; UES, commonly found at many sites has been studied. Inc., Dayton, OH, United States. These compounds including 2 and 3-ring PAHs: Plasma-enhanced chemical vapor deposition naphthalene, methyl naphthalene, anthracene, and (PECVD) allows deposition of conformal, ultrathin, phenanthrene have relatively low water solubility and and uniform polymer coatings from gaseous, liquid differing mobility in the soil. The study will help to or solid precursors onto a variety of materials. Our better understand the influence of these accumulated process uses a modified afterglow plasma reactor nano-materials on contaminants mobility and soil operated at room temperature where plasma remediation technologies such as encapsulation. polymerization occurs downstream from plasma Understanding physical and chemical interactions of generation. This allows controllable retention of the nano-particles with contaminants leads to the use of precursor’s functionality needed for surface-induced nanomaterials for in-situ soil treatment technologies. biomineralization on soft or delicate substrates that cannot withstand high temperature or multiple wet- 96. Plasma Enhanced Chemical Vapor chemistry treatments. Amine-functionalized Deposition for Fabrication of Biologically substrates, derived from the plasma polymerization of Sensitive Films L-tyrosine, enabled biomineralization of gold 1,3 1,2 1 nanoparticles from a solution of gold chloride. Jesse Enlow, Hao Jiang, Daniel Gallagher, 1 1 1 Templated gold nanoparticle coatings were formed Lawrence Brott, Rachel Jakubiak, Rajesh Naik, by the placement of a shadow mask on the substrate Timothy J. Bunning.1 1Materials & Manufacturing during plasma deposition creating a micropatterned Directorate, AFRL, WPAFB, OH, United States; plasma polymerized tyrosine film. Subsequent gold 2General Dynamics Information Technology, Dayton, chloride exposure created a gold nanoparticle OH, United States; 3UES, Inc., Dayton, OH, United network replica of the initial micropattern. This States. method of templated biomineralization is adaptable Plasma enhanced chemical vapor deposition to a variety of practical inorganic and organic (PECVD) has recently been investigated as a substrates, such as silicon, glass, nitrocellulose, fabrication tool for highly sensitive chemical vapor polytetrafluoroethylene, and woven silk fibers. sensors. Since PECVD is a solvent-free, well controlled, room temperature process it is amenable

to deposition of films onto materials that cannot Kevin J. Sanders,1 Michael C. Davis,1 Derrick C. withstand wet chemical processing or high Kaseman,1 Sahar M. Parvani,1 Philip J. Grandinetti,1 temperature environments. Plasma polymerization Dominique Massiot,2 Pierre Florian.2 1Department of produces highly crosslinked amorphous films with Chemistry, The Ohio State University, Columbus, smooth surface morphologies, robust mechanical Ohio, United States; 2CNRS and Universite d properties and strong thermal, chemical and Orleans, Orleans Cedex 2, France. environmental resistances. These pp-films can be Two-dimensional magic angle flipping (MAF) NMR derived from a variety of monomers including gases, was employed to measure the Q(n) distribution in a liquids and solids, and can be engineered to retain 29Si enriched potassium disilicate glass (K O · 2 some, if not all, of the chemical characteristics of the 2 SiO ). Relative concentrations of [Q(4)] =7.23 +/- original monomers as well as creating new features 2 0.339 %, [Q(3)] =82.97 +/- 0.118 %, [Q(2)] = 9.80 +/- that do not exist in the precursor materials. A 0.660 % were obtained. Using the thermodynamic modified flowing afterglow plasma reactor is utilized model for Q(n) species disproportionation these to deposit high density functionalized polymer thin relative concentrations yield an equilibrium constant films onto several different sensor motifs including k = 0.01029 +/- 0.00084, indicating, as expected, RFIDs and silicon cantilevers to detect several 3 that the Q(n) species distribution is close to binary in chemical vapors including water, nitrobenzene and the potassium silicate glass. A Gaussian distribution half mustard gas. Systematic variation of the pp- of isotropic chemical shifts was observed for each film’s thickness and density resulted in measurable Q(n) species with mean values of -82.74 +/- 0.03 ppm, changes in sensor response to analyte exposure. -91.32 +/- 0.00 ppm, and -101.67 +/- 0.02 ppm, and standard deviations of 3.27 +/-0.03 ppm, 4.194 +/- 97. Structural Motifs in Carbon Cages and 0.003 ppm, and 5.09 +/- 0.03 ppm for Q(2), Q(3), and Clusters: Insights from C24 Q(4), respectively. Additionally, nuclear shielding Roderick M. Macrae, Davin Rose. School of anisotropy values of ζ =-85.0 +/- 1.3 ppm, η=0.48 +/- (2) Mathematics and Sciences, Marian University, 0.02 for Q , and ζ = -74.9 +/- 0.2 ppm, η =0.030 +/- (3) Indianapolis, IN, United States. 0.006 for Q were observed in the potassium disilicate glass. Bonding in carbon-containing systems is typically considered from the perspective of sp, sp2, or sp3 hybridization at the carbon centers. However, while this picture is valid for typical organic molecules such as hydrocarbons, it breaks down for elemental carbon clusters in which, except for certain limiting cases (the cyclic polyynes or cumulenes, polyhex nanotori, and the fullerenes) all possible finite structures lead to dangling bonds. Using C24 as a prototype, the relative energies of structures dominated by sp, sp2, and sp3 carbon centers are considered by means of density functional theory

calculations. In agreement with considerations based on the balance between s-strain and p-resonance [1], The distribution of Q(n)-species is consistent with the a graphenic structure is found to be the most theoretical charge balance. The value of k3 calculated energetically stable, followed by fullerene and non- in this study is also consistent with previously fullerene cage structures. Structural modifications reported trends for disproportionation equilibria by observed during geometry optimizations yield insight Stebbins et al. [1] and Murdoch et al. [2], who into favored motifs in initially trigonal and initially observed a linear relationship between modifier tetrahedral clusters and are relevant to the phenomena cation field strength and kn. Trends in nuclear of surface and edge modification known in shielding anisotropy were also observed for Q(2) and macroscopic systems. Q(3) sites that are consistent with previous observations reported by Grimmer et al. [3,4]. [1] T. G. Schmalz, W. A. Seitz, D. J. Klein, and G. E. Results indicate that as the nucleus becomes more Hite, J. Am. Chem. Soc. 110, (1988), 1113-1127. shielded (i.e. ζ increases), that the silicon-non- bridging oxygen (Si-NBO) bond length decreases. 98. Q(n) Species Distribution in K2O·2SiO2 Since Si-NBO bond distance is primarily influenced Glass by 29Si Magic Angle Flipping NMR by the field strength of the modifying cation, as the

field strength of the modifying cation increases, the with the organoclay functionalized with the longer Si-NBO bond length increases, and the shielding at alkyl chains (Mg-BTES). Significant differences in the 29Si nucleus decreases. texture and strength between the pure polymer and the nanocomposites were also observed. [1] J. F. Stebbins, Effects of temperature and composition on silicate glass structure and dynamics: 100. Investigating Mesoporous Si-29 NMR results, J. Non Cryst. Solids 106 (1988) Organosilicates as Carriers for Controlled 359–369. Delivery of the Anticancer Agent Doxorubicin

[2] J. B. Murdoch, J. F. Stebbins, I. S. E. Carmichael, Emilee Knue, Adam McCallum, Isabelle Lagadic. High resolution 29Si NMR study of silicate and Chemistry, Northern Kentucky University, Highland aluminosilicate glasses: the effect of network- Heights, KY, United States. modifying cations, Am. Mineral. 70 (1985) 332–343. Currently, the most effective and common cancer treatment is the use of chemotherapeutic drugs. When [3] A.-R. Grimmer, E. F. Gechner, G. Molgedey, 29 administered in high systemic doses, these drugs High resolution Si NMR in solid silicates. while treating malignant and metastatic cancer cells, Correlations between shielding tensor and Si-O bond can cause severe toxicity to healthy tissue cells, length, Chem. Phys. Lett. 77 (1981) 331–335. resulting in hair loss, nausea, and decreased immunity. One way to reduce this toxicity, while [4] A.-R. Grimmer, Correlation between individual 29 allowing high concentrations of the drug to be Si-O bond lengths and the principal values of the Si delivered directly at the tumor site is through drug chemical-shift tensor in solid silicates, Chem. Phys. encapsulation into delivery particulates. Our ongoing Lett. 119 (1985) 416–420. research has focused on mesoporous inorganic-based silica particles as possible carriers for the anticancer 99. Synthesis of Polymer-Layered Silicate agent, Doxorubicin (Dox). These mesoporous Nanocomposites Using One-Step Prepared silicates were synthesized without and with the Organoclays presence of organic functional groups (Sulfonate (SO -Na+) and Carboxylate (CO -Na+)) that can Thomas Morgan, Isabelle Lagadic. Chemistry, 3 2 interact with Dox through and ion-exchange process Northern Kentucky University, Highland Heights, and increase the capability of conjugating Dox. The KY, United States. - non-functionalized (SBA), the sulfonate (SBA- SO3 + - + Polymer-layered silicate nanocomposite materials Na ) and carboxylate (SBA- CO2 Na ) functionalized where polymer matrices are reinforced by mesoporous silicate materials, were treated with nanoscopically dispersed organically modified aqueous solutions of Doxorubicin in a 4:1 solid to layered silicates have attracted increasing research drug weight ratio. Based on their Doxorubicin interest as such materials exhibit enhanced loading capacity, the materials can be ranked as - + - + mechanical, thermal and gas impermeability follows: SBA- SO3 Na > SBA- CO2 Na > SBA, with - + properties. SBA- SO3 Na capable of loading up to 200 mg of In this project, we investigated the synthesis of Doxorubicin per gram of solid. The release profiles polymer-layered silicate nanocomposites using one- of Doxorubicin from the three Dox-loaded materials step prepared organoclays containing either amino in saline solution (0.9 wt% NaCl) were monitored at groups (Mg-APTES) or alkyl groups (Ethyl: Mg- 37°C. The non-functionalized SBA material exhibits ETES, n-Butyl: Mg-BTES). Mg-BTES and Mg- a rapid but incomplete (only 60%) and unreliable BTES were combined with polystyrene (PS), and release of Dox. Doxorubicin releases completely - + - + Mg-APTES was combined with polyvinylpyrrolidone from both SBA-SO3 DoxH and SBA-CO2 DoxH . (PVP). Nanocomposites were prepared using two However, Dox releases with a slower release rate - + - + processes: 1) A solution process where the from SBA-SO3 DoxH than from SBA-CO2 DoxH . organoclay is added to a polymer solution in various amounts (1, 5, 10, 25%wt). 2) A melt process where 101. Synthesis and Reactivity of Nickel PCP- the polymer is melted in presence of the organoclay. Pincer Thiolate Complexes We found that grinding the organoclay prior to its addition to the polymer improved the transparency of Jie Zhang, Jeanette A. Krause, Hairong Guan. all the nanocomposite films prepared by solution Department of Chemistry, University of Cincinnati, process. For both processes, a better organoclay layer Cincinnati, OH, United States. dispersion and a complete exfoliation were observed

A series of Nickel PCP-pincer thiolate complexes, One of the largest challenges currently facing our [2,6-(Ph2PO)2-C6H3]NiSAr, were synthesized and society is the energy crisis. As a result of increasing characterized. The reactivity of these complexes were fuel consumption and growing environmental investigated. concerns, there is a strong push to develop new sustainable and renewable energy sources. Biological 102. Gold Nanorods and Nanoprisms: systems offer inspiration for designing transition Synthesis, Characterization, and Self- metal complexes that have the potential to participate Assembly in multi-electron transfer reactions. As a step toward this goal, we have developed Pd(II) and Pt(II) 1 2 1 Kristina L. Tran, Kirpal Bisht, Vinay K. Gupta. complexes that are capable of undergoing two- 1 Department of Chemical and Biomedical electron oxidation reactions. These complexes are Engineering, University of South Florida, Tampa, square planar, with a bidentate chelating ligand 2 FL, United States; Department of Chemistry, containing a nucleophile which dangles near the open University of South Florida, Tampa, FL, United axial site of the metal center. Upon the transfer of States. two electrons, the dangling nucleophile and a second Gold nanomaterials offer attractive potential for a nucleophile (from the solvent, or the solvent itself) variety of applications such as sensing, imaging, and will coordinate with the Pd(II) center, converting drug delivery due to their unique optical properties. Pd(II) to Pd(IV), which is octahedral. In this presentation, we will investigate the two-electron Because of this, isotropic gold nanoparticles have + been of great research interest over the past decade. behavior of Pd(phpy)tacn when exposed to chemical In comparison, work on anisotropic nanoparticles has oxidants (e.g., Bromine) under different solvent not been as prevalent in literature. Anisotropic gold conditions. nanoparticles, such as nanorods and nanoprisms, are known to have strong absorption in the visible and 104. Using a Flow-Through Reactor (FTR) near-infrared regions which can be controlled To Investigate near Equilibrium Dissolution through synthesis and surface modification. We have Kinetics of Calcite and Effects of Sample studied the self-assembly of gold nanorods using two History types of bowl-shaped macrocyclic compounds called resorcinarenes as linkers. The first type of Michael Mante, Steven R. Higgins, Kevin G. resorcinarene (R2S) consisted of thiol(SH)- Knauss. Chemistry, Wrighty State University, terminated alkyl chains on both rims. The second Dayton, Ohio, United States. type (R1S) contained thiol-terminated alkyl chains on In mineral dissolution reactions, surface only one rim. The monolayer formation of these morphologies play important roles particularly in resorcinarenes on planar gold surfaces was near equilibrium fluids where generation of new sites characterized by FTIR spectroscopy. The FTIR of reactivity (e.g., pit nuclei) is thermodynamically spectra showed that both resorcinarenes formed disfavored. Following CO2 injection in geologic stable monolayers. Micromolar quantity of formations, dissolution of primary carbonate minerals resorcinarenes was added to an aqueous solution of and crack-sealing cements will occur. The impact of surfactant-stabilized gold nanorods, and self- these reactions on fluid chemistry requires better assembly was monitored through UV-Vis understanding of the reaction kinetics of major spectroscopy, dynamic light-scattering (DLS), and minerals at close-to-equilibrium conditions. Initial transmission electron microscope (TEM) imaging. A investigations have focused on quantifying calcite similar approach has been extended for gold dissolution using short residence time (∼ 10 min) nanoprisms synthesized in solution through a flow through reactors to obtain dissolution rates at o -4 kinetically controlled preparation in the presence of 60 C, pH = 8.33 and P CO2 = 3.8 × 10 atm. surfactants. In the presentation, the synthesis, Dissolution rates decreased exponentially with time, characterization, and self-assembly results will be however, the time to achieve a steady dissolution rate discussed. was approximately 120 h, suggesting that surface morphology undergoes significant changes during 103. Reactions between Pd(phpy)tacn+ and reaction rate decay. These observations are important Chemical Oxidants in the context of the interplay between surface microtopography and reaction rates and will be Allison M. Muldoon, William Connick, Sayandev discussed in light of atomic force microscopy Chatterjee. Department of Chemistry, University of investigations. Cincinnati, Cincinnati, OH, United States.

105. Quartz Crystal Microbalance with Scroll alkoxy and organosilicon nanopolymers are of Dissipation Monitoring (QCM-D) To Analyze interest because they have the potential to give useful Nanoparticle Self-Assembly and Surface materials. Such polymers can be made from the Interactions natural scroll silicate chrysotile, Mg3Si2O5(OH)4. Chemistry has been developed that allows the Stephen Hussey. Biolin Scientific Inc., Linthicum preparation of these polymers with various pendent Heights, MD, United States. groups. The scrolls have the potential to be used to make flexible silicone-insulated metal nanowires. Research on nanoparticles is a rapidly growing area One possible method of producing these is by filling of study with applications in energy, nanocomposite chrysotile-derived polymer scrolls with metal salts materials, the environment and healthcare. and then chemically or thermally reducing these salts. Nanoparticles are being incorporated or used in solar Thus far we have been able to introduce lead in the panels, nanomachines, and a variety of thin films and scrolls and attempts have been made to introduce coatings to generate more desirable properties. platinum. When these metal-filled scroll Although their use and benefits are unquestioned, nanopolymers have been developed further they have there are potential risks in their widespread use to the potential to serve as insulated nanoconductors. health and the environment. Therefore, there is a

need for new techniques to analyze nanoparticle self assembly, aggregation and surface interactions as well as track nanoparticle interactions and stability in environmental or physiological settings.

Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D) is an analytical technique that enables real-time characterization of nanoparticle interactions between other particles and a variety surfaces, including glasses, polymers and Natural Organic Matter (NOM). The QCM-D technology measures changes in mass occurring at surfaces by tracking changes in frequency of an oscillating quartz crystal. QCM-D also reveals changes in the viscoelastic properties of nanoparticle films or assemblies by measuring the dissipation parameter or energy decay of the freely oscillating crystal.

Here the QCM-D technology is shown to be a useful tool in analyzing nanoparticle self-assembly processes and surface interactions related to the formation of new coatings as well as analyzing nanoparticle/surface interactions for environmental applications. 107. Carbazole Donor and Carbazole or In summary, QCM-D is a useful analytical technique Bithiophene-Bridged Sensitizers for Dye- to study nanoparticles and to quantify their interactions with other particles and surfaces as a Sensitized Solar Cells critical step in the development of new nanoparticle- Krishna Panthi, Anthony C. Onicha, Felix N. containing materials and the ability to track Castellano, Thomas H. Kinstle. Center for nanoparticle effects on the environment. Photochemical Sciences, Department of Chemistry, Bowling Green State University, Bowling Green, 106. Metal-Filled Alkoxy and Organosilicon Ohio, United States. Nanopolymers Three metal-free organic sensitizers consisting of Plousia E. Vassilaras, Malcolm E. Kenney. carbazole as an electron donor, carbazole or Department of Chemistry, Case Western Reserve bithiophene as the linker and cyanoacrylic acid as the University, Cleveland, OH, United States. electron acceptor and anchoring groups were designed and synthesized for use in dye-sensitized solar cells (DSSCs). The sensitizers were fully

characterized by 1H and 13C NMR, MALDI-TOF (or preparing via electrospinning technique with FDA HRMS), UV-vis, photoluminescence, approved Celox in in vitro human blood coagulation electrochemistry. The photovoltaic performance of and in vivo in liver injury rodent model. In vitro the sensitizers in operational liquid junction-based experiment, blood coagulation was assessed by blood DSSCs under AM 1.5 G one-sun excitation (100 clot index (BCI) and absorbability of the dressing mW/cm2) indicate that the sensitizers are promising with Na-citrate whole human blood and stimulated candidates for use in DSSCs. Sensitizers 1 and 2 body fluid (SBF) at physiological condition. The produce a power conversion efficiency of 2.70% with chitosan-based material dressing show promising a maximum IPCE of 75% at 450 nm, while sensitizer result which is comparable to Celox. Liver injury 3 has a power conversion efficiency of 2.23% with a model in rodent was used to study the blood clot maximum IPCE of 66% at 440 nm. Under identical ability and the tissue adhesion of dressing. The conditions, the benchmark N3 sensitizer produced a dressing containing chitosan, chitin and CMCh power conversion efficiency of 6.04 % with a showed the hemostatic efficacy similar to Celox. maximum IPCE of 71 % at 550 nm. 109. A Modified Microscale Method To Determine Coefficients of Thermal Expansion for Two-Photon Dye Solutions Daniel A. Lyons,1,2 Matthew J. Dalton,1,3 Ramamurthi Kannan,1,4 Christopher A. Bailey,1,5 Michael F. Durstock,1 Byron P. Edmonds,1 Loon- Seng Tan.1 1Materials & Manufacturing Directorate, Air Force Research Laboratory, WPAFB, OH, United States; 2Southwestern Ohio Council for Higher Education, Dayton, OH, United States; 3General Dynamics Information Technology, Dayton, OH, United States; 4SynCon, Cincinnati, OH, United States; 5National Research Council Fellowship, United States. Dimensional stability is an important factor to consider especially when a material configuration is subjected to frequent thermal stress during

fabrication and deployment. While there are several established methods to determine the coefficients of thermal expansion (CTE’s) for solid samples, there are very few choices for neat liquids or solutions, and 108. Development of Chitin and Chitosan- practically none which would work with the very Based Materials as Hemostatic Dressing small sample sizes dictated by the scarcity of Jirapun Paraboon,1 Daniel Smith,1 Mark Van materials of interest. Here, a rapid method modified Dyke.2 1Department of Chemistry, University of from the set-up previously described by Wiant [1] Akron, Akron, Ohio, United States; 2The Wake was employed to determine the coefficient of thermal Forest Institute for Regenerative Medicine, Wake expansion (CTE) of microliter amounts of solution in Forest University School of Medicine, Winston the temperature range -20°C to 60°C. Salem, NC, United States. Experimentally, the sample solution was sealed in a capillary tube, and the change in length of the Exsanguination is the number one leading cause of confined liquid as a function of temperature was death in the military trauma and the second cause of monitored using a microscope and heat stage. By this death in the civilian trauma. For many years, there method, ethanol was found to have a CTE of 1230 ± are many researches being conducted to improve the 30 ppm °C-1 between 25°C and 60°C, which early management of uncontrolled hemorrhage in compared well to literature values. Similarly, the order to promote the survival of casualty. The CTE values of concentrated solutions of several two- research on hemostatic agent is one of the areas that photon active chromophores (AFX dyes developed at have been focused as the alternative method to AFRL/RX) in tetrahydrofuran (THF) were achieve this goal. The purpose of this study is to determined in the temperature region 25°C to 60°C. It compare the hemostatic efficacy of the chitin, was found that for all dyes, regardless of structure, chitosan, and chitosan derivative-based dressing

CTE decreased linearly with concentration from 1400 with TMIO to yield phenols, which may be ± 40 ppm °C-1 for pure THF to 1070 ± 30 ppm °C-1 derivatized with an appropriate silylating agent, and for a 0.2M solution of AF-457.[2] As expected, when analyzed using GC-FID and GC-MS methods. The larger temperature ranges were probed, the change in reactivity and selectivity of reaction of hydroxyl CTE with temperature became more apparent with radical with various aromatic compounds is some values varying by up to 10% across the 80°C determined at different temperatures to obtain range.[3] relative reaction rates. In this work, the reactivities and selectivities for HO• reactions with simple [1] David Wiant, PhD Dissertation (2009, Kent State arenes, such as toluene and xylene are investigated. University), pg. 95. [2] Kannan, R.; He, G.S.; Lin, L.-C; Prasad, P.N.; 111. Understanding the Fundamentals of Vaia, R.A.; Tan, L.-S. Chem. Mater 2004, 16, 185- Nanoparticle Self-Assembly: An 194. Experimental and Simulation Study [3] Abe, A.; Flory, P.J. J. Am. Chem. Soc. 1965, 87, 1 2 1838. Chakra Prasad Joshi, Yevgen Kryukov, Jacques 2 1 1 G. Amar, Terry P. Bigioni. Department of Chemistry, University of Toledo, Toledo, OH, United States; 2Department of Physics and Astronomy,the Wright Center for Photovoltaics Innovation and Commercialization, University of Toledo, Toledo, OH, United States. Self-assembly of nanoparticles has potential to be a useful technological tool in the near future. Until now, nanoparticle self-assembly has been understood empirically; a complete theory is lacking. In this paper, we provide insights into nanoparticle- nanoparticle interactions and their effect on critical nucleus size and subsequent monolayer self-assembly and growth. Thiol-passivated gold nanoparticles were used as a model system for this study, since they are

known to form compact and highly-ordered monolayers by an interfacial self-assembly 110. Selectivity of Hydroxyl Radical Addition mechanism that is reminiscent of epitaxial growth. Using epitaxial theory as a starting point, we studied to Aromatic Hydrocarbons nanoparticle self assembly with both experiments and Stephen B. Benzinger, James S. Poole. Department simulations. Our epitaxy-based analysis was able to of Chemistry, Ball State University, Muncie, IN, validate the concept of flux, determine a critical United States. nucleus size, and relate it to nanoparticle-nanoparticle interactions through the solvent. These results, Hydroxyl Radical (HO·) is a highly reactive radical combined with simulations of the nanoparticle species which typically has an extremely short system, support the idea that epitaxial theories can be lifetime under most experimental conditions, and is used to model nanoparticle self-assembly. In contrast hard to characterize by conventional methods used to epitaxy, however, we have also identified for study of carbon-centered free radical kinetics. In anomalous diffusion of the monolayer islands on the this study we propose a aminoxyl-based method for interface. In particular, the Stokes-Einstein law does relative reactivities and regioselectivities of hydroxyl not hold. Curiously, this anomalous diffusion appears radical reactions with aromatic compounds in organic to be the cause of ordering of the nanoparticle solvents. Hydroxyl radical is generated by the islands, which could be an entirely new phenomenon. thermolysis of a tert-butyl azohydroperoxide which dissociates to yield hydroxyl and tert-butyl radicals, nitrogen, and acetone. The aminoxyl 1,1,3,3- 112. Synthesis and Characterization of Silver tetramethylisoindolin-2-oxyl (TMIO) is used to trap Nanoclusters Protected by Glutathione the tert-butyl radical, but is less likely to trap Santosh Kumar, Terry P. Bigioni. Department of hydroxyl radical, which is thus free to react with the Chemistry, University of Toledo, Toledo, OH, United target arene to yield a hydroxycyclohexadienyl States. species. These species undergo hydrogen abstraction

Small metal nanoparticles with <100 core atoms and an inorganicmaterial, commonly semiconductors, diameters <2 nm have properties that are distinct not acting as the electron acceptor. While the critical only from the bulk but also from larger nanoparticles. portion of these materials is the electron donor- Their properties depend upon both their core size and acceptor interface, where electron transfer occurs, the the ligands surrounding and passivating the core. structure of these interfaces is poorly understood. In Such small silver nanoclusters have not been this work, water-soluble CdS nanoparticle, passivated extensively explored due to their poor stability and withthioglycerol, are combined with a polymer to higher reactivity. A one-pot synthesis of stable Ag form a composite. The bulk and interfacial regions of nanoclusters protected by glutathione ligands has these composites have been characterized using 1H, been developed. The synthetic process has been 113Cd and 13C solid state NMR (SSNMR) to studied by varying the solvent, the ratio of metal to determine the structure of each component ligand, speed of reducing agent addition, and the (polymer,thioglycerol (TG), nanoparticles) in each reaction temperature. Each of these reaction region. These studies have revealed specific conditions affected nucleation and growth and intermolecular interactions between the TG and ultimately the distribution of sizes in the final polymer. In order to gain additional insights into the product. The nanoclusters were separated by interface structure, CdS nanoparticles coated with TG polyacrylamide gel electrophoresis and the isolated have been coupled with small molecules. In order to clusters were further characterized by electron mimic the polymer systems of interest, the small microscopy, powder x-ray diffraction, optical molecules used are sulfonic and phosphonic acid salts spectroscopy, NMR, and other techniques. that contain an aromatic moeity. The interface has been probed with 23Na, 7Li, 31P and 13C SSNMR and 113. Synthesis and Characterization New the composition, morphology/order and interactions Influenza A M2 Ion Channel Blockers have been determined. Application of REDOR NMR has provided specific internuclear distances and the Tracy Olin, Jacob J. Weingart, Jun J. Hu. combination of these results has allowed the Department of Chemistry, University of Akron, development of model for the interface structure. Akron, OH, United States. A new set of Amantadine® analogs are designed and Symposium title:(CeRMACS003) Chemistry and synthesized for screening anti-influenza activities. Materials for Alternative Energy. Similar compounds in the past were known to exhibit antiviral activity through blocking the virus M2 ion 115. Aluminosilicate Aerogels: Synthesis and channel. However, drug resistance has developed in Characterization the most common strains and rendered these drugs 1 2 2 Anna M. Pischera, Tracy C. Olin, Marlyssa Ittes, much less effective. Though the mechanism of action 2 2 Deng-Yuan Liou, Frances Hurwitz, Matthew P. of the ion channel blockers has recently been 1 1 Espe. Department of Chemistry, The University of elucidated, questions still remain particularly 2 Akron, Akron, Ohio, United States; NASA Glenn surrounding the development of the drug resistance. Research Center, Cleveland, Ohio, United States. Thus, there is a great need for a new series of compounds to be synthesized and tested to overcome Aluminosilicate aerogels are being studied for their drug resistance. In this study, we report the synthesis applications as high temperature thermal protection and characterization of potential antiviral compounds systems. The systems being developed have a as ion channel blockers. The drug activity was composition and structure similar to mullite. studied by monitoring the host-guest interactions as a Synthesis conditions have been varied including the model of drug action via 2D NOESY NMR aluminum precursor, Al:Si ratio, water content, spectroscopy and tandem mass spectrometry prior to presence of propylene oxide and aging time. The in vitro testing. focus of this work is to determine the relationship between the structure and morphology of the aerogel 114. Hybrid Photovoltaic Materials: backbone under different synthetic conditions and to Characterization of Polymer-Nanoparticle correlate these results with the materials thermal Composites properties in order to optimize their thermal performance. The aerogels have been characterized Bimala Lama, Matthew P. Espe. chemistry, by a number of techniques such as scanning electron University of akron, akron, Ohio, United States. microcopy (SEM), Fourier transform infrared (FTIR) and most recently solid-state nuclear magnetic Polymer composite hybrid photovoltaicdevices 29 consist of a polymer, acting as an electron donor, and resonance (SSNMR). Si SSNMR shows that a much larger fraction of the Si sites contain an –OH group

than does typical silica. Also the linewidths are much First principles calculations and grand-canonical broader, indicating larger structural heterogeneity at Monte Carlo simulations have been implemented to the Si sites. These results are consistent with high investigate the interaction of hydrogen, both atomic surface area and low density materials. With Al:Si of and molecular, in models of carbon nanoporous ratios of 3-8, the 27Al SSNMR data show that there structures. The studies involved both pure and metal- are regions of pure alumina which contain doped carbon structures. Their potential for hydrogen predominantly 6-coordinate Al sites. Coupled with storage application is evaluated by calculations of the 29Si results, the NMR studies show that the bulk hydrogen mass uptake and heats of sorption at of the Si sites contain at least one Si-O-Al linkage moderate temperatures and pressures. and that there is a distribution in the number of Al near each Si. Polarization and coherence transfer 118. Enhancement of Electrochemical techniques are being applied to these systems to gain Capacitor Performance of Graphene by detailed insights into the chemical structure of the Nitrogen Doping Si/Al sites and their relative populations. Dingshan Yu, Liming Dai. Department of Chemical Symposium Title: (CeRMACS006) Materials for Engineering, Case Western Reserve University, Aerospace and Space Applications. Cleveland, OH, United States. Bulk quantities of N-doped graphene have been 116. Investigation of Self Assembled prepared through thermal annealing of exfoliated Naphthalene Diimides Using Picosecond Time graphite oxide (GO) sheets in ammonia. X-ray Correlated Single Photon Counting photoelectron spectroscopy (XPS) analysis reveals 1 2 1 the doping level of 5 % N and pyridinic N as the Natalie C. Romano, Hui Shao, Tuan Nguyen, Jon 2 1 1 dominate form in N-doped graphene samples. R. Parquette, David A. Modarelli. Department of Electrochemical measurements show that N-doped Chemistry and The Center for Laser and Optical graphene, compared with undoped graphene, exhibits Spectroscopy, The University of Akron, United 2 an enhanced capacitive behavior with better States; Department of Chemistry, The Ohio State reversible charging/discharging ability and higher University, United States. capacitance values. This can be attributed to the Research in the area of organic photovoltaics is an combined contribution from both the unique increasingly important area for the development of properties of graphene (e.g., large surface area and clean energy. We have recently investigated good electrical conductivity) and the pseudo- compounds, the disubstituted naphthalene diimides capacitive effect of incorporated nitrogen. It is (NDIs) 1-5. Compounds 1 and 2 are based on suggested that pyridinic species could modify the bolaamphiphiles, while compounds 3-5 are based on electron donor/acceptor properties of the graphene the dipeptide lysine. All of these compounds undergo surface and thereby contribute to an enhanced, fast self assembly under certain conditions as a result of and reversible faradaic redox reaction. pi-pi stacking, hydrogen bonding, and hydrophobic interactions, leading to the formation of twisted 119. Aligned Electrospun Fibers by Air- nanotapes, twisted nanoribbons, and nanotubes. Blowing Picosecond time-correlated single-photon counting 1,2 2 1 (TCSPC) was used to investigate the fluorescence Feng Du, Liming Dai. Department of Chemical and Materials Engineering, University of Dayton, lifetimes and time-dependent fluorescence 2 anisotropies of these self assembled NDI Dayton, OH, United States; Department of Chemical nanostructures. The fluorescence lifetime Engineering, Case Western Reserve University, measurements were used to determine the average Cleveland, OH, United States. lifetime of the self -assembled molecules, while the Aligned polymer fibers with a diameter in the range time-dependent fluorescence anisotropy from nanometer to submicrometer have been measurements yielded information about energy produced by electrospinning under a constant air migration thru the nanostructures. flow. The air-blowing method allows polymer fibers to be aligned in a preferred direction on most 117. Computational Investigations of common substrates in the absence of any external Hydrogen Interaction in Carbon Nanopores magnetic or electric field. This is a simple, but cost- effective, approach for producing aligned electrospun Jared M. Duncan, Rachel S. Aga. Department of fibers with various structures for a large variety of Chemistry, Wright State University, Dayton, Ohio, potential applications, for example, in tissue United States.

engineering, sensing, smart textiles, filtration and Technol., 41, 2007, 6333. Ulbricht, H. Surface catalyst supporting systems. Science, 603, 2009, 1853.

120. Binding of Ethene to Single Walled 2. Kong, J.; Franklin, N. R.; Zhou, C.; Chapline, Carbon Nanotubes M.G.;Peng,S.; Cho, K.; and Dailt, H. Science 2000, 287, 622. Daniel B. Lawson. Natural Sciences, University of Michigan-Dearborn, Dearborn, MI, United States. 3. Denis, P. A. Chemical Physics, 353, 2008, 79. Carbon nanotubes are allotropes of carbon and a single walled carbon nanotubes, SWNT, is often 4. Jakobtorweihen, S.; Keil, F. J. Molecular described as a monolayer graphene sheet rolled into a Simulation, Vol 35, (2009) 90. Denis, P. A. Chemical cylinder. SWNTs have electrical and physical Physics 353, 2008, 79.] [Zhang, J.; Liu, X.; Blume, properties that depend on the diameter of the tube and R.; Zhang, A.; Schlögl, R.; Su, D. S. Science, 322, the orientation of the carbon atoms. Though 2008, 73. nanotubes have a variety of possible applications, the interaction of SWNT with gases is an area of 121. Experimental Probing of Photonic significant interest within the chemical literature.1 Density of States in Hyperbolic Metamaterial Applications for both pure and doped SWNTs 2 2 3 3 M. A. Noginov, H. Li, D. Dryden, G. Nataraj, Yu include catalysis, gas storage and chemical sensors. 2 2 1 A. Barnakov, M. Mayy, Z. Jacob, E. E. Molecules absorbed on the surface transfer charge to 1 1 Narimanov. Birck Nanotechnology Center, Purdue the nanotubes thereby inducing changes to the 2 University, West Lafayette, IN, United States; conductivity nanotubes. SWNT’s have diameters of 2 Center for Materials Research, Norfolk State a few nm and lengths of up to 100 mm resulting in a 3 University, Norfolk, VA, United States; Summer large surface area. In the application of chemical Research Program, Center for Materials Research, sensors, the altered conductivity of these molecular Norfolk State University, Norfolk, VA, United wires produce a measured response specific to the States. gas. The large surface area gives SWNTs their capacity to store gases. 3 Gases absorbed onto the In the metamaterial with hyperbolic dispersion (an surfaces of SWNTs would also have an altered array of silver nanowires in alumina membrane) we electronic structure, thereby increasing the molecular have observed six-fold reduction of the emission life- reactivity of the absorbed gas. time of dye deposited onto the metamaterial’s surface. This serves as the evidence of the earlier Recently, hydrocarbon gases interacting with SWNTs predicted high density of photonic states in have become of interest as they have the benefit of hyperbolic metamaterials. strong carbon-carbon of carbon-hydrogen bonding. It has also been suggested that the large surface makes 122. Examination of the Boron Oxygen Bond SWNTs ideal for gas storage of low weight and the Platinum Sulphur Bond in Oxoboryl hydrocarbons. SWNT also serve as a possible 4 Thiophenyl Complex by Comparison of the catalysts for conversion of alkanes to alkenes. Gooch Structure to the Standard Model

In this work, the RHF, B3LYP and MO6 binding Lewis Structure energies of ethene to a series of CNTs including 5x0, Todd W. Gooch. Department of Physical Geometry, 6x0, 7x0, 8x0, 9x0 and 5x5, 6x6, 7x7, 8x8, 9x9 using Gravitational Unit Theory Unified Field Theory, a 6-31+g* basis are presented. Several orientations of Hebron, Kentucky, United States. ethene on the nanotubes are explored as there are substantial differences in the binding energy that Poster consisting of Gooch structure and standard depend on the orientation of the ethene to the model Lewis structure for Oxoboryl Thiophenyl nanotube. Initial geometries were obtained using the Complex. Close examination of bonding in molecule semi-empirical method PM3. Binding energies, shows bonding of Boron and Oxygen to be a 2 1/2 HOMO-LUMO gaps and molecular orbitals are bond, predicted by gravitational unit theory in 2008, evaluated using single point all electron calculations. and not a triple bond. The single bond between Platinum and Sulphur shown to be more complex 1. Lee, K.; Jin-Woo, L.; Ki-Young D.; Byeong-Kwon than previously thought with similarities to Nitrogen J. Sensors and Actuators B: Chemical, 135, 2008, Tri-iodide but stabilized by an unusual “one way” 214. Pejcic, B.; Eadington, P.; Ross A. Environ. Sci. covalent single bond.

123. Prediction of the LSER s Coefficient of H H H 16 Phosphorus and Sulfur-Containing Gas log SP=c1+r1R2+s1π 2+a1∑α 2+b1∑β 2+l1 log L Chromatographic Stationary Phases Using Quantitative Structure-Solubility The s coefficient computed in the LSER equation Relationships represents the ability of the solvent phase to engage in dipolar/polarizability interactions. Previous results Michael S. Arnold, David S. Ballantine. Department suggested that the PBE1PBE/Sadlej//PBE1PBE/6- of Chemistry and Biochemistry, Northern Illinois 311G(d,p) and B3LYP/6-311+G(2d,p)//PBE1PBE/6- University, DeKalb, IL, United States. 311G(d,p) computational model chemistries would provide trustworthy data describing such interactions. Linear solvation energy relationships (LSER) can be Reliability of these methods was established by used to predict a variety of solubility-related comparison of predicted dipole moments and properties based on a set of solute and solvent polarizabilities against a test set of experimental parameters found in the equation: values for polar and polarizable solutes. The

calculated dipole moments of the test set molecules log SP=c +r R +s πH +a ∑αH +b ∑βH +l log L16 1 1 2 1 2 1 2 1 2 1 exhibited similar small average absolute errors for -30 both methods, ca. 0.30x10 C·m. However, the The s term refers to the ability of the solvent phase 1 calculated polarizabilities using the former model to engage in dipolarity/polarizability interactions. chemistry were substantially more accurate than Quantitative structure-solubility relationships (QSSR) those using the latter. Consequently, computational use molecular descriptors to predict solubility-based studies of amino-, cyano-, and phosphorous- properties, including the value of LSER coefficients. containing stationary phases of interest in evaluating In this work, molecular properties/descriptors for the s coefficient were carried out using the former sulfur- and phosphorus-containing GC stationary approach. The utility of calculated polarizabilities phases were calculated using several theoretical and dipole moments as descriptors for prediction of and/or computational methods, and the resulting the s coefficient was evaluated for the selected set of values were evaluated for prediction of the s 1 solvent phases. coefficients. Molecular properties/descriptors included dipole moments, molecular polarizabilities, and molecular connectivity indices (χ). A strong 125. Prediction of the H-bond Acceptor correlation was found for phosphorous containing Coefficient a1 in LSER Applications Using phases between the coeffecient and calculated ∆χ QSSR values normalized by molecular volume. For sulfur- Andrew Prochaska, David S. Ballantine. containing phases, a correlation was found between, Department of Chemistry and Biochemistry, and calculated ∆χ and total polarizability values. The Northern Illinois University, DeKalb, IL, United predictive ability of molecular polarizability values States. obtained from computational software (Gaussian) were compared with polarizabilities calculated using This work used quantitative structural solubility the approach of Miller to aid in development of a relationships (QSSR) to predict the solvent phase QSSR equation. variables in the linear solvation energy relationship equation (LSER),

124. DFT-Calculated Polarizabilities and H H Log SP= c1+r1R2+s1π2+a1α 2+b1β 2+l1logL. Dipole Moments for Development of Molecular Descriptors for QSSR/LSER For the H-bond acceptor coefficient, a1, this was Studies accomplished by correlation involving two sets of Daniel J. Renfus, Brendan C. Dutmer, Thomas M. molecular descriptor methods: mass percents of Gilbert, David S. Ballantine. Department of nitrogen- and oxygen-containing functional groups, Chemistry and Biochemistry, Northern Illinois and a variety of molecular descriptors for each University, DeKalb, IL, United States. solvent phase. The solvent phases used for this study included 72 phases from the McReynolds set and Density functional theory (DFT) methods were used additional phases that were characterized in our labs. to develop molecular descriptors for quantitative Molecular descriptors were calculated using the structural solubility relationships (QSSR). These molecular modeling software CAChe and Spartan, QSSR descriptors were then used to determine the s including connectivity (χ) and shape (κ) indices, coefficient in the linear solvation energy relationship dipole moment, molar volume, and total equation (LSER):

polarizability. Performing regressions using the mass Andrew J. Rusnak, Ronald C. Brown. Department percents of functional groups yielded the best results of Chemistry and Biochemistry, Mercyhurst College, with an R2 value of 0.95. Functional groups Erie, PA, United States. containing nitrogen and oxygen in various The energetic stability of SWNT (single-walled environments have excellent predictive capability of carbon nanotube) surface carbon atoms was the hydrogen bond acceptor basicity value. investigated by performing ab initio calculations on Regressions using the connectivity indices did not 2 nanotube models. Full optimizations at the B3LYP/6- produce desirable results with an R value of 0.41. 31G(d,p) level were performed in order to determine Connectivity indices have poor predictive capabilities the energy per carbon atom as a function of varying for hydrogen bond acceptor basicity due to the fact SWNT size and geometry. The models were designed that they are only measures of size and structure of to simulate the armchair and zigzag nanotube each stationary phase. geometries. The (3,3) to (6,6) armchair nanotubes and the (5,0) to (9,0) zigzag tubes were modeled. The 126. Heat Induced Structural Rearrangement cross-sectional radii of these tubes vary from 1.97 Å and Crystallite Formation in Thin Films of to 4.08 Å. A model of a graphene sheet, effectively a Room Temperature Plasma-Polymerized tube of infinite cross-sectional radius, was also Titanium (IV) Isopropoxide included. The results were compared as a function of 1,2 1,2 1,3 tube size and geometry. It was found that as the Hao Jiang, Lirong Sun, John T. Grant, Kurt Eyink,1 Timothy J. Bunning,1 Rachel Jakubiak.1 radius is increased the surface carbons become more stable. These results provide a benchmark for the 1Materials & Manufacturing Directorate, AFRL, atomistic study of chemical adsorption to carbon WPAFB, OH, United States; 2General Dynamics nanotubes walls. Information Technology, Dayton, OH, United States; 3University of Dayton Research Institute, Dayton, OH, United States. 128. Photochemical Studies of Corannulene Derivatives; an Approach towards Designing Demand for polymeric optical components and Photoswitches devices increased dramatically in the past decade due 1 2 to their light weight and good optical transmittance; R. A. A. U. Ranaweera, Chester Williamson, Qian 1 1 1 however, the index of refraction of polymers (1.4 – Li, Derek Jones, James Mack, Anna D. 1 1 1.6) is too low for many applications. This limitation Gudmundsdottir. Department of Chemistry, was overcome through plasma polymerization of the University of Cincinnati, Cincinnati, OH, United 2 metallo-organic monomers titanium (IV) isoproxide States; Department of Chemistry, Central State where the index of refraction scaled with the cross- University, Wilberforce, OH, United States. linking density and metal atom concentration both of Corannulene derivatives have potential use as which were controlled through varying the deposition molecular tweezers and molecular switches. We and post-processing parameters. Annealing investigated the photoreactivity of corannulene (1a) amorphous films of plasma-polymerized (PP-) and its derivatives 2a and 3a. We used laser flash titanium (IV) isopropoxide at 300, 500 and 700ºC photolysis, product studies and computational caused densification of the 3-D cross-linked network calculations to identify the intermediates formed by and crystallite generation. Films annealed at 300ºC irradiating 1a, 2a and 3a. Photolysis of 2a and 3a had a substantial decrease in film thickness coupled results in formation of aldehyde derivatives. The with increased refractive index (n-D = 1.95 to 2.07) mechanism for the formation of the aldehyde will be and extinction coefficient attributed to the presented. densification of the 3-D cross-linked amorphous structure. At higher temperatures, 500ºC and 700ºC, the loss of carbon components coincided with the formation of TiO2 crystal phases leading to even higher refractive index (n-D = 2.16).

127. Computational Analysis of Surface Carbon Energetics as a Function of Carbon Nanotube Size and Geometry 129. Synthesis and Characterization of Pyrene-Containing Compounds for the Non-

Covalent Functionalization of Carbon Shirley Rosenzweig,1 George A. Sorial,1 E. Sahle- 2 1 Nanotubes Demessie. Department of Civil and Environmental 1,2 1,3 Engineering, University of Cincinnati, Cincinnati, John K. Riley, David H. Wang, Loon-Seng OH, United States; 2Office of Research and 1 1 Tan. Materials & Manufacturing Directorate, Development, NRMRL, U.S. Environmental Nanostructured & Biological Materials Branch Protection Agency, Cincinnati, OH, United States. (AFRL/RXBN), Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio, United Currently, there is inceasing interest in studying States; 2Student Research Program, Southwestern engineered nanoparticles for different applications. Ohio Council for Higher Education, Dayton, Ohio, Their novel properties, including size, special United States; 3Multiscale Composites and Polymers geometry and features, create a wide range of Division, University of Dayton Research Institute, applications in many fields of science and Dayton, Ohio, United States. manufacturing. Applications of carbon nanotubes (CNTs) and carbon Multi-Wall Nanotubes (MWNTs) Carbon nanotubes (CNTs) are promising materials have been increasing in the microelectronic and due to their excellent mechanical, electrical and composite materials industry. We are interested in the thermal properties. However, CNTs, forming application of MWCNT in water remediation, agglomerates and bundles by van der Waals forces particularly for adsorption of metal ions. The during production, are insoluble in organic solvents. concentration of metal ions is determined by While covalent functionalization proves an efficient ultraviolet-visible spectroscopy (UV-vis) analysis way to improve their solubility and processibility, the and the kinetics and thermodynamics of adsorption is structural integrity of CNTs is damaged and their being studied. aspect ratios are substantially reduced frequently, which would adversely affect the CNT’s basic Most commercially available carbon MWNTs have properties. The noncovalent functionalization route is around 5 percent of impurities, such as ash (catalyst an alternative route to effecting useful dispersion and residue), ions, and other nanoparticles. In order to exfoliation of CNTs in organic solvents. In this evaluate any adsorption properties it is necessary to presentation, three compounds containing mono-, di- create a method to clean most of these initial and tri-pyrenes were synthesized via multi-step contaminants. As part of this study, we are syntheses. Noncovalently bonding behaviors between conducting experiments with different cleaning three pyrene-containing compounds and few-walled protocols of MWNTs, including mechanical CNT (FWNT) were investigated in tetrahydrofuran filtration, acid washing, and organic solvent (THF). Thus, the pyrene-containing compounds and conditioning. Inductively coupled plasma FWNT were sonicated in THF to afford spectrometry (ICP) technique is used to determine pyrene/FWNT complexes, which were obtained by impurities present before and after these cleaning filtration. The amounts of unbounded pyrene- steps. Atomic absorption spectroscopy (AA) containing compounds were measured and calculated technique is used to determine the residual according to UV-Vis calibration curves. Then, the concentrations of selected metal cations in the amounts of absorbed pyrene-containing compounds aqueous system during the adsorption study on on FWNT were obtained. The tri-pyrene (tripod) MWNTs. Residual concentrations of metal cations compound showed the highest ability of noncovalent are also compared to values obtained by ICP functionalization on FWNT, followed by di-pyrene technique. Thermal gravimetric analysis (TGA ) is one. FWNT absorbed the least amounts of mono- used to confirm the amount of residuals in the carbon pyrene compound. Raman spectral analysis shows in the MWNT samples. The study also includes that the carbon nanotube structure remains relatively transmission electron microscope (TEM) analysis for intact after the functionalization has occurred. IR surface area and size characterization of the MWNTs, spectra indicates that the amide C=O bond vibrational which are important parameters for understanding the frequency is significantly red-shifted. Proton NMR adsorption properties. absorption peaks of the complexes are also shifted to lower magnetic field due Π-Π stacking between the 131. Surface-Functionalized Antimicrobial FWNT and pyrene-containing compound. Future Peptides for Antifouling Coatings research will be discussed in the presentation. Caitlin L. Knight,1,2 David N. Garcia,3 Matthew B. 1,4 1 1 130. Study of Adsorption of Metal Cations Dickerson, Wendy J. Goodson. Nanostructured into Carbon Multi-Wall Nanotubes and Biological Materials Branch, Materials and Manufacturing Directorate Air Force Research Lab, Wright-Patterson AFB, OH, United States;

2Biological and Nanoscale Technologies and cost and high efficiency. In this work, we report the Materials Division, UES, Inc., Dayton, OH, United results of an investigation on the molecular design, States; 3United States Air Force Academy, USAFA, preparation, spectral, and photo-electrochemical CO, United States; 4Research Associateship Program, properties of novel metal-free organic dyes and metal National Research Council, Washington, DC, United complexes for dye-sensitized solar cells. New States. perylene bisimide dyes bearing Ru-terpyridine complex units have been synthesized and Biofilms are cooperative communities of bacteria that 1 13 characterized by UV-Vis, IR, and H and C NMR live on surfaces. They are composed of single but spectroscopies. The fluorescence and electronic more often multiple species of bacteria. These properties of these new materials are investigated. microorganisms excrete polymeric substances that SEM are used to study the novel properties of nano- provide structure and protect the biofilm from the scale structures that could be fabricated by self- environment. Biofilms can be both beneficial, i.e. in assembly due to metal ion coordination, π-π stacking waste water treatment, but are often detrimental. interactions of perylene rings, and hydrogen-bonding Biofilm formation on medical implants can act as of the strucutre contained amide groups. The results sources of chronic infection while in industrial are anticipated to lead to improvements in photo- settings they can contribute to corrosion of pipelines, electrochemical organic systems. reduced flow, and fouling of materials transported.

While biofilms may be managed by regular mechanical removal or biocidal treatments, biofilms rapidly recolonize surfaces and the polymeric substances they excrete reduce the effectiveness of biocides. Preventing initial biofilm formation is a much more economical solution than regular maintenance intervals that may require pipelines to be shut down, or application of biocidal agents that may be costly or have negative environmental impacts. In our work, we propose the use of antimicrobial peptides (AMPs) to create a permanent antimicrobial surface. AMPs are an attractive choice due to their stability and broad spectrum of activity against both bacteria and fungi. We pre-screened ten commercially available peptides for their efficacy against multiple environmental isolates. From these we chose cecropin A and magainin 2 for functionalization studies. These AMPs have been tethered to surfaces through silane and maleimide 133. Bulk Heterojunction Photovoltaic Cells: chemistry. Their effectiveness at preventing biofilm formation will be presented. The Effect of Interlayer Morphology on Device Performance 132. Design and Characterization of Ru- Eric S. Harper.1 1Department of Chemistry, Terpyridine Complex Functionalized University of Dayton, Dayton, OH, United States; Perylene Bisimide for Photo-Electrochemical 2RXBN, Air Force Research Laboratories, Wright Devices Patterson Air Force Base, OH, United States. Tawfik A. Khattab,1 Mark D. Soucek.2 1Department An investigation into the interlayer of bulk- of Chemistry, University of Akron, Akron, Ohio, heterojunction P3HT:PCBM organic photovoltaic United States; 2Departments of Chemistry and (OPV) devices was conducted. Various experimental Polymer Engineering, University of Akron, Akron, treatments were applied to the interfacial layer Ohio, United States. (PEDOT:PSS) of OPV devices and the resulting device performance was measured to determine a link In photo-electrochemical devices, suitable dyes are between interlayer morphology and device used with wide band-gap semiconductors for light performance. It was found that the interlayer surface harvesting and electron transfer processes. With morphology could be modified through UV-ozone environmentally friendly and freely available solar and oxygen plasma treatments. The results showed energy, Dye sensitized solar cells are especially that the interlayer morphology does impact the device interesting and extremely promising due to their low performance, with increased device performance

resulting from rougher surfaces. This approach could We investigated the oxidation behavior of 5-ethyl-4a- provide a simple and inexpensive route to improved hydroxy-3-methyl-4a,5-dihydrolumiflavin device efficiency. (pseudobase Et-FlOH) in acetonitrile in the presence of pyridine as the base with the aim of investigating 134. Fiber-Based Bulk-Heterojunction Solar proton coupled electron transfer. We also studied the Sells Using Coaxial Electrospinning oxidation of Et-FlOH with the purpose of 1 2 determining whether the two-electron oxidized Et- Nicholas M. Bedford, Matthew B. Dickerson, FlOH2+ leads to the formation of 5-ethyl- Kristi Singh,2 Lawrence F. Drummy,2 Michael F. + 2 2 1 3methyllumiflavinium cation (Et-Fl ) with the Durstock, Rajesh R. Naik, Andrew J. Steckl. possibility of releasing protons. The cyclic 1 Nanoelectronics Laboratory, University of voltammogram of Et-Fl+ exhibits two reversible 2 Cincinnati, Cincinnati, OH, United States; Materials peaks at +0.17 and –0.52 V vs. normal hydrogen and Manufacturing Directorate, Air Force Research electrode (NHE), which correspond to the reduction Laboratory, Wright-Patterson Air Force Base, OH, of Et-Fl+ to produce semiquinone (Et-FlŸ) and United States. hydroquinone (Et-Fl–), respectively. The cyclic The potential of conjugated polymer/fullerene-based voltammogram of Et-FlOH consists of a reversible bulk heterojunction organic photovoltaics (BHJ- peak at E1/2=+0.95 V due to one-electron oxidation of OPVs) to deliver low-cost PV devices has prompted Et-FlOH, and a second irreversible peak at E=+1.4 V that arises due to another one-electron oxidation to the increased investigation of these material systems. 2+ In order for BHJs to become economically viable produce di-cation, Et-FlOH .However, when the however, power-conversion efficiencies need to be voltage is scanned back to negative potentials, we ∼ observe a growth of peaks at +0.17 and –0.52 V that increased to 10%. Common strategies to increase the + efficiencies of BHJ-OPVs include the engineering of correspond to Et-Fl . This shows that two-electron the OPV active layer morphology by heat and/or electrochemical oxidation of Et-FlOH leads to the production of Et-Fl+ possibly be releasing protons. solvent annealing techniques. It has been recently + shown that crystalline conjugated polymer nanofibers The reaction of Et-Fl with water to produce its generated through solution processing techniques pseudobase Et-FlOH is readily monitored by UV/VIS could be incorporated into and increased the absorption spectroscopy as shown in figure 1. The efficiency of the active layer of BHJ-OPVs. first oxidation potential of Et-FlOH at +1 V is reversible in the absence of pyridine. After addition In this study, fibers of poly(3- of pyridine we observe, a shift of the potential to a lower value, suggesting a proton-coupled electron hexylthiophene):phenyl-C61-butyric acid methyl ester (P3HT:PCBM) are created by coaxial electrospinning transfer (PCET) and an increase in the anodic current and incorporated into the active layer of a BHJ-OPV suggesting additional oxidation process with an device. The P3HT:PCBM material is contained in the irreversible peak. We initially thought that the proton core of the fiber with polycaprolactone (PCL) as the is released from the –OH group of Et-FlOH. We sheath. The P3HT portion of the electrospun fibers is prepared Et-FlOMe derivative expecting to observe crystallized and the PCL is removed in polar organic no reaction with pyridine. But, the same PCET solvents. The P3HT:PCBM fibers are subsequently process was observed, suggesting that the proton is deposited onto devices by spin coating, followed by being removed from N-CH2 group. We therefore, the deposition of an interconnecting backfill layer. concluded that the removal of H+ from Et-FlOH Devices containing P3HT:PCBM fibers have radical cation leads to additional one-electron increased efficiencies post annealing compared to oxidation to form iminium ion [Et(-H+)-FlOH+]. devices made from only thin films (3.3% from 2.3%). This study shows the potential of using coaxial KEY WORDS: flavinium salt, pseudobase, electrospun fibers as a means to improve device electrochemical oxidation, cyclic voltammetry, performance in BHJ-OPVs. pyridine, proton-coupled electron transfer (PCET).

135. Electrochemical Oxidation of 5-Ethyl-4a- Hydroxy-3-Methyl-4a, 5-Dihydrolumiflavin (Pseudobase Et-FlOH ) Vincent A. Sichula, Ying Hu, Ekaterina V. Mirzakulova, Ksenija D. Glusac. Chemistry and Photochemistry, Bowling Green State University, Bowling Green, Ohio, United States.

Fluorescence spectroscopy is a useful, non- destructive method for analyzing a variety of different samples. This project focuses on the implementation of a fiber based fluorescence spectrometer for use in an undergraduate physical chemistry lab. Beyond installation and set up of the instrument, it was necessary to determine how to obtain a valid spectrum and to write standard operating procedures for the device so it can be used in a turn-key fashion by students in laboratory classes. This challenge required understanding the basics of fluorescence spectroscopy as well as interpreting the specifics of the particular instrument so that meaningful and instructive information could be readily obtained. Because of the simplicity of its components, some work had to be done to prepare

the spectrometer in this fashion. A linear variable 136. Computational Studies with Iridium filter with an adjustable bandwith is used to select appropriate excitation wavelengths from a xenon PCP Pincer Comlpexes for Hydrogen Release flashlamp. This filter had to be calibrated and set up Omar Bibi, Jeff Seyler. Chemistry, University of for easy use by students in a variety of different Southern Indiana, Evansville, Indiana, United States. experiments. A pre-existing physical chemistry lab measuring the amount of fluorescent material in With a need to pursue alternative fuels to reduce commercial products has been modified to fit the greenhouse gas emissions and preserve petroleum spectrometer and adjusted to be a working lab for an resources, research efforts have turned to the promise undergraduate physical chemistry course. of hydrogen. This has inspired the search for viable CO2-free hydrogen generation and storage methods. With onboard storage of hydrogen in liquid organic 138. H2 Reactivity of Pd Nanoparticles materials in mind, iridium pincer complexes as Coated with Mixed Monolayers of Alkyl dehydrogenation catalysts have been reported in Thiols and Alkyl Amines for Sensing and literature. We have employed semi-empirical Catalysis Applications computational studies for relatively rapid screening Monica Moreno, Francis P. Zamborini. Department of pincer complexes and intermediates in the catalytic of Chemistry, University of Louisville, Louisville, mechanism. The pincer complexes have been based Kentucky, United States. on the well known phosphine and phosphonite PCP ligands, 2,6-(R2PCH2)2-C6H4 and 2,6-(R2PO)2-C6H4. Here we describe the reactivity between H2 and Reports by others have shown that Ir complexes with solutions or films of Pd nanoparticles protected with i t these PCP ligands, R = Pr and Bu, are effective octylamines (C8NH2), hexanethiols (C6S), and mixed catalysts in the dehydrogenation of organic monolayers of the two ligands. The average substrates. Our computational studies have examined composition of the Pd MPCs was Pd919(C8NH2)168- these PCP complexes in comparison to other R x(C6S)x, where we varied x to be 0, 3, 10, 17, 34, 84, substituted phosphines. With the cyclopentyl and 168 by synthesizing pure C8NH2 Pd MPCs and derivative, R = C5H9, showing promise, we have liquid-phase place-exchanging the C8NH2 with initiated synthesis and catalytic studies. This report various amounts of C6S. We studied the reactivity of will discuss both computational and synthetic results. the various Pd MPCs with H2 by bubbling H2 through solutions of Pd MPCs and monitoring the UV-Vis 137. Fiber-Based Fluorescence Spectroscopy spectrum with time and by monitoring the change in with a Variable Bandpass Filter for Use in an resistance of solid-state film of Pd MPCs when Undergraduate Physical Chemistry exposed to H2 of various concentrations. The reactivity between Pd MPCs and H varied as a Laboratory 2 function of the C8NH2:C6S ratio. When x = 0-10, the Katherine Macri, David Styers-Barnett. Pd MPCs react strongly with H2, leading aggregated Department of Chemistry, University of Indianapolis, particles in solution or large irreversible changes in Indianapolis, IN, United States. the morphology of films. This is accompanied by a loss of the C8NH2 ligands and increased film

conductivity by 2-5 orders of magnitude. When x = In an attempt to improve the performance of jet 168, the Pd MPCs are stable against aggregation or turbine engines, mechanical bearings with greater large morphology changes, but they are also not hardness have been developed. This increase in highly reactive to H2 as determined by minimal hardness was achieved by carburizing the steel changes in resistance or optical properties in the surface to form metal carbides. The chemical and presence of H2. Finally, when x = 17, 34, and 84, the physical characteristics of transition metal carbides Pd MPCs are fairly stable, exhibiting minimal allow for higher operating temperatures. aggregation or morphology changes, and they readily react with H2 based on the measurable reversible However, it has been found that carbides interact changes in film resistance in the presence of H2 from with lubricants and additives differently than the 100% down to 1.0% H2 and small changes in the UV- metal oxides normally found on the surface of alloys. Vis spectrum. The use of Pd nanoparticles with In particular the additive, tricresyl phosphate (TCP), mixed monolayers offers H2 reactivity, while is intended to aid in the lubrication role at high maintaining structural stability necesary for sensing temperatures and pressures. Instead TCP reacts with or catalysis applications. the surface and the ester to initiate the decomposition of the lubricant blend. 139. Observation of FRET between Fluorescently Labelled Silica Particles In order to understand how TCP is able to initiate this complex series of reactions, the interaction of the Mouhamad Khalil. DON, IPCMS institut de molecule with carbide surfaces must be explored. physique et chimie des matériaux de Strasbourg, Density functional theory (DFT) calculations were Strasbourg, Alsace, France. used to model both the TCP molecule and a carbide Monodisperse colloidal silica spheres with various surface. These models were then used to study what surface coatings are of considerable interest to many happens when TCP attached to the surface. This fields, such as ceramics, colloids, catalysis, example system was able to show stress and chromatography, and glass preparation. We are distortion of both the TCP as well as the surface. It is interested in these particles for their use as a model also seen that TCP bonds to the surface using three colloid. Silica particles are easily prepared by using a bonds to both carbon and the metal. The distortion method developed by Stöber and al. A monodisperse caused by the bonding is the likely source of the colloidal silica spheres were prepared by hydrolysis initial decomposition of TCP. and condensation of tetraethoxysilane (TOES) in a mixture of water, ammonia and a lower alcohol. 141. Thermodynamic Parameters of These silica spheres were woated with the coupling Exchange in Solution of Adducts Formed agent 3-aminopropyltriethoxysilane (APS) in the from [PCl2N]3 and Group 13 Lewis Acids reaction medium. APS in known for its stability in basic solutions. The amine functionality of APS Zin-Min Tun, Matthew J. Panzner, Doug A. coated silica particles allows the coupling with Medvetz, Brian D. Wright, Linlin Li, Deepa Savant, carboxyl group COOH of Alexa Fluoro, and leads to Peter L. Rinaldi, Wiley J. Youngs, Claire A. Tessier. the formation of fluorescent silica nanoparticles. A Department of Chemistry, The University of Akron, mixture of Alexa 488 and Alexa 647 coated silica Akron, OH, United States. nanoparticles leads the FRET phenomenon by laser Functionalized phosphazene polymers are mainly excitation of acceptor if the particles are distant by derived from the chlorophosphazene polymer, which less then 5 nm. Particles were characterized by FTIR in turn is traditionally synthesized by the ring- Spectrum, UV-Visible Spectometer, FX- opening polymerization (ROP) of [PCl2N]3. To study Spectroscopy, elemental analysis and images have the mechanism of the ROP, we focus on the been made on home built Confocal Fluorescent fundamental acid-base chemistry of [PCl2N]3. Microscopy. [PCl2N]3 is a weak base and its reaction with relatively strong Lewis acids gave adducts . 140. Computational Investigations of the [PCl2N]3 MX3 (MX3 = AlCl3, AlBr3, GaCl3) under . Interactions between Phosphate Esters and rigorous anaerobic conditions. [PCl2N]3 MX3 adducts Metal Carbides were characterized by X-ray crystallography, and multi-nuclear and variable-temperature NMR studies. J. Eric Hils, David W. Johnson, Vladimir Benin. Dynamic NMR studies were done to investigate their Depatment of Chemistry, University of Dayton, fluxional behavior and thermodynamic parameters Dayton, OH, United States.

were determined. The values of the parameters critical solution temperature (LCST) by adjusting the suggest an intramolecular exchange process. percent modification of HPEI with isobutyryl amide groups (IBAm). Specifically, 10% (HPEI-IBAm0.10), 2+ 142. Role of Ca Ions on Acid-Induced 54% (HPEI-IBAm0.54), and 70% (HPEI-IBAm0.70) Conformational Changes in Horseradish amidated samples were synthesized. Additionally, HPEI-IBAm0.54 was further modified with hydroxyl Peroxidase 1 13 ethyl groups (HPEI-IBAm0.54-Eox0.56). H and C 2 1 Daniela M. Vasquez, Scott M. Tremain. NMR spectroscopy data confirmed the percent 1 Department of Chemical Sciences, Raymond modification. Ultraviolet-visible spectroscopy clearly Walters College, University of Cincinnati, showed the LCSTs, at a pH of 7.4, for HPEI- 2 Cincinnati, OH, United States; Department of IBAm0.54 and HPEI-IBAm0.54-Eox0.56 to be 24°C and Chemistry, Eastern Illinois University, Charleston, 26.5°C, respectively. Additionally, the systems IL, United States. displayed a strong inverse relationship of the LCST We investigate acid-induced conformational changes with pH. This data suggests a strong potential for in Ca2+-bound and Ca2+-depleted horseradish using modified HPEI systems as nonviral gene peroxidase (HRP) by monitoring heme Soret vectors. absorbance. We observed that when the concentration of HCl is 1 mM or lower, the Soret absorbance (λmax = 403 nm) of Ca2+-bound HRP remains unchanged after 30 minutes. At an HCl concentration greater than 31.6 mM, no changes in the Soret absorbance (λmax = 370 nm) are observed (acid-denaturation occurs before the first spectrum is collected). However, at an intermediate HCl concentration of 5.6 mM, the Soret absorbance blue-shifts slowly from 403 nm to 370 nm over 30 minutes. This allows us to monitor the process of acid-denaturation on an accessible time scale. Heme Soret absorbance spectra collected over 30 minutes at eight pH values ranging 2+ from 4.00 to 1.75 for the acid-denaturation of Ca - bound and Ca2+-depleted HRP will be presented. 2+ Results show that the acid-denaturation of Ca - 144. Surface Initiated Polymerization in the depleted HRP occurs at a faster rate, illustrating the Presence of Cholesteric Liquid Crystals important role Ca2+ ions play in the structural stability of HRP. Jennifer Hurtubise, Michael E. McConney, Timothy J. White, Vince P. Tondiglia, Lalgudi V. Natarajan, 143. Temperature and pH Responsive Timothy J. Bunning. Materials and Manufacturing Polyethyleneimine Systems as Potential Directorate, Air Force Research Laboratory, Nonviral Gene Vectors WPAFB, OH, United States. Cholesteric Liquid crystals are highly promising for S. Chad Skidmore, Eric Fossum. Department of their ability to form photonic band-gaps. The Bragg Chemistry, Wright State University, Dayton, Ohio, reflection of CLCs is dependent on the concentration United States. of chiral molecules in the CLC mixture. Furthermore, Increasing evidence has shown the ability of polymerization in the presence of CLCs, acting as an polycationic systems to work as nonviral gene anisotropic solvent is quite can impart the forming vectors. Modified hyperbranched-polyethyleneimine polymer with helical structure. Here, we present (HPEI) has strong potential as such a vector due to its investigations on polymerization of mesogenic notable transfection efficiencies and relative stability. monomers in the presence of a cholesteric liquid Some modified HPEIs are considered “smart” due crystal “solvent”. The polymerization is surface their ability to undergo reversible conformational localized by including the photo-initiator in the changes with applied stimuli. polyimide mixture used to form the LC anchoring film. By localizing the polymerization reaction to one However, modifications resulting in ideal in vitro surface of the cell, the photonic properties of the cell conformational changes have yet to be determined. are significantly altered by changes in the Therefore, this study focused on tuning the lower concentrations of chiral and achiral molecules in the

volume of the cell. The resulting surface polymer tablets, and SmartBoards. Chemistry courses where stabilized CLCs can have photonic band gaps that are these technologies are being used include: general very wide, or even contain more than one photonic chemistry lecture and lab, physical chemistry, and band gap. Such broad reflection notches are highly chemical education courses for future chemistry and promising for many applications, such as switchable physics teachers. Teaching pedagogy relevant to mirrors. using these technologies, and moreover, the advantages and disadvantages associated with using 145. Investigation of Recombination these technologies in teaching chemistry will be Mechanisms in Ultrathin Film Iron Oxide discussed. Photoelectrodes 147. Laser Flash Photolysis Study of Different Kelley M. Hutchins, Benjamin M. Klahr, Thomas Substituted Phosphorylazides W. Hamann. Department of Chemistry, Michigan State University, East Lansing, Michigan, United Hoi Ling Luk, Sivaramakrishnan Muthukrishnan, States. Matthew S. Platz, Christopher M. Hadad. Department of Chemistry, Ohio State University, Columbus, OH, Hematite (Fe2O3) has many desirable properties for United States. use as an electrode material in photovoltaic devices including a low band-gap of 2.2 eV, the very large Phosphoryl azides are potential photoaffinity labels abundance of iron in the Earth’s crust, the extremely for characterizing the active site of human low material cost, and electrochemical stability. paraoxonase-1 (HuPON1), which is a potential The effective use of Hematite as a photoelectrode has bioscavenger against organophosphorus. We are generally been prevented, however, due to the using photoaffinity labeling (PAL) to identify the key combined poor material characteristics of low hole residue of the active site of PON1. Hence, study of mobility and fast electron-hole recombination, which photochemistry of different substituted phosphoryl results in a very short charge collection length. We azides is of great interest in assisting the design of a have recently shown that use of ultrathin films of suitable PAL. Hematite prepared by Atomic Layer Deposition can partially overcome the short charge collection length. Laser flash photolysis experiments were conducted In this work we investigate the limiting for different para-substituted diphenylphosphoryl recombination pathways in such ultrathin film azides (Scheme 1). Transient absorptions observed at hematite photoelectrodes. Steady state current density 340 nm were assigned to the corresponding triplet vs. applied potential measurements were employed to nitrenes. The assignment was also supported by our determine the photovoltaic performance density functional theory calculations. The lifetimes characteristics in response to variations of the of the triplet nitrenes were recorded in different incident light intensity, pH of the contacting solvents including dichloromethane, methanol and electrolyte, and concentration of both oxidized and cyclohexane. The electronic nature of substituents on reduced species at the semiconductor-liquid interface. the aromatic rings of the phosphoryl azides has a Nearly ideal behavior was observed which allowed us significant effect on the lifetime of the triplet nitrenes to identify the dominant recombination pathway relative to the unsubstituted compound. The electron- which limits the photovoltage. Initial attempt to withdrawing nitro groups increase the lifetime of the overcome this recombination mechanism – a key to triplet nitrenes and electron-donating groups decrease improving the efficiency – will also be presented. the lifetime of the triplet nitrenes. Relevant data for this work will be presented. 146. e-Volving Student Learning in Chemistry Using Technology Larry Kolopajlo. Chemistry Department, Eastern Michigan University, Ypsilanti, MI, United States. Using technology in the chemistry classroom can make the subject more interesting to students, and can better e-volve their learning. In this poster, several technologies used in chemistry classroom teaching at the college level will be presented including animations, animated cartoons, flip-video camcorders, podcasts, vodcasts, Smartpens, graphics

porphyrin and N-confused porphyrin derivatives substituted with trialkoxybenzene groups at the meso phenyl positions using amide, hydrazide and ether linkage were prepared. The synthesis, absorption and fluorescence measurements of these compounds in solution will be presented.

150. Synthesis and Photophysical Properties of Peripheral Modification of N-Confused Tetraphenylporphyrins Dimer and Trimer Rashid Altamimi, David A. Modarelli. Department of Chemistry, The University of Akron, Akron, Ohio, United States. The photophysical behavior of porphyrins and their derivatives have attracted much attention during the past three decades due to their interesting optical properties and similarities to pigments found in biological organisms. The aim of this research involves the synthesis and photophysical 148. Design and Synthesis of Corannulene- characterization of 1,3,5-tris[4-(N-benzyl)- Based Organic Light Emitters 5,10,15,20-tetraphenyl N-confused free-base Derek Jones, James Mack. Department of porphyrin] benzene and 1,3-bis[4-(N-benzyl)- Chemistry, University of Cincinnati, Crestview Hills, 5,10,15,20-tetraphenyl N-confused free-base KY, United States. porphyrin] benzene. We intend to use a combination of steady state fluorescence, as well as time-resolved Since their discovery, fullerenes and nanotubes have fluorescence and transient absorption pump probe spearheaded the development of nanotechnology. experiments to measure the energy transfer rate However, they are difficult to synthesize and modify constants in these molecules. In this poster we for specific tasks. Corannulene, which is 1/3 of present the synthesis and preliminary photophysical fullerene [60], has unique fluorescent and properties of these macromolecules. electrochromic properties that can be applied in a variety of fields. Furthermore, corannulene-based 151. Synthesis and Photophysical Properties organic materials have the potential to advance of Corannulene Based Organic Materials organic light emitting diode (OLED) technology. Corannulene-based organic molecules have been Praveen Bachawala, James Mack. Department of designed and synthesized. Studies have shown a Chemistry, University of Cincinnati, Cincinnati, OH, significant red shift in the absorbance spectra and United States. increased luminescence of these molecules compared Palladium catalyzed Sonogoshira coupling reactions to the parent structure. Further studies of these were employed to extend corannulene’s arom. system corannulene-based materials will help unravel at the 1,8 and 1,5 positions with corannulene and applications suitable for uses in an assortment of different corannulene derivs. UV spectroscopy results nanotechnological fields. indicate a significant bathochromic shift of these novel derivs. when compared to corannulene itself. 149. Synthesis and Photophysical Properties Furthermore, computational data performed at of Meso Substituted N-Confused Porphyrins B3LYP 6-31G level supports our exptl. results. The Rajendra Acharya, David A. Modarelli. Department knowledge gained from our study will further help us of Chemistry, University of Akron, Akron, OH, in understanding the structural importance of the 1,8 United States. and 1,5 positions on corannulene’s rim. This will allow us to design a better and more efficient blue N-Confused porphyrins have attracted much attention light emitter. in recent years. Part of the interest in these molecules results from their absorption spectra that are red 152. Nanotechnology & Energy shifted towards longer wavelengths than regular porphyrins. In the work presented here, three sets of

Wade Adams. Richard E. Smalley Institute for fabricate polymer bilayers allow us to study the Nanoscale Science and Technology, Rice University, influence of the semiconductor-dielectric interface in Houston, TX, United States. transistors. Second, we will discuss recent efforts on the use of Nanotechnology at Rice University has been huge nanopatterned layers on controlling the performance since the discovery of the BuckyBall in 1985 and the of bulk heterojunction photovoltaic devices. Nobel Prize that followed in 1996 to Rick Smalley and Bob Curl at Rice. The Richard E. Smalley Institute, following the death of Smalley in 2005, 154. Strateges for the Development of Highly now advocates and supports research and education Efficienct Oragnic Solar Cell Materials in nanotechnology with over 150 faculty members in Yue Wu, Jianhui Hou. Solarmer Energy Inc, El sixteen different departments. Major areas of Monte, CA, United States. emphasis include nanomaterials, nanobiology, nanophotonics, nanoelectronics, nanoenvironmental In recent two years, innovation in organic solar cell research, outreach to the public, and nanotechnology active materials has pushed polymer solar cell in energy. Although research in all these areas is efficiency up to around 8%. This presentation will important and all receive substantial funding, review the progress in solar cell materials, research in energy was considered by Rick Smalley particularly Solarmer’s approaches for achieving to be both the single most important problem facing highly efficient polymer solar cells by tuning humanity today and a magnificent scientific and polymer bandgaps and HOMO/LUMO level. In technical opportunity. Rick’s vision of a long-term addition we will also present the development of future energy system transporting energy around the highly efficient polymer solar cells, transparent solar world as electrons on a smart, high-capacity world- cells, and tandem solar cells by selecting suitable wide grid system can only be realized by a revolution materials and their combinations. in nanotechnology. Solving the world’s energy and climate challenges will demand revolutionary 155. Polymer:Polymer Organic Photovoltaics breakthroughs in the physical sciences and Using Polyfluorene Based Electron Acceptors engineering, and nanotechnology offers Christopher A. Bailey,1 Barney E. Taylor,2 Jianguo unprecedented opportunities for new physical and Mei,3 John R. Reynolds,3 John J. Henderson,1 chemical properties to meet those challenges. Benjamin J. Leever,1 Michael F. Durstock.1 1RXBN, Air Force Research Lab, Dayton, OH, United States; 153. Interfaces of Semiconducting Polymers 2Universal Technology Corporation, Dayton, OH, in Transistors and Solar Cells United States; 3Department of Chemistry, University Michael Chabinyc, Justin Cochran, Neil Treat, Craig of Florida, Gainesville, FL, United States. Hawker. Materials Department, University of Synthetic control over the Highest Occupied California, Santa Barbara, CA, United States. Molecular Orbital and Lowest Unoccupied Molecular The solution-processability of semiconducting Orbital has been of significant importance in organic polymers represents an opportunity to revolutionize photovoltaics due to the nature of charge separation the manufacture of large area electronic devices. in donor/acceptor blends. One technique for Applications for these materials range from low-cost obtaining tunability with polymer synthesis is to displays and e-readers to solar cells. Molecular combine electron donating and electron accepting interfaces are critical features in organic electronic moieties separated by a conjugated linkage unit. In devices. In thin film transistors (TFTs), the charge this work, we report the material and device carriers accumulate in the first few nanometers of characterization for poly(2,7-divinylene fluorene-co- material near the dielectric interface. In photovoltaic benzothiadiazole) (F10DVBT), which utilizes a devices (OPVs), heterointerfaces of semiconducting vinylene linkage between the fluorene and polymers and small molecules allow charge benzothiadiazole. This material shows improved separation. Processing conditions such as thermal open circuit voltages when mixed with poly(3- annealing have a strong influence on the molecular hexylthiophene) (P3HT) when compared with (1-(3- organization and thereby electrical properties. We methoxycarbonyl)propyl-1-phenyl-(6,6)C61 (PCBM), will describe recent efforts at rational methods to however the short-circuit current is reduced due to form controlled interfaces in organic electronic the lower electron mobility of F10DVBT. devices that allow a more detailed understanding of Morphological studies suggest that the lower their impact on charge transport. First, we will mobility may be due to the amorphous structure, describe how dry thin film transfer methods to which prevent efficient intrachain electron transport

resulting in increased charge recombination. Our containing both electron donors (D) and acceptors results will be compared with similar published (A), makes them highly promising candidates for this materials that highlight some of the more interesting purpose. In the research presented here, we describe considerations for future studies using donor/acceptor the photophysical characterization of D-A systems conjugated polymers. containing covalently bound porphyrin-fullerene dyads, where different numbers (1-4) of C60- 156. Directed Morphology of Molecular fullerenes were attached to a porphyrin core to Device Components and Student-Amenable enhance the electron transfer efficiency. In this Frameworks for Understanding Bulk presentation, we describe the results from Heterojunction Photovoltaics fluorescence quantum yield measurements, as well as the results of time-resolved fluorescence and Brian D. Pate. Department of Physics & Department femtosecond transient absorption spectroscopic of Chemistry, Central Michigan University, Mount studies used to determine the electron transfer rate Pleasant, MI, United States. constants (kET). Derivatives of phthalocyanine are of interest as candidate active layer components of organic 158. Impedance Analysis and Modeling of electronic devices, such as photovoltaic cells based P3HT:PCBM Organic Photovoltaic Devices on molecular heterojunctions. The relevant physical Benjamin Leever,1,2 Michael Durstock,1 Tobin properties of thin films of the phthalocyanine family Marks,2 Mark Hersam.2 1Materials & Manufacturing are influenced by molecular aggregation and Directorate, Air Force Research Laboratory, Wright- orientation. In this context, recent studies of the field- Patterson AFB, OH, United States; 2Department of directed assembly of thin films of fluid-processed Materials Science, Northwestern University, tetraazaporphyrin derivatives, including Evanston, IL, United States. phthalocyanines, will be described. Effects due to coupling of interfacial phenomena with applied Impedance spectroscopy has been a powerful tool in (magnetic, shear, electric) fields are particularly understanding the role of interfaces in myriad relevant to directing the morphological evolution of materials and devices. Since the importance of these systems as well as their resultant optical and interfaces in bulk heterojuntion organic photovoltaics electronic characteristics. Correlations between is well know, this work employs impedance photoconversion efficiencies, molecular structure, spectroscopy to analyze bulk heterojunction morphology, and exciton dynamics allow for P3HT:PCBM devices over the frequency range of 1 establishing a framework for selecting candidate Hz -10^6 Hz. The contributions of numerous active layer components for bulk heterojunction parameters were evaluated, including device devices. Such a framework is potentially amenable illumination intensity, the ratio of the bulk for introduction into a multidisciplinary heterojunction components, and the thickness of both undergraduate laboratory setting. the bulk heterojunction and interfacial layers. These results are used to suggest a simple equivalent circuit 157. Photoinduced Electron Transfer Studies model, which corresponds well with experimental in Porphyrin-Fullerene Dyads-Tetrads data. The technique may prove to be an alternative to time-consuming microscopic analysis of these Jojo Joseph,1 Tuan Nguyen,1 Chien-Lung Wang,2 devices. Stephen Z. D. Cheng,2 David A. Modarelli.1 1 Department of Chemistry, The University of Akron, 159. Structure of Irreversibly Adsorbed 2 Akron, Ohio, United States; Department of Polymer Polymers by Off-Lattice Monte Carlo Science, The University of Akron, Akron, Ohio, Simulation: Molecular Weight Effects United States. Vikram K. Kuppa. University of Cincinnati, United The development of efficient alternate energy sources States. is becoming increasingly important. Photovoltaic cells in particular have attracted much interest and Monte Carlo simulations of polymers irreversibly are quite promising for their potential to generate adsorbed onto a flat surface are studied using a clean electricity. Photovoltaic cells based on coarse-grained, freely rotating chain model. inorganic materials have the highest efficiencies to Monomer interaction with the surface is several times date. However, the great potential flexibility for higher than the thermal energy, kT, and the device manufacture and the low costs projected for interaction between polymer beads is adjusted so as the production of organic photovoltaic cells, to mimic the presence of a good solvent. The effect

of chain lengths and chain length distributions are an insight into the structure, energetics, and dynamics investigated by employing a Monte Carlo move suite of the selective interaction of metal ions with organic that permits the exchange of beads between polymer acids and the role of cations in the colloidal molecules. The structure of the adsorbed polymer aggregation of NOM molecules. layer, including the density and bond orientation order parameter profiles, the adsorbed monomer 161. Single-Walled Carbon Nanotube fractions and topology populations are all shown to Stability as a Function of Size and Geometry: be strongly influenced by the molecular weight A Computational Analysis of Surface Carbon distributions of the adsorbing species. These results Energetics are explained in terms of interaction strengths, segregation effects, and the competition between Ronald C. Brown. Chemistry & Biochemistry, chains to make contact with the surface. Mercyhurst College, Erie, PA, United States. A series of computational models of single-walled 160. Molecular Dynamics Simulations of carbon nanotubes (SWNT) were designed and Metal Ion Complexation with Aqueous optimized to determine the relative stability of the Carboxylates surface carbon atoms as a function of nanotube size Eugeniya Iskrenova-Tchoukova,1 Andrey G. and geometry. The models were designed to simulate Kalinichev,1,2 R. J. Kirkpatrick.3 1Department of zigzag(n,0) [n = 5 to n = 9], and armchair(n,n) [n = 3 Chemistry, Michigan State University, East Lansing, to n = 6] nanotube geometries. The cross-sectional Michigan, United States; 2Department of Geological radii of the SWNT in this study ranged from 2.2 Å to Sciences, Michigan State University, East Lansing, 4.4 Å. The tube ends were truncated to create cross- Michigan, United States; 3College of Natural sectional models and the dangling bonds at the ends Sciences, Michigan State University, East Lansing, of the cross-sections were capped with hydrogen Michigan, United States. atoms. For each nanotube size and geometry studied, a series of models of increasing lengths were fully Knowledge of the molecular mechanisms of selective optimized at the B3LYP/6-31G** level of theory. interaction of metal ions with carboxylate groups The results of the full optimizations were then used to advances the understanding of a variety of industrial, compute the relative energetic contributions of environmental, biophysical, and geochemical carbon atoms on each specific SWNT size and processes. In aqueous solutions, dissolved natural geometry. For comparison to a hypothetical tube of organic matter (NOM) tends to form colloidal infinite cross-sectional radius, a similar process was supramolecular aggregates depending on the nature used to compute the relative carbon energy on a and composition of the ionic species in solution, pH, single graphene sheet. It was found that the relative temperature, and the nature of NOM itself. We energy per carbon atom decreases uniformly as the present a molecular dynamics study of the interaction tube radius increases. These results may be useful 2+ + 2+ of Ca , Na , and Mg with carboxylic groups in a toward better understanding adsorption processes to model NOM molecule, acetate, and bicarbonate in SWNT. water at ambient conditions. Site-specific potentials of mean force characterizing these interactions are 162. Methanation on Fe Surface: First- developed from umbrella sampling simulations and Principles and Microkinetic Modelling equilibrium simulations. Estimates of the equilibrium constants of the metal-carboxylate association as well Dominic Alfonso, Dan Sorescu. Chemistry and as of the residence times of metal ions in different Surface Science, National Energy Technology coordinations with the carboxylic groups are Laboratory, Pittsburgh, PA, United States. presented. In water, the average residence time of a A microkinetic model for the production of methane Ca2+ ion in a contact ion pair with the carboxylic from CO and H on a clean Fe(100) surface will be groups is estimated to be on the order of 1 ns, while 2 presented. A reaction scheme which consists of the corresponding residence time of a Na+ ion is only dissociative adsorption of H and CO followed by between 0.01 and 0.07 ns. The average residence 2 step wise hydrogenation of C and O giving rise to time of a Ca2+ ion in a bidentate coordinated contact methane and water was considered. A microkinetics ion pair vs. a monodentate coordinated contact ion code was developed which enables the simulation of pair is estimated to be 0.05 ns and about 2 ns, hosts of elementary steps. The thermodynamics and respectively. The mechanisms by which calcium ions kinetic parameters were derived from periodic promote the aggregation of NOM molecules in density functional theory. Consistent accounting of aqueous solutions are discussed. The study provides entropic effects was carried out in the determination

of surface coverages of the reaction intermediates. A simulation method using Atom-centered Density statistical thermodynamic treatment was applied Matrix Propagation (ADMP) and molecular throughout to obtain values for enthalpy and entropy dynamics implemented in ONIOM. The specific under realistic conditions. The surface behavior under focus of this work is phosphoric acid (PA)-doped a wide range of temperatures, pressures and initial polybenzimidazoles. concentrations will be presented. As a first step, an appropriate DFT functional and 163. Molecular Dynamics Simulation of basis set for ADMP calculations was determined Thermoset Fracture and Its Integration with through gas-phase proton affinity studies of PA. Micromechanics Analyses Results indicated that B3LYP/6-31++G(d,p) provided the best trade-off between computational cost and 1,2,3 4 1 James C. Moller, Logan Ward, Vernon Bechel, accuracy in modeling PT events in PA systems as 1 1 1,5 Rajiv Berry, Timothy Breitzman, Endel Iarve, compared to MP2/aug-cc-pVTZ calculations. Then a 1 1 1 David Mollenhauer, Marilyn Unroe. AFRL/RXBC, series of quantum mechanism (QM) calculations Air Force Research Laboratory, Wright-Patterson using B3LYP/6-31++G(d,p) DFT and molecular 2 AFB, OH, United States; Department of Mechanical dynamics simulations at different temperatures and Manufacturing Engineering, Miami University, utilizing the COMPASS forcefield were performed 3 Oxford, OH, United States; Universal Technology on PA. Preliminary ADMP simulations were also 4 Corporation, Dayton, OH, United States; The Ohio performed on a PA cluster consisting of 3 PA State University, Columbus, OH, United States; molecules for 1 ps at 298 K. 5 University of Dayton Research Institute, Dayton, OH, United States. QM calculations were used to calculate gas-phase Molecular dynamic behavior associated with proton affinities and interaction energies of various thermoset resin fracture is investigated with the aim components in the PA system. Results predict proton of indentifying fracture toughness in the context of a affinities corrected for zero point energies and thermal enthalpies in descending order (unit: kJ/mol): composite matrix. Models have been applied which 4- 3- 3- P2O7 (2584.5) > PO4 (2404.4) > HP2O7 (2165.7, react resin and linker molecules to a high extent. A 2- 2- 2091.8) > HPO4 (1892.4) > H2P2O7 (1667.1, bond scission model has been developed and - - deployed in strain-rate-controlled tensile fracture 1740.9) > H2PO4 (1359.8) > H3P2O7 (1242.4) > H4P2O7 (857.5) > H3PO4 (822.4) > H2O (684.1) > tests. The effects of resin chain extensibility and + dilution on fracture behavior are studied by testing a H5P2O7 (434.9). Detailed single coordinate driving, variety of molecular systems. The molecular bases followed by quadratic synchronous transit for precursors to fracture are studied by examination optimization was used to determine energy barriers of the demography of free volume growth, bond for different PT pathways in PA. Determined energy barrier heights in ascending order are (unit: kJ/mol): scission sites, and positions of free chain ends. The + H3O –>H3PO4 (0); H4P2O7–>H3PO4 (2.6); H3PO4– critical energy release rate is identified by tracking - + the energy partitions related to the molecular system. >H2PO4 (5.3); H4PO4 –>H3PO4 (∼7.3); H3PO4– The stiffness, strength, and fracture properties >H4P2O7 / H3PO4–>H3PO4 (16.0); H4P2O7–>H2O inferred can be provided to micromechanics-based (28.6); H3PO4–>H2O (47.1). The COMPASS force composite simulation. field was used to study condensed-phase properties of PA. Good agreement between experimental data and 164. Computational Chemistry and MD results including density, radial distribution functions (RDF), and self-diffusion coefficient at Molecular Simulation of Phosphoric Acid- different temperatures provides validation of the Doped Polybenzimidazoles: Preliminary COMPASS force field for PA. The RDF results are Studies of Phosphorous Acid summarized in Table 1. Shuo Li,1 Joel R. Fried,1 Douglas S. Dudis.2 1Department of Chemical & Materials Engineering, University of Cincinnati, Cincinnati, OH, United States; 2Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright Patterson AFB, OH, United States. The ultimate goal of this project is to investigate the mechanism of proton transport (PT) in a typical fuel cell proton-exchange membrane by use of a hybrid

check the applicability of the Wade–Mingos theory within the n+1 electron pairs rule. It will be shown that the presence of bridging hydrogen atoms reduces the compactness of the corresponding polyhedron that makes it to lose the closo properties as this rule expects. With the aim to brace our conclusions, we have extended our treatments to the gallanes homologous clusters. The computation was realized at B3LYP/6–311+G(d,p), BPW91/6–311G(d,p) and B3LYP/6–311+G(3df,2p) levels of theory.

166. Nickel Hydride Complexes Supported by PCP Pincer Ligands: Efficient Catalysts for Aldehyde and CO2 Reduction Preliminary ADMP studies show that the ADMP approach can reasonably describe the PT and self- Sumit Chakraborty, Jeanette A. Krause, Hairong dissociation processes in PA, as shown in Figure 1. Guan. Chemistry, University of Cincinnati, Cincinnati, OH, United States. PCP pincer ligand-supported nickel hydride complexes were synthesized. These nickel hydride complexes react very rapidly with aldehydes and carbon dioxide to generate nickel alkoxide and nickel formate complexes respectively. A catalytic hydrosilylation process has been developed based on the aldehyde insertion reaction which showed a lagre functional group tolerance and chemoselectivity. The carbon dioxide insertion reaction has also been successfully utilized in reducing CO2 to methanol derivative in a catalytic manner.

167. Ruthenium Complexes [Ru(bpy)2(DMSO)Cl]PF6 and [Ru(tpa)(DMSO)Cl](ClO4) as Potential Photodynamic Therapeutic Agents Srikanth R. Banda,1 Jeff Rack,2 Patty K.-L. Fu.1 165. Is the (n+1) Electron Pairs Rule 1Department of Chemistry, Governors State Applicable to Alanes? A DFT Structural University, University Park, IL, United States; 2 Study of AlnHn+2 (n=4, 5,…8) Chemistry, Ohio University, Athens, OH, United Mohamed Maatallah,1 Driss Cherqaoui,1 Joel F. States. 2 1 1 Liebman, Abdellah Jarid. Chemistry, Cadi Ayyad Ruthenium complexes have been developed to University, Faculty of Sciences Semlalia, Marrakech, overcome the downfalls of cisplatin such as cellular Morocco; 2Department of Chemistry and resistance and limited activity against most common Biochemistry, University of Maryland, Baltimore forms of breast and gastrointestinal tumour. County, Baltimore, Maryland, United States. Ruthenium complexes can bind to the DNA forming adducts which block the DNA and RNA synthesis It has been suggested recently that the alanes AlnHn+2 can be treated by the polyhedral skeletal electron pair and induce programmed cell death. In this study, theory (PSEPT) as it was successful for their boranes novel octahedral ruthenium complexes were 2– synthesized and characterized. Various strategies congeners like BnHn . 2– + have been employed to improve the sequence AlnHn+2 have been considered as AlnHn + 2H . The additional hydrogens donate their electrons to the selectivity, binding capability, and photocleavage potential to native double-stranded DNA. Ruthenium AlnHn polyhedral framework and according to the n+1 electron pairs rule; these clusters should have complexes are inactive and non-reactive until they some closo polyhedral structures. In this work the enter the cancer cells where they are reduced to more active forms (activation by reduction). For a metal AlnHn+2 (n=4-6) is structurally studied with the aim to

compound to be active in vivo, it must have a terpyridine ligands was investigated extensively as biologically accessible reduction potential, which can DNA photo nuclease in vitro. This work has led to vary with the ligands attached. Both the complexes in the realization that the complex binds to DNA this study have their absorbance maximum in the purines and upon irradiation leads to the spontaneous visible region (415 nm). Upon irradiation, cleavage of DNA. Owing to the low molar absorptive [Ru(bpy)2(DMSO)Cl]PF6 is able to photocleave of these complexes in the visible region, direct plasmid DNA. In contrast [Ru(tpa)(DMSO)Cl](ClO4) cleavage of duplex DNA by this complex requires did not cleave the plasmid DNA under similar irradiation in the near UV region. The observation of conditions. Cytotoxicity and phototoxicity of both DNA photo cleavage in vitro makes this system good complexes towards the human normal and cancerous candidate for further investigation. In order to skin cells were measured and the LD50 is calculated. observe the penetration and cytotoxic nature of the complex, cell studies were done using human skin 168. Ruthenium Complexes as DNA cells. The cytotoxicity of the drug was higher in Photonuclease in the Treatment of Malignant when irradiated than in the dark proving it to be a Skin Carcinoma very good photo sensitizer. In future, the cytotoxic nature of this complex will be tested on the cancer 1 2 Devi Kalyan Karumanchi, Jeff Rack, Patty K.-L. cells in vitro. In the present study, we explored the 1 1 Fu. Department of Chemistry, Governors State DNA photo cleavage using gel electrophoresis, university, University Park, IL, United States; cytotoxicity and photo cytotoxicity tests. 2Department of Chemistry, Ohio University, Athens, OH, United States. 169. 2-Phenyl-1-10-Phenanthroline: Sun exposure creates a significant risk factor for Reactivity with Gold(III)Salts developing skin cancer. According to the American Sibrina N. Collins,1 Jeanette A. Krause,2 Sara E. Cancer Society, more than 1 million cases of non- Wiswell,1 John C. Warren,3 Sayan D. Chatterjee,4 melanoma skin cancer are diagnosed yearly in the William B. Connick.2 1Department of Chemistry, United States. In addition, melanoma, the most College of Wooster, Wooster, Ohio, United States; severe type of skin cancer, will account for about 2Department of Chemistry, University of Cincinnati, 68,720 cases of skin cancer in the year 2009. Each Cincinnati, Ohio, United States; 3Department of year, melanoma claims about 11,590 lives in the Chemistry, Youngstown State University, United States. American Academy of Dermatology Youngstown, Ohio, United States; 4Pacific Northwest (AAD) has indicated that as the incidence of National Laboratory, Richland, WA, United States. melanoma skin cancer continues to increase in this country, so does the need for early detection and Cisplatin and Carboplatin are well-known treatment of these tumors. AAD further attested the pharmaceuticals used to treat various forms of use of sunscreens can reduce the destructive effects cancer. However, severe side effects and drug of UV radiation. Melanoma is the most serious form resistance limit their use. In an effort to synthesize an of skin cancer. It often starts as a new spot, thickness, alternative to these, we investigated the coordination or color on the skin’s surface. Melanomas often have of gold(III) salts with 2-phenyl-1,10-phenanthroline a variety of colors and are usually irregular in shape. (PNP). Gold(III) complexes are considered a Existing moles can develop into melanomas. If promising alternative because they are isoelectronic untreated, metastatic melanomas can spread to and isostructural to platinum(II). Crystal engineering internal organs and cause death. Since 2003 more techniques were used to react gold salts (e.g. HAuCl4 than 477,000 people have been diagnosed with or KAuCl4) with PNP in a 1:1 CH3OH/CH2Cl2 melanoma skin cancer and it has claimed more than solvent mixture. The reaction between HAuCl4 and 10,000 lives yearly. PNP formed a salt complex [PNPH][AuCl4]. A monodentate complex, (PNP)AuCl3 was the product Photodynamic therapy (PDT) has received quite a bit from the reaction of K[AuCl4] and PNP. The 1 of attention in the past few years due to its ability to products were characterized using H NMR destroy cancer cells selectively without harming spectroscopy, infrared spectroscopy, and X-ray normal tissue, thus in turn eliminating patients having crystallography. severe adverse side effects. A minimal side effect not only can improve the quality of life for cancer 170. Ligand Redox Activity Observed at patients, it can release both patients and caregivers Cu(II) and Zn(II)- Pyridyl(pyrrolide) from tremendous burden. Ruthenium complex with Complexes strong oxidizing ligands like malonate and 2,2,6,2 -

Jaime A. Flores, Robert J. Wolfe, Jose G. Andino, Arsenic occurs naturally in ground water due to Hyunsoo Park, Kenneth G. Caulton. Department of mineral dissolution and is associated with an Chemistry, Indiana University, Bloomington, IN, increased incidence of skin, lung, and bladder United States. cancers. Contemporary remediation relies on adsorption to remove toxic arsenic from drinking 2-(2’-Pyridyl)-pyrrolides (L) with different water. However, adsorption methods best remove substitution patterns at the aromatic rings were used As(V), while As(III), the more toxic and more mobile as monoanionic supporting ligands for Cu(II) and form of arsenic, is more difficult to control. Merloc Zn(II) bis(chelate) adducts. These fully characterized B9, a synthetic dithiol compound designed to capture coordination compounds show interesting redox- mercury from water as an irreversibly bound, non- active features at the ligands in accordance with leaching compound, also forms covalent bonds with cyclic voltammetry and mass spectrometry analyses As(III). This offers distinct advantages over currently as well as DFT calculations. Species produced in this used, easily reversible arsenic capture techniques. way include M(L) q where M = Cu or Zn and q = +1 2 Laboratory batch tests on arsenic-contaminated water or +2. Oxidation with Br will also be discussed. 2 demonstrated that solid Merloc B9 effectively cleared the water column of arsenic under a range of pH 171. Electronic Structure Effects on the conditions. A prototype filtration column containing Photoinduced Ligand Exchange and DNA Merloc B9 was field tested in West Bengal, India on Binding of Ru(II) Polypyridine Bisthioether 40 potable water wells having arsenic concentrations Complexes up to 220 µg L-1, 22 times higher than EPA and Robert N. Garner, Lauren E. Joyce, Claudia Turro. WHO limits for safe human consumption. The prototype column reduced ground water arsenic in Department of Chemistry, The Ohio State University, -1 Columbus, OH, United States. these wells to ≤ 5 µg L ; competing ions present in the well water had no effect on arsenic removal. 2+ [Ru(bpy)2(L)] (bpy = 2,2´-bipyridine; L = 1,2- bis(phenylthio)ethane, 3,6-dithiaoctane, 173. The Effects of the Dimethylether eythlenediamine, 1,2-dianilinoethane) complexes Bridging Moiety in the H-Cluster of the were synthesized and their photochemistry was Clostridium pasteurianum Hydrogenase on the investigated. Photolysis experiments show that the bisthioether ligands are more easily photosubstituted Mechanism of H2 Production: A Quantum - Mechanics/Molecular Mechanics Study by Cl , bpy, and H2O than the corresponding diammine complexes. In addition, these complexes Steven Trohalaki, Ruth Pachter. Air Force Research show photoinduced binding to nucleic acids. DFT Laboratory, Materials & Manufacturing Directorate, Calculations show that bond elongation is greater for Wright-Patterson Air Force Base, OH, United States. complexes containing bisthioether as compared to bidentate nitrogen atoms in the minimized triplet [Fe-Fe]-hydrogenases are naturally occurring excited state relative to the ground state. The metalloenzymes that catalyze the reversible calculations also show that the sulfur containing production of H2 from two protons and two electrons. complexes have low-lying Ru(σ*)-based orbitals that [Fe-Fe]-hydrogenases found in two species – can be implicated in ligand dissociation. Clostridium pasteurianum (CpI) and Desulfovibrio desulfuricans (DdH) – were shown with x-ray 172. Remediation of Ground Water Arsenic crystallography to have active sites that are very similar, although several atoms were unresolved. In Using a Synthetic Dithiol, Merloc B9 earlier work, we employed density functional theory Lisa Y. Blue,1,2 Abhijit Mukherjee,3 E. Railey (DFT) within a QM/MM method to investigate two White,2 Alan Fryar,4 David A. Atwood.2 1Department previously proposed mechanisms of hydrogen of Research and Development, Merloc, LLC, production by DdH and CpI hydrogenases but we Lexington, KY, United States; 2Department of assumed that the active sites were identical, with a Chemistry, University of Kentucky, Lexington, KY, dimethylamine bridging moiety in the active site. Our United States; 3Bureau of Economic Geology, results were consistent with the two hydrogenases University of Texas, Austin, TX, United States; having different mechanisms. Recent experimental 4Department of Earth & Environmental Sciences, evidence, however, shows that the dimethylamine University of Kentucky, Lexington, KY, United moiety is indeed present in the DdH hydrogenase States. while recent quantum mechanics simulations, based on a newer, more refined crystal structure, indicate that the CpI hydrogenase has a dimethylether

bridging moiety in the active site. We describe in this behavior. Tissue engineering strategies require a paper QM/MM simulations of the CpI hydrogenase scaffold matrix for cell growth to provide both a with a dimethylether bridging moiety. Our new mechanical support and synthetic cell growth results for the CpI hydrogenase together with our environment. A scaffold is typically a highly porous previous results for the DdH hydrogenase are structure made of biodegradable polymers that serve consistent with a single mechanism for the as a three-dimensional (3D) template for cells to production of H2 by these two hydrogenases. adhere, proliferate, differentiate and generate tissue.2,3 The polymeric scaffolds are designed with a 174. Advances in Combinatorial and High- high concentration of microporosity as pathways to Throughput Screening of Biofunctional diffuse-in nutrients and toxins, growth factors, and Polymers air, as well as for removal of waste products.

Carson Meredith. School of Chemical & Our design includes micro and nanoporous Biomolecular Engineering, Georgia Tech, Atlanta, biodegradable polymer blend for 3D scaffolds to GA, United States. serve as the platform for formation of a tissue of choice. And here we present a systematic study of 2D The past ten years have witnessed the emergence of a substrates with controlled nanotopology. new set of tools, combinatorial and high-throughput screening in polymeric biomaterials development. Our experiments demonstrated that the osteoblast These tools, developed initially in the drug-discovery show sufficient attachment to the untreated surface of industry, and later applied to catalysts and inorganic the phase-separated polymer blend, namely: materials, allow orders of magnitude increases in the polycaprolactone (PCL) and poly(D,L-lactide) rate of exploration and characterization of new (PDLA) and PCL and poly(L,L-lactide) (PLLA). materials. This talk will review recent examples of However, this cell line preferentially differentiates on high-throughput and combinatorial studies of a narrow range of composition and processing biofunctional polymers. Biofunctional polymers parameter window. This is in good agreement to our exhibit chemistry or physical properties specifically previous osteoblast cell attachment behavior studies designed to function in a biological context. that readily attached to the phase separated blend Examples include polymers with unique binding surfaces.4 In particular, we showed that a 50:50-blend affinities or surface physical properties for gene- and ε drug-delivery, tissue engineering scaffolds, anti- of a semi-crystalline polymer, poly( -caprolactone) fouling and anti-bacterial coatings, and biocatalytic (PCL) and amorphous polymer, poly(D,L-lactide) applications. An emphasis will also be placed on (PDLLA) annealed for 2 hours at 110°C yielded a recent developments in our laboratory, including phase morphology that significantly enhanced multi-component reactive composition gradient osteoblast differentiation. Currently, we show surface polymer libraries and metal-coated latex beads for analysis of the above mention blend systems that enabling high-throughput spectroscopic bioassays. relates to the cell proliferation window. We show that 50:50-blend of PCL/PDLA polymers annealed for 2 hours at 110°C has the highest roughness in 175. Nanotopography of Phase Separated comparison to other blend compositions. In addition, Polymer Blend Scaffolds for Cell Seeding 50:50-blend is the only composition that has surface Jolanta E. Marszalek,1 Alamgir Karim,1 Charles K. composition representing the bulk composition of the Thodeti,2 Ravi Kumar Adapala,2 Carl G. Simon.3 sample. As expected, time of annealing has a 1Department of Polymer Engineering, University of significant influence on domain size and surface Akron, Akron, OH, United States; 2Northeastern composition, but it was shown that 2 hours exposure o Ohio Universities Colleges of Medicine and to 110 C resulted in largest PCL-rich domain sizes on Pharmacy, Rootstown, OH, United States; 3Polymer the surface. Division, NIST, Gaithersburg, MD, United States. 1) Discher, D. E.; Janmey, P.; Wang, Y. L. (2005), Cells are naturally sensitive to physical, biochemical 1 Science, 310, 1139 and chemical stimuli from their surroundings. In 2) Shea, L. D., Wang, D., Franceschi, R. T., and vivo, cells are constantly exposed to the extracellular Mooney, D. J. (2000) Tissue engineering, 6, 605 matrix (ECM). The ECM, which is formed from a 3) Langer, R., and Vacanti, J. P. (1993), Science, 260, complex connection of proteins, glycoproteins, and 920 proteoglycans, presents the cells not only with 4) Meredith, J. C., Sormana, J., Keselowsky, B. G., structural support but also with a set of signals, like Garcia, A. J., Tona, A., Karim, A., and Amis, E. J. growth factors, that guide cellular anchorage and

(2003), Journal of Biomedical Materials Research A, throughput hydrophobic dye binding called High- 66, 483. Throughput Thermal Scanning (HTTS) which can be applied using automation and a real-time PCR 176. Block Copolymer Thin Films for Protein machine 96-wells at a time. This system is being used Nanopatterning to directly test the “rules” of protein design, taking those rules as hypotheses and sorting the resulting Kevin A. Cavicchi. Department of Polymer libraries for structure and stability. Here we will Engineering, The University of Akron, Akron, OH, discuss the in-depth analysis of a library of United States. hydrophobic core variants, as well as initial results A current interest in biotechnology is the patterning from surface libraries and rational design based on and immobilization of biomolecules on surfaces for library statistics. application in biosensors, tissue engineering, and proteomics. Block copolymers are good candidate 178. Interaction of Nanomaterials with materials to template protein patterns because they Human Blood Proteins and Platelets form periodic, ordered patterns at length scales of Silvia H. De Paoli Lacerda. CBER, FOOD AND tens of nanometers. These templates are generated by DRUG ADMINISTRATION, BETHESDA, MD, using AB block copolymers where the two blocks United States. have widely different affinities for protein adhesion and solvent casting them to form a thin film with a Different engineered nanomaterials (NM) have a periodic, heterogeneous chemical surface. The main profound impact on the development of diagnostic challenge in this approach is obtaining chemically biosensors, drug delivery nanosystems, imaging patterned surfaces in block copolymer thin films nanoprobes for intravascular use, or other devices because there is typically a large enthalpic driving that come in contact with blood. Little is known, force for placing one block at the film surface. This however, about the toxicity of nanomaterials talk will focus on the processing of the block introduced into the bloodstream in the course of copolymer films using solvent vapors to alter the therapeutic or diagnostic applications or impact of surface interactions and film thickness to kinetically environmental exposure to NM. Thus, the assessment trap desirable metastable morphologies. of a potential nanotoxicity in blood is a critical safety Combinatorial approaches to simultaneously monitor issue (J. Simak, In: Nanotoxicity, John Wiley & the effects of the film thickness and solvent Sons, 191-225, 2009). Interaction with plasma concentration on the surface morphology and protein proteins is a key initial event affecting nanomaterial adhesion will be discussed. biocompatibility/toxicity in blood. We have found that different nanoparticles (NP) bind to an array of 177. Combinatorial Design of a Four-Helix plasma proteins (albumin, fibrinogen, globulins, Bundle Protein Using High-Throughput histone and insulin) leading to an adsorbed protein Thermal Scanning layer or “corona” that largely defines the biological identity of these particles. Proteins drive Thomas J. Magliery. Departments of Chemistry and nanoparticles to self-assemble in higher order Biochemistry, The Ohio State University, Columbus, structures determined by the nature of proteins, type OH, United States. of NP core, and surface coating (S.H. Lacerda et al., Both the prediction and design of protein structure, ACS Nano, 4, 365-369, 2010). Effect of using computational and rational approaches, remain nanomaterials on blood platelets is another critical significant challenges in protein chemistry. A major element in determining nanomaterial limitation to developing a comprehensive thrombogenicicty, anticoagulation properties, or physicochemical model of the protein structure- other activities in inflammatory reactions. We have sequence relationship is the vastness of sequence shown recently that different agglomerates of non- functionalized carbon nanotubes (CNTs) activate space and the low-throughput nature of biophysical 2+ studies. We are pursuing a combinatorial approach to human platelets by inducing extracellular Ca influx understand better the sequence structure-relationship: (J. Semberova et al., Nano Lett., 9, 3312-3317, sorting large libraries of protein variants for 2009). In contrast, fullerene (nC60) and polystyrene structured proteins. We have developed a high- beads (20 nm and 200 nm) did not induce platelet throughput cell-based screen for activity of the well- aggregating activity. In a follow-up study (to be studied four-helix bundle protein Rop. To collect presented at the TechConnect World, Anaheim, CA, quantitative stability data for large numbers of June 21-25), we found that a phosphate buffer soluble variants, we have developed a method of high- carboxylated CNTs activate blood platelets in a fashion similar to their pristine hydrophobic

counterparts. The mechanism of CNT-induced 181. IP 101 for Entrepreneurial Companies platelet activation is being investigated. The findings and conclusions in this presentation have not been Harry J. Guttman. Stipkala LLC, Stipkala LLC, formally disseminated by the Food and Drug Cincinnati, OH, United States. Administration and should not be construed to Protection of intellectual property is critical to the represent any Agency determination or policy. survival and success of chemical and biotechnology companies. This presentation will review some basic 179. Support Groups That I Use mechanisms and tools to protect and enhance a company’s intellectual property. Trade secrets, Ronald J. Versic. Administration, Ronald T. Dodge trademarks and copyrights will be discussed briefly. Co., Dayton, Ohio, United States. Patents and the patenting process will be emphasized. The Ronald T. Dodge Co. was incorporated in 1979 The presentation will also include tips on interacting as a manufacturer of microcapsules. with your IP attorney to maximize the value of your IP portfolio. The Company was founded upon the three principles of: 182. Access to Capital 1. Methods: many methods of microencapsulation would be used to achieve controlled release, Amy J. Stose, Deborah A. Fitzwater. Department 2. Measurement: product properties would be stated of Business Banking, PNC Bank, Dayton, OH, in quantifiable terms such as a release profile; and, United States. 3. Milieu: the culture and morale of the Company Cash flow isn’t just the most important thing to your would be based upon the “Lion and the Lamb”. business. It’s everything to your business.

Over time it was recognized that three other imputs to PNC’s five tenants of cash flow: business management were needed, namely, Machines, Materials and Manpower. * Accelerate the Collection of Receivables

This presentation describes how these three * Improve the Ways You Make Payments additional resources were drawn from and supported by the local community to complete the six inputs to * Invest Your Excess Cash Effectively professional business management. * Leverage Online Financial Reporting Tools 180. Government Contracting for Chemical and Materials Small Businesses * Access the Credit You Need, When You Need It

Meredith Threatt. (SWCO PTAC), Southwest Access to Capital is where the focus of the Central Ohio Procurement Technical Assistance presentation will be. Center, Dayton, OH, United States. Government Contracting is a lucrative market for Topics will include: Types of Financing, Preparing to Chemical and Materials Small Businesses, provided meet the Bank, Business Plan, Application Process, those businesses have the tools they need to navigate Credit Profile of the Borrower, Small Business the market. SWCO PTAC is one of 94 Procurement Administration (SBA) loans. Technical Assistance Centers across the United States offering free training and assistance to 183. Synthesis of Photo-Open Polymer government contractors. This session will provide an Nanocapsules: A New Approach towards overview of government contracting at the state and Gene Delivery federal levels. Small Businesses will walk away from Tejal J. Deodhar,1 Jacob J. Weingart,1 Yun Chen,2 the session with an understanding of what the 1 2 1 government market looks like, how to register to Jun J. Hu, Liu Qin. Department of Chemistry, University of Akron, Akron, OH, United States; compete, where to find opportunities and the most 2 effective market research tools available to them. Department of Biology, University of Akron, Akron, They will also understand the small business OH, United States. programs specifically designed to level the playing Gene delivery involves the introduction of exogenous field between small and large contractors competing genes into host cells. An effort towards the for government opportunities. development of a new delivery system is the

synthesis of a photo-open polymer nanocapsule for (> 40oC) through the encapsulation of enzymes in the selective releasing and targeted delivery of DNA temperature responsive N-isopropylacrylamide into cells. This can be achieved by incorporating (NiPaaM) colloidal nanoparticles. Two enzymes, photo cleavable sites within a polymer which is glucose oxidase and organophosphorus hydrolase capable of forming a nanocapsule. DNA/RNA can be were functionalized with hydrophobic and encapsulated within the polymer capsule and on polymerizable chemical groups and encapsulated exposure to UV light the polymer can open up and within (NiPaaM)/Styrene particles using emulsion result in the release of the genetic material. The polymerization. The NiPaaM particle contraction at advantages of using this nanocapsule for gene high temperatures, from approximately 100 nm to 60 packaging and delivery is that it allows controlled nm, enhances enzymatic stability by supporting the photo degradation of the polymer and hence enzyme’s tertiary structure and preventing unfolding. controlled release of the nucleic acids into the cells. Thermal stability studies up to 70oC show that A novel preparation method for the fabrication of enzyme catalytic activity is higher relative to that of photo cleavable nanocapsules with a DNA/RNA native or functionalized enzyme. Lyophilization of loaded core has been designed. A di functional cross these novel materials extends their shelf life over that linker having photo cleavable sites at defined of native enzyme. Encapsulated enzymes are locations was synthesized and used in an inverse catalytically active after storage at 70oC for over one emulsion radical polymerization reaction with month, whereas native enzyme loses all activity by 3 poly(allylamine) and tertiary butyl acrylate weeks at 70oC. Our novel enzyme encapsulation monomers using a water/oil emulsion system. The motif has the ability to respond to harsh external cross linking of self assembled comb polymer, environments to protect the encapsulated enzyme containing the tertiary butyl acrylate and while maintaining its enzymatic activity. The poly(allylamine), leads to the formation of polymer encapsulation design could provide utility in various nanocapsule structures which allow for the applications such as industrial catalysis, point of care incorporation of guest molecules These nanocapsules diagnostics and chemical decontamination. have a hydrophobic shell (poly(tert-butyl acrylate), a hydrophilic interior (poly(allylamine) and 185. Actuation of Oxidation Responsive photocleavable sites (within cross linker). DNA/RNA Nanoparticles by Oxidoreductase Enzymes can be loaded within the polymer nanocapsules due to ionic interactions between DNA and amino groups Jermaine D. Johnson, Justin J. Bohn, Jeremy P. of the poly(ally amine) at physiological pH. The Walker. ICx Technologies, Pittsburgh, Pa, United surface or outer shell of the nanocapsules can also be States. synthetically manipulated and functionalized with Oxidoreductase enzymes have a potential utility for a water soluble biocompatible polymers to achieve host of multi-disciplinary fields ranging from stable dispersion, increased retention time and biological wound care to toxic chemical agent biocompatibility. In vivo studies with the photo open detection. These catalysts are proficient in their vector can be carried out, using zebra fish as a model generation of powerful oxidative species such as organism. This gene delivery system can be used as peroxides and chlorites. In this study, we seek to an attempt to study embryonic development in zebra utilize these enzyme generated products to drive fish embryos. A method that can determine whether a swelling of poly(sulfide) nanoparticles. Using the gene is involved in formation of an organ or a tissue monomer propylene sulfide and a tetrafunctional is crucial for the understanding of molecular thioester crosslinker pentaerythritol tetrakis(2- mechanisms underlying animal development. mercaptoacetate), we have been able to consistently generate nanoparticles under 200 nm in size. Initial 184. Thermal Stability of Enzymes Is sizing kinetics from Dynamic Light Scattering Significantly Increased by Encapsulation into (DLS), show our nanoparticles have exhibited N-Isopropylacrylamide Nanoparticles significant volume increases (>200%) as a function of various concentrations of oxidizer from 100 – 500 Anna M. Leech, Jeremy P. Walker. ICx Agentase, ppm. Increasing the oxidative sensitivity to lower Pittsburgh, PA, United States. concentrations of oxidizer will allow us to actuate the Enzymes demonstrate great potential for numerous swelling of our colloidal nanoparticles with enzymes applications; however their practicality is limited by themselves. We have also demonstrated the ability to their instability in harsh environments, such as lower the response time by altering the concentration temperature extremes. In this work, we seek to of crosslinker in the reaction. Enzymatic actuation of overcome enzyme instability at elevated temperatures nanoparticle swelling provides the framework for biologically controlled payload molecule release.

186. Developments in Polymer/Carbon delivery. Recently, many research efforts have been Nanotube Composite Films and Fibers focused on carbon nanotube (CNTs) membranes, which possess many advantageous and unique Satish Kumar. School of Polymer, Textile and Fiber attributes that include: 1) atomically flat graphite Engineering, Georgia Institute of Technology, surface allows for ideal fluid slip boundary Atlanta, Ga, United States. conditions 100,00 times faster than conventional Polymer/carbon nanotube composite films and fibers pores 2) the cutting process to open CNTs inherently have been processed using polymers such as places functional chemistry at CNT core entrance to polyacrylonitrile(PAN), polyvinyl alcohol (PVA), act as chemical gatekeepers and 3) CNT are poly (methyl methacrylate) (PVA), poly(ether ether electrically conductive allowing for electrochemical ketone) (PEK) and biopolymers such as DNA, silk, reactions and application of electric fields gradients and cellulose. Single wall carbon nanotubes, multi at CNT tips. Thus CNT membranes are an ideal wall carbon nanotubes, as well as vapor grown candidate as a rate-controlling component in a carbon nano fibers have been used in these studies. transdermal drug delivery device. CNT membranes Composite films have been processed that contain up were functionalized with highly-charged anionic dye to 90% carbon nanotubes and continuous fibers have molecules to induce a highly efficient electroosmotic been processed that contain up to 30 wt% carbon flow. The anionic charge density on CNTs was first nanotubes. Carbon fibers from PAN/CNT precursor enhanced through an efficient diazonium fibers have been processed with significantly electrochemical modification followed by a quad- improved mechanical properties when compared to anionic dye amine functionalization. It was found the carbon fibers processed from only PAN that fluxes of both cationic and neutral molecules precursor. Carbon nanotubes act as a template for through the CNT membrane have been greatly polymer orientation and nucleating agent for polymer increased under negative biases. High electro- crystallization. Films and fibers with electrical osmotic flows of 0.05 cm/s at -300mV bias have been conductivity as high as 100,000 s/m have been observed with 15% ion efficiency. Electro-osmosis processed, and these materials are also expected to be within CNT membranes is strongly related to electric good candidates for thermal conductivity field strength, ionic strength and surface charge applications. Mesoporous PAN/CNT electrodes have density. Employing this phenomenon, the been processed for supercapacitor electrodes with transdermal nicotine delivery device was able to specific capacitance exceeding 400 F/g. successfully switch between high (1.3±0.65 µmol/hr- cm2) and low (0.33±0.22 µmol/hr-cm2) fluxes that 187. Programmable Transdermal Delivery of coincide with therapeutic demand levels for nicotine cessation treatment. Applying the same phenomenon, Addictive Drugs Using Carbon Nanotubes the transdermal clonidine delivery rate can be Membranes enhanced from 1.6 nano-moles/hr.cm2 under 0 mV 2 Ji Wu,1 Kalpana Paudel,2 Caroline Strasinger,2 Dana bias to 8.1 nano-moles/hr.cm under -600 mV bias. Hammell,2 Audra Stinchcomb,2 Bruce Hinds.1 The traditional five-day opioid withdrawal symptom 1Chemical and Materials Engineering Department, treatment requires variable clonidine delivery rates 2 University of Kentucky, Lexington, KY, United ranging from 1.7 to 5.4 nano-mole/hr.cm . It is States; 2College of Pharmacy, University of notable that slower transdermal clonidine delivery Kentucky, Lexington, KY, United States. rates can be easily obtained applying smaller biases. The CNT membrane acted as the rate-limiting Proper treatment of drug addiction and abuse is component and observed flux values are consistent critically important since it is estimated that the total with a simple diffusion in series model that is based overall costs of substance abuse in the United States on Fick’s law. For a 10 cm2 (commercially available exceed half a trillion dollars annually as reported by size) clonidine transdermal patch made of a CNT National Institute on Drug Abuse (NIDA). Compared membrane, a button cell battery with a capacity of to syringe injection and oral drug delivery, 247 mWh can be pumping continuously for ∼30 days, transdermal patches possess many advantages, while the same button cell battery can work & 2 including reduction in pain bioharzadous waste, continuously for 12 days using a 25 cm nicotine sustained drug delivery, low cost and self- transdermal patch made of a CNT membrane. These administration. Conventional transdermal patches can highly energy efficient programmable devices with provide a constant flux of drug in an easy and non- minimal skin irritation and no skin barrier disruption invasive way. However many drug abuse and would open an avenue for single application long- addiction treatments, such as nicotine, fentanyl and wear patches for therapies that require variable or clonidine, require variable rates of transdermal programmable delivery rates.

188. Thermal Conductivity of Nanofluids thermal conductivity of resulting nanofluids. Future Containing Polyalphaolefins (PAOs) and research will be discussed in the presentation. Multiwalled Carbon Nanotubes (MWNTs) Keywords: Nanofluids, Thermal Conductivity, 1,3 2,4 David H. Wang, Javier Narvaez, Lois Poly(alpha-olefin), MWNT, Functionalization. Gschwender,2 Loon-Seng Tan.1 1Materials & & Manufacturing Directorate, Nanostructured 189. Electrodeposited V2O5 as a Prospective Biological Materials Branch (AFRL/RXBN), Air Catalyst for an H2S Amperometric Biosensor Force Research Laboratory, Wright-Patterson Air Force Base, Ohio, United States; 2Materials & Jason A. Bennett, James E. Pander III. School of Manufacturing Directorate, Thermal Sciences & Science, Penn State Erie, The Behrend College, Erie, Management Branch (AFRL/RXBT), Air Force PA, United States. Research Laboratory, Wright-Patterson Air Force Gasotransmitters are gaseous signaling molecules, 3 Base, Ohio, United States; Multiscale Composites which regulate ion channels within the body either and Polymers Division, University of Dayton directly or indirectly. The regulation of these ion Research Institute, Dayton, Ohio, United States; channels significantly influences cellular functions. 4 Department of Chemical and Materials Engineering, Nitric oxide (NO) is the most popular of these University of Dayton, Dayton, Ohio, United States. molecules as it has been studied extensively for Poly(α-olefin), or PAO, is a high performance, several decades. However, carbon monoxide (CO) synthetic base lubricating oil for automotive and and more recently hydrogen sulfide (H2S) have also aerospace applications. Nanofluids, which contain emerged as gasotransmitters produced endogenously suspended particles of nanometer size, have been within the body. In fact, the interaction between the under intense investigation recently due to their different gasotransmitters is of significant interest in significantly higher thermal conductivity than neat understanding the role of these molecules and their fluids. Multiwalled carbon nanotubes (MWNTs), influence on several diseases. There is a need to be demonstrating high aspect ratios and thermal able to selectively detect each gasotransmitter in the conductivity, are promising additives for the presence of other gasotransmitters in order to gain a nanofluids. In this presentation, the thermal complete understanding of each molecule’s conductivity of PAO/MWNT nanofluids was physiological role(s). There is currently no method to measured using transient hot wire method. Two detect H2S in vivo. pristine MWNTs (from Aldrich and Arkema each), a covalently functionalized MWNT, and a surfactant- Vanadium oxide catalysts have been extensively bound MWNT were blended with PAO studied for catalytic H2S oxidation for industrial and (ExxonMobil, 2cst) at 1 wt% (0.5 vol%) via environmental applications. An electrochemical sonication. The covalently functionalized MWNT investigation on the use of electrodeposited V2O5 to was obtained by reacting MWNT with 1,3,5- oxidize H2S in a physiologically relevant solution trimethylphenoxybenzoic acid in polyphosphoric acid will be presented. Additionally, the effect of different to afford 1,3,5-trimethylphenoxybenzoyl- deposition parameters on the electrocatalytic functionalized MWNT (TMPB-g-MWNT). The properties as well as the potential selectivity over CO surfactant, 3,7,11-trimethyl-2,6,10-dodecatrien-1-yl and NO will also be presented. 4-(pyren-1-yl)butanoate (TDPB; an ester), was synthesized by dehydration of 3,7,11-trimethyl- 190. On-Trap Derivatization of Short-Chain 2,6,10-dodecatrien-1-ol and 4-(pyren-1-yl)butyric Fatty Acids acid with dicyclohexylcarbodiimide (DCC). Two Mace Mattieson. Department of Chemistry, Eastern pristine MWNT/PAO nanofluids are highly viscous Michigan University, Ypsilanti, Michigan, United and stable colloids over months. TMPB-g- States. MWNT/PAO nanofluid is also viscous, but less stable than previous two samples. The MWNT/PAO It has recently been hypothesized that gastrointestinal nanofluid, which contained 1wt% TDPB surfactant microbiota modulate immune response by the and displayed a much lower viscosity, is the least production of short-chain fatty acids (SCFAs). There stable probably due to polar ester groups in TDPB. is a need for rapid, selective analytical methodology The thermal conductivity of all the nanofluids is 8- capable of trace analysis of SCFAs in complex 10% higher than the PAO base fluid. Both covalent biological matrices. Previous studies by others using and noncovalent functionalization of MWNT multibed-sorbent traps, solid phase microextraction surfaces have shown a minimum effect on the (SPME), and on-fiber derivatization with SPME

showed that it is possible to achieve low limits of though a more recent report [3] suggests such a detection (LODs) for the gas chromatographic (GC) correlation. headspace analysis of SCFAs. The goal of this project is to achieve low ppb-range LODs for SCFAs We have studied the electrografting and spontaneous by using a derivatizing agent incorporated onto a grafting of several aryldiazonium ions. We observe multibed-sorbent trap. The preconcentration and spontaneous grafting for nitrophenyl, carboxyphenyl, derivatization of the SCFAs by the trap prior to and anthraquinone groups, in agreement with entering the GC column should produce low LODs previous studies. For these cases, exposure to with flame ionization detection. The most significant diazonium ion solution results in significant challenge results from the manual construction of alteration of the diazonium ion cyclic voltammetry as sorbent traps, which can negatively impact well as in the appearance of electrochemical chromatographic reproducibility. A number of trap signatures for bound nitrophenyl and anthraquinone designs will be considered in order to minimize trap groups. Further, our preliminary results show that to trap variation. systems with more negative reduction potentials (benzenediazonium, N,N-diethylbenzenediazonium 191. Elemental Analysis of a Variety of Dried, and 3,5-di-tert-butylbenzenediazonium ions) behave Powdered, Kelp Food Supplements for Heavy differently, and do not seem to spontaneously graft. Metals Via Energy Dispersive X-Ray Finally, our results suggest that spontaneous grafting Fluorescence occurs primarily at one type of carbon surface site, and that further electrografting at other sites is Danielle Garshott, Elizabeth MacDonald, possible with the application of negative potentials. Meghann Mouyianis, Elizabeth Roberts-Kirchhoff, Mark A. Benvenuto. Department of Chemistry & [1] J. Pinson, F. Podvorica, Chem. Soc. Rev. 34 Biochemistry, University of Detroit Mercy, Detroit, (2005) 429-439. MI, United States. [2] F. Barriere, A. Downard, J. Solid State Seventeen kelp dietary supplements, purchased Electrochem. 12 (2008) 1231-1244. directly from health food or drug stores, have been analyzed by energy dispersive X-ray fluorescence [3] F. LeFloch, J.-P. Simonato, G. Bidan, (EDXRF) spectroscopy. The supplements were Electrochim. Acta 54 (2009) 3078-85. examined to determine the presence of arsenic, lead, and mercury. Before analysis of the sample set, a series of standards for was created, because no 193. Spectroelectrochemical Sensing of established NIST standards for such food Pyrene Metabolites 1-Hydroxypyrene and 1- supplements appear to exist. The findings for these Hydroxypyrene-Glucuronide in a Single items are presented, as is the method for heavy metal Analysis standards production. Robert A. Wilson, Carl J. Seliskar, William R. Heineman. Department of Chemistry, University of 192. Insights into Spontaneous Grafting of Cincinnati, Cincinnati, OH, United States. Aryldiazonium Ions for the Modification of Carbon Electrodes Spectroelectrochemical sensing was successfully used for detection of the polycyclic aromatic Kristin K. Cline, Rachel Saylor, Christa Snyder. hydrocarbon (PAH) biomarkers 1-hydroxypyrene (1- Department of Chemistry, Wittenberg University, pyOH) and 1-hydroxypyrene-glucuronide (1-pyGlu). Springfield, OH, United States. The novel sensing method presented here allows for detection of the glucuronic acid conjugate of pyrene When aryldiazonium ions are reduced as well as free 1-pyOH in a single 30 min analysis. electrochemically, the resulting aryl radical can bind This is achieved by utilizing a thin-layer covalently to the electrode surface [1]. For metal spectroelectrochemical approach which allows for electrodes, spontaneous grafting occurs when the electrochemical modulation (in approximately 15 min open circuit potential is more negative than the for each analyte) of what would otherwise be the potential for onset of diazonium ion reduction. overlapping absorbance and emission spectra of the Spontaneous grafting has also been observed for metabolites in a mixture. A calibration curve carbon electrodes, but variable open circuit potentials consisting of the fluorescence change vs. analyte and diazonium ion reduction potentials have concentration for 1-pyOH and 1-pyGlu yields a linear obscured attempts to verify a similar relationship [2], dynamic range down to 10 nM and 1.0 nM

respectively, with calculated detection limits within Poly(phenylene vinylene)s (PPVs) are well known the physiological range for 1-pyGlu. electroluminescence components and have been used as the emissive layer in organic light emitting diodes 194. Purification of Gold Nanoplates Directly but exhibit limited solubility. Terephthalates having on Surfaces for Enhanced Localized Surface phenyl and alkyl substituents, generated from Plasmon Resonance (LSPR) Biosensing cyclopentadienones, have been shown to be precursors to PPVs with enhanced solubility and Srinivas Reddy Beeram, Zamborini Francis. color tunability. Related reports employ alkoxy department of chemistry, university of louisille, substituted aromatic subunits as backbone donor louisville, ky, United States. components in the construction of unique PPVs for Gold nanoparticles have interesting optical properties many electronic materials applications. The current which can be used for applications in biosensing. research has revealed an efficient synthesis of diethyl We synthesized Au nanostructures (Au nanoparticles 5-hydroxy-2,3-diphenylterephthalate employing and triangular, hexagonal or circular Au nanoplates) ethynylboronate MIDA ester. This phenol provides on silicon and glass by a seed-mediated growth access to a donor substituted (alkoxy) PPV backbone method. We produced surfaces of pure Au nanoplates precursor. A review of methods employed in the by selective removal of Au nanopartcles and used the synthesis of 5-hydroxy-2,3-diphenylterephthalate and nanoplates for human IgG detection after its conversion to selected derivatives will be immobilizing anti humanIgG through covalent presented. linking. The size of the nanoplates was ∼200 nm. UV-vis spectroscopy provided information about the 196. Synthesis of Haplomyrtin Analogs collective optical changes during antibody/antigen Arnoud M. van Duijn, William A. Feld. Chemistry, coupling to Au nanoplates and Atomic Force Wright State University, Dayton, Ohio, United Microscopy (AFM) allowed direct imaging of the States. antibody and antigen on the surface of the nanoplates. Selective functionalization of the edges of Au The arylnaphthalene lignan lactones occur nanoplates with antibody occurred by performing a widespread in nature and have a diverse range of thiol place exchange reaction between biological activity. A route to the synthesis of mercaptoundecanoic acid (MUA) and Haplomyrtin has been investigated in which 12 mercaptoethanol (ME)-functionalized nanoplates separate steps were employed with an overall yield of before coupling the antibodies to the acid groups via 13%. In order to improve the overall synthesis route, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide yield and purity of the final product, a novel (EDC) and N-hydroxy succinimide (NHS) activation. approach is being investigated in which phthalide is The number of antibodies immobilized at the edge or employed as the starting material. As a preliminary vertex sites increased as the MUA concentration study for the use of an appropriately substituted increased for the place-exchange strategy. UV-VIS phthalide in the synthesis of Haplomyrtin, an spectra showed that the surface Plasmon band of the investigation of the electrophilic aromatic Au nanoplates changes more significantly for substitution reactions of phthalide as well as the antibody/antigen coupling on the place-exchanged generation of several hydroxy, alkoxy and halo surfaces, where the antibody attached to edge sites. phthalide precursors has been undertaken. These studies show that the sensitivity of the optical properties of Au nanostructures depends on the 197. Nickel-Catalyzed Direct Synthesis of 1,4- location of the biological receptor. This is an Difunctionalized Compounds important finding for optimizing these materials for Sanjeewa K. Rodrigo, Hairong Guan. Department of biosensing applications. Chemistry, University of Cincinnati, Cincinnati, A major goal of our work is to determine the Ohio, United States. detection limit of these optical protein sensors, which is of importance for disease diagnostics and A new catalytic system for the synthesis of 1, 4- biological studies. difunctionalized compounds has been developed. The method involves Ni(COD)2 with an N-heterocyclic 195. Synthesis of Phenylated carbene ligand as the catalyst and triethylsilane as the Alkoxyterephthalates reducing agent to couple an ynone and an aldehyde to give the target product. Optimization of the reaction Rachel Sayers, William A. Feld. Chemistry, Wright conditions with different ligands and substrates is State University, Dayton, OH, United States. underway to improve the reactivity.

198. New Spin Trap Nitrone Conjugate of Sreekanth Thota,1 Subhas Somalingappa Karki,2 Jan 3 4 1 Calix[4]pyrrole: Design, Synthesis, and Balzarini, Erik De Clecq. DEPARTMENT OF Characterization PHARMACEUTICAL CHEMISTRY, S.R.COLLEGE OF PHARMACY, WARANGAL, 1,2 1 2 Shang-U. Kim, Kevin M. Nash, Yangping Liu, ANDHRA PRADESH, India; 2department of 2 3 Jay Zweier, Antal Rockenbauer, Frederick A. pharmaceutical chemistry, kles college of pharmacy, 1,2 1 Villamena. Department of Pharmacology, Davis BANGALORE, India; 3department of pharmacology Heart & Lung Research Institute, College of Medine, and medicine, rega institute of medical reasearch, Ohio State University, Columbus, OH, United States; leuven, Belgium; 4department of pharmacology and 2 Center for Biomedical EPR Spectroscopy and medicine, rega institute of medical reasearch, Imaging, Davis Heart & Lung Research Institute, Belgium. College of Medicine, Ohio State University, Columbus, OH, United States; 3Chemical Research In the search for antitumor active metal complexes Center, Institute of Structural Chemistry, Budapest, several ruthenium complexes have been reported to Pusztaszeri, Hungary. be promising as anticancer drugs. A series of mononuclear Ru(II) complexes of the type 2+ ’ The nitrone spin traps have been employed as probes [Ru(T)2(L)] , where T=2,2 -bipyridine/1,10- for the identification of transient radical species in phenanthroline and L= 4-CH3-BINH, 4-OH-BINH, chemical and biological system using electron 3,4-(OCH3)2-BINH, 4-CH3-BTSZ, 4-OH-BTSZ, 3,4- paramagnetic resonance (EPR) spectroscopy. (OCH3)2-BTSZ have been prepared and characterized •- 1 Superoxide radical anion (O2 ) is an important by UV-Vis, IR, H-NMR, Mass spectroscopy. The precursor of reactive oxygen species. Since title compounds were subjected to in vitro cytotoxic calix[4]pyrroles have exhibited high affinity towards activity against human cancer cell line Molt 4/C8, anions, the design, synthesis, and physico-chemical CEM and Murine tumor cell line L1210. In vitro characterization of a nitrone spin trap conjugate of evaluation of these ruthenium complexes revealed calix[4]pyrrole (CalixMPO) were carried out. cytotoxic activity from 0.21 to 24 µM against Molt Computational studies suggest a pendant-type linkage 4/C8, 0.16-19µM against CEM, and 0.75 to 32 µM between the calix[4]pyrrole and the nitrone to be the against L1210. •- most efficient design for spin trapping of O2 giving an exoergic reaction free energy of ∆G298K,aq = -2.1 Graphical abstract: kcal/mol compared to the endoergic ∆G298K,aq for •- some common spin traps. CalixMPO trapping of O2 Where L=4-CH3-BINH,4-OH-BINH,3,4-(OCH3)2- exhibited distinctive EPR spectrum and kinetic BINH,4-CH3-BTSZ,4-OH-BTSZ,3,4-(OCH3)2- •- analysis of O2 adduct formation and decay gave BTSZ. exceptionally high rate constant (k = 682.3 ± 82.7 M- 1 -1 s ) and longer half-life (t1/2 = 25 min) compared to T=2,2’-bipyridine/1,10-phenanthroline. other cyclic nitrones. The unusually high reactivity of •- CalixMPO to O2 was rationalized to be due to the 200. Innovative Technology Needs To Meet synergy between the alpha and electrostatic effects of Air Force Operation Energy Requirements •- the calix[4]pyrrole group on the O2 and nitrone moiety, respectively. William E. Harrison. Propulsion Directorate, Air Force Research Laboratory, Wright-Patterson AFB, OH, United States. The Department of Defense is the single largest user of energy in the nation consuming about 1.8% of all the energy used in the US. The Air Force is the single largest consumer of energy in the DoD, with ∼80% of the energy consumed by aircraft. Energy is an operational concern as energy demand increases globally and fewer new supplies of petroleum are being found globally. Energy and the environmental

impact of producing and using energy must be 199. Synthesis, Characterisation and In-Vitro considered and new technologies developed to reduce greenhouse gases and other pollutant emissions. The Cytotoxic Activities of Mononuclear Ru(II) Air Force has developed an energy plan with three Complexes main pillars: reduce demand, increase supply, and to

change the culture. To reduce the demand, new However, toxicity has been a key concern since the energy efficient technologies must be developed and introduction of CNTs. Several studies have these technologies have a strong need for new investigated the toxicity of CNTs, but the influence materials and new processes to make stronger, light of residual metal catalysts on cells has yet to be weight parts. Integration of new technologies must be determined. The aim of this study was to analyze the considered at the systems level and waste heat trace amounts of metal catalyst residues in CNT managed more effectively. New technologies to structures and the in vitro uptake in cells and the harvest waste heat and energy and convert it to culture media. electricity should be explored. Advanced engines, aeronautic designs, coatings, and power generation In this study neurosphere cells derived from new top the list of technologies where advanced materials born C57B/L6 black mice were cultured with CNT will play a significant role in achieving increases in structures. The cells and the culture media as well as energy efficiency. To increase supply, the Air Force the CNT structures were then screened for trace is developing alternative and bio-based fuels and is metal catalysts using microwave assisted acid incorporating renewable solar and wind at bases to digestion and inductively coupled plasma mass generate electricity. spectrometry (ICP-MS). The results showed low concentrations of metals in the cells and the media. Advances in technologies to reduce the cost of alternative fuels and renewable energy would 202. Quantitative Determination of significantly enhance their use by both the military Securinine, a Potential Anticancer Agent, and commercial sector. The Air Force is also looking from Securinega suffruticosa Plant Leaves by changing the culture of all airman such that energy is LC-ITMS a consideration in all they do. The lecture will describe the AF energy plan and the need for Simuli L. Wabuyele,1 David Wald,2 Yan Xu.1 advanced technologies developed by chemists and 1Department of Chemistry, Cleveland State chemical engineers. University, Cleveland, Ohio, United States; 2Department of Pathology, Case Western Reserve 201. Screening for Residual Metals in CNT University, Cleveland, OH, United States. Structures and Their Bioavailability In Vitro Securinine is a major alkaloid of plant Securinega Using ICP-MS suffruticosa. It has been previously reported as a Julia Kuhlmann,1 Karolin K. Kroening,1 Chaminda useful agent for the treatment of non-cancer related Jayasinghe,2 Sarah Pixley,3 Vesselin Shanov,2 Joe A. diseases such as poliomyelitis, aplastic anemia and Caruso,1 William R. Heineman.1 1Department of diseases related to the central nervous system (CNS) Chemistry, University of Cincinnati, Cincinnati, OH, acting as a GABA receptor antagonist. Securinine has United States; 2Department of Chemical and also been reported to induce apoptosis in human Materials Engineering, University of Cincinnati, leukemia cells (HL-60) and furthermore it has Cincinnati, OH, United States; 3Department of recently been implicated in solid tumors, as a novel Cancer and Cell Biology, University of Cincinnati, compound that preferentially inducing apoptosis in Cincinnati, OH, United States. p53 deficient colon cancer cells while protecting normal cells. Hence, it has potential for clinical use There has been increasing interest in carbon as a therapeutic agent for cancer. A sensitive and nanotubes (CNTs) since their discovery in 1990 due reliable analytical method is therefore needed for to their unique physical properties. During this time a pharmaceutical and toxicological studies of this variety of synthesis methods and types of CNT compound. In this work, we have developed a liquid structures have been developed leading to various chromatography-ion trap mass spectrometry (LC- potential applications in electronics, nanotechnology, ITMS) method for quantitative determination of materials and biomedical engineering. One promising securinine. A liquid-liquid extraction protocol has application in the field of biomedical engineering been developed for isolation of securinine from would be the use of CNT threads in neural repair Securinega suffruticosa plant leaves. after traumatic brain injury or injury to the peripheral Chromatographic separation of securinine and nerve. The linear morphology and electrical internal standard was achieved on a Gemini Nx C18 conductivity of the CNT thread could enhance column by isocratic elution at a flow rate of 0.2 neuronal outgrowth and neurogenesis at the injured ml/min, and the total run time was less than 5 min. region. Detection of securinine and internal standard was carried out by a Bruker Esquire ion trap mass

spectrometer which was operated in positive Eric B. Twum,1 Xiaohong Li,1 Elizabeth F. electrospray ionization mode. The multiple-reaction- McCord,2 Peter A. Fox,3 Peter L. Rinaldi.1 monitoring (MRM) method was used for 1Department of Chemistry, University of Akron, quantification using mass transitions m/z 218 → 84 Akron, OH, United States; 2Central Research and for securinine and m/z 294 → 200 for the internal Development, E. I. duPont de Nemours and Co., 3 standard. The analytical performance of the method Wilmington, DE, United States; Experimental was evaluated in terms of linear dynamic range, limit Station, DuPont Performance Polymers, Wilmington, of quantification (LOQ), intra- and inter-assay DE, United States. precision, as well as percent recovery of securinine PVF2 is an extremely important fluoropolymer due to by extraction. The developed method has been used its excellent properties, such as extreme resistance to for quantitation of securinine in Securinega heat and electricity. Thorough microstructural suffruticosa plant leaves. characterization is important as this allows the polymer microstructure to be correlated with the 203. Forensic Proteomics – Rapid Protein different reaction pathways occurring during the Analysis by MALDI-TOF/TOF MS with On- polymerization process. PVF2 is usually prepared by Plate Digestion and Stable Isotope Labeled free radical polymerization. The free radical Peptide Standards polymerization process is not completely regiospecific; there is the formation of inverted units Colin G. Barry. U.S. Food and Drug Administration, in addition to the regular monomer addition units. Forensic Chemistry Center, Cincinnati, Ohio, United The CF groups from the defect units (inverted States. 2 addition) are very weak compared to the CF2 from The Forensic Chemistry Center of the U.S. FDA is a the regular addition, making the characterization of national resource for forensic analysis relevant to the defect units challenging. This study employs a foods, drugs, cosmetics and medical devices. variety of solution multidimensional NMR Recently, a number of protein-based drugs have techniques to characterize the microstructure of become popular targets for illict off-label use. Human PVF2. Through a combination of 1D and 2D NMR 19 19 13 19 19 growth hormone (hGH) is easily accessible though experiments such as F 1D, F- C HSQC, F- F the internet and has become a popular component of gradient double quantum filtered COSY and selective anti-aging and weight management therapies as well ECOSY experiments, the microstructure of PVF2 has as a performance enhancing drug. Concerns over been identified. Very weak peaks, which have been product diversion, illegal importation, and reported (without assignment) in literature, are counterfeiting, fueled by the popularity of off-label characterized using pulse sequences implemented in use, have created a need for efficient methodology our laboratory. In addition to the main chain that can withstand legal scrutiny. Common sequence, the end groups of PVF2 are characterized approaches to identify and quantify biologic-drugs and presented. rely on molecular biology (ELISA) and/or conventional proteomics techniques (protein 205. Modeling NMR Features of Secondary hydrolysis and LC-MSn). While sensitive and Metabolites from Black Raspberry (Rubus selective, these approaches are often time consuming occidentalis L.) Fruits Against Chemical and labor intensive. To overcome these drawbacks, Assay Results for Identifying Active we sought to develop methodology that offers rapid Components and compelling protein identification as well as relative quantitative analysis with minimal sample Liladhar Paudel,1 Faith J. Wyzgoski,2 Peter L. workup. Following the determination of molecular Rinaldi,1 R. Neil Reese,3 Mustafa Ozgen,4 Artemio Z. weight by MALDI-TOF-MS, sequence information is Tulio,6 A. Raymond Miller,5 Joseph C. Scheerens,5 obtained by a MALDI-TOF/TOF-MS analysis of a James K. Hardy.1 1Department of Chemistry, tryptic digest which is conducted on-target. University of Akron, Akron, Ohio, United States; Anticipated fragments which have been isotopically 2Department of Chemistry, The Ohio State labeled serve as internal standards. This approach has University-Mansfield, Mansfield, Ohio, United been applied to hGH and shows promise for States; 3Department of Biology and Microbiology, additional biotherapeutics. South Dakota State University, Brookings, South Dakota, United States; 4Department of Horticulture, 204. 2D Nuclear Magnetic Resonance (NMR) Gaziosmanpasa University, Tasliciftlik, Tokat, 5 Spectroscopic Analysis of Polyvinylidene Turkey; Department of Horticulture and Crop Fluoride (PVF2) Science, The Ohio State University, Ohio

Agricultural Research and Development Center, (showing two and three bond correlations), reveal Wooster, Ohio, United States; 6Department of United connectivity information between proton and carbon. States Food and Drug Administration, Center for 1H-1H correlations can be observed in the homonuclei Food and Safety and Applied Nutrition (CFSAN), dqCOSY experiment. Compared with regular COSY Summit-Argo, Illinois, United States. experiment, the huge singlet signals from main chain units were suppressed in dqCOSY so that the weak Modeling 1H NMR spectral features of minimally chain end structures can be identified. Then, the manipulated black raspberry (BR) fruit extracts chain length of each component in a series of PLA- against chemical assays for total monomeric PEG copolymers with varying weight percentages of anthocyanin (TMA) content and antioxidant capacity 1 lactide and ethylene glycol were measured based on has been performed. In this work, high field H NMR 1 quantitative H NMR spectra. spectra of 19 BR samples were carefully aligned and divided into bins having variable width of 0.004 ± 0.002 ppm. The intensities of the bins were correlated 207. 2D-NMR Studies of the Backbone and with the measurements of TMA, ferric reducing Chain End Structure in PFPE antioxidant power (FRAP) and 2, 2-diphenyl-1- Fluoropolymers picrylhydrazyl (DPPH); using partial least squares Xiaohong Li,1 Elizabeth F. McCord,2 Peter A. Fox,2 regression. Spectral regions responsible for Jon L. Howell,3 Peter L. Rinaldi.1 1Department of variability in assay results were identified and Chemistry, University of Akron, Akron, OH, United quantified by the model. In order to validate the States; 2Experimental Station, DuPont Performance model, resonance assignments of four anthocyanins Polymers, Wilmington, DE, United States; (cyanidin 3-rutinoside, cyanidin 3-O-(2(G))- 3Experimental Station, EI DuPont de Nemours and xylosylrutinoside, cyanidin 3-glucoside, and cyanidin Co, Wilmington, DE, United States. 3-sambubioside, the primary polyphenolic antioxidant components of BR fruits) have been 2D NMR techniques were used to study the verified by using 1D 1H-NMR, and 1H-13C 2D structures of perfluoro(polyalkyl ether) (PFPE) and correlation spectra. Our results showed that the its mechanism of polymerization. Model compounds antioxidant capacity of the extracts is the result of K4, E4, and E2; containing four and two PFPE repeat synergy between several secondary metabolites, with units, respectively, were analysed to interpret the cyanidin 3-rutinoside, cyanidin 3-O-(2(G))- patterns of the spectra from the polymers. Selective 19 13 xylosylrutinoside, cyanidin 3-glucoside being F- C gradient HSQC experiments provided significant contributors to the variability in assay information about the C-F attachments within results. This study validated our approach to monomer units of the backbone and chain-ends. A 19 19 modeling spectral variation against assay data and series of selective F- F COSY 2D NMR suggested its relevance for identifying relationships experiments were performed. When selective among fruit bioactive components that prevent and/or experiments were combined with selective inversion inhibit cancer and other degenerative diseases. pulses to remove most of the JFF couplings in the f1 dimension, greatly simplified 2D NMR spectra were 206. Characterization of Poly(lactide)- obtained. This made it possible to resolve signals Poly(ethylene Glycol) by NMR from various stereosequences and monomer inversions present in the polymer. Resonances from Linlin Li, Amanda R. Knapp, Peter L. Rinaldi, Wiley all of the structures detected in the polymer have J. Youngs. Department of Chemistry, University of been identified and attributed to the various Akron, Akron, OH, United States. mechanisms for initiation and termination of the Poly(lactide)-poly(ethylene glycol) (PLA-PEG) is polymerization. one of the most popular synthetic polymer used for biomedical application. The properties of PLA-PEG can be controlled readily by adjusting the molecular weight of this copolymer and the relative chain length of two components. Due to the important commercial use of PLA-PEG, it is important to understand the detailed structure of this copolymer. In our study, the combined use of 1D and 2D NMR can provide unambiguous resonance assignments for PLA-PEG. 2D heteronuclei experiments, like HSQC (showing one-bond correlations) and HMBC

208. Development of Peer-Led Team structure properties relations for ROH, RCOOH and Learning: Lessons Learned and New RCOOR’ functional groups. Directions Important advances in the recognition of structures Pratibha Varma-Nelson. Center for Teaching and and correct classification of many chemicals used in Learning, IUPUI Indiana University Purdue polymer science were register and evaluated after University Indianapolis, Indianapolis, IN, United practicing with Octachem Model for 4 weeks. States. PLTL is an instructional model (http//www.pltl.org) 210. Development of an Inquiry-Based that advances student achievement through active Organic Instructional Laboratory Using learning in a peer-led workshop. During the past 15 Microwave-Assisted Organic Synthesis years the method has demonstrated its effectiveness (MAOS) in improving student academic performance, as demonstrated in more than 20 studies. Conservative S. Shaun Murphree, Theodore G. Bean. Department estimates are that PLTL is now used in more than of Chemistry, Allegheny College, Meadville, PA, 100 institutions—four-year colleges, community United States. colleges, and research universities. Over 20,000 A first-semester sophomore-level instructional students, 150 professors, and 1,500 peer leaders are laboratory was developed using microwave-assisted engaged in PLTL workshops each year, as an synthesis. Four microwave reactions were important part of their science courses. This talk will introduced: a) the alkylation of theophylline (1); b) draw from the recently published book by Gafney & the dehydration of α-tetralol (3); c) the borohydride Varma-Nelson, “Peer-Led Team Learning: reduction of acetophenone (5); and d) the epoxidation Evaluation, Dissemination, and Institutionalization of of estragole (7). The rapid reaction times afforded by a College-Level Initiative.” Generalizable lessons the microwave techniques allowed for more real-time learned during the development and dissemination of analysis, reflection, and self-direction during the this pedagogy and future directions in the laboratory period. Discussion will include both the development and applications of Peer-Led Team synthetic adaptations and the development of Learning (PLTL) will be discussed. laboratory materials.

209. Alcohols, Acids and Esters, Their Structure-Nomenclature Can Be Easy and Fun with Octachem Model Joaquin Palacios. Physical-chemistry, Universidad Nacional Autónoma de México, Mexico City, D.F, Mexico. In my teaching experience with chemical engineering students, for several years I observed, they had some difficulties concerning with the identification of the 211. Engineering Low Bandgap Polymers organic chemistry functional groups, specifically the That Utilize Quinoidal Resonance Structure structure and names of esters and poly esters. In Stabilization by Thienothiophene with Fine- consequence it was a problem for this groups to give Tuning of HOMO Energy Level: the correct names of organic substances, like Applications in Organic Solar Cells solvents, plastizicers and additives. in our polymer courses. Nabil Kleinhenz, Huaxing Zhou, Sam C. Price, Liqiang Yang, Wei You. Department of Chemistry, As a possible solution to this situation the use of University of North Carolina - Chapel Hill, Chapel Octachem Model was presented. Hill, NC, United States.

This presentation describes a study of several new Octachem Model is a three dimensional interactive semiconducting polymers for photovoltaic toy, useful to practice the Organic Chemistry applications. All polymers share a common structural nomenclature rules. Trough several especially created unit, thieno[3,4-b]thiophene. The quinoidal resonance cooperative group activities, the students review the structure afforded by the thienothiophene exemplifies concepts of: functional group, compounds family, an approach that is far less common than the donor acceptor approach in which the HOMO from the

electron donor monomer and the LUMO from the acceptor monomer ideally yield the low band gap of the copolymer. A disadvantage of the quinoidal approach is that it is more difficult to control the HOMO due to the lack of a designated electron donor. Nevertheless, a copolymer of alternating thieno[3,4-b]thiophene and benzodithiophene units (BnDT-TT) has set world record power conversion efficiencies of greater than 7% in polymer solar cells. The goal of this research was to replace the BnDT comonomer with other novel aromatic monomers of varying electron donating ability to determine whether the HOMO could in fact be controlled by the electron donating ability of the “donor” monomer as predetermined in donor-acceptor type polymers. This study was also intended to answer the question of whether the record-breaking BnDT-TT polymer was simply an exceptional combination, or if the quinoidal approach involving other fused aromatic monomers with thienothiophene could yield polymers of similarly high performance. The thieno[3,4-b]thiophene monomer was synthesized in two variations, with and without an electron- withdrawing fluorine, and copolymerized with two different aromatic monomer units, dithieno[3,2 f:2’,3’-h]quinoxaline, and naphtho[2,1-b:3,4- b’]dithiophene, allowing for a photovoltaic study of 4 new polymers. It was observed that the HOMO energy level could in fact be lowered by incorporating weaker donor moieties. In addition, the introduction of an electron withdrawing fluorine on the thienothiophene comonomer consistently lowered 212. Incorporation of Civic Engagement into the HOMO level further. Open circuit voltages increased consistently with decreasing HOMO levels. the General Chemistry Curriculum: The short circuit current density, however, was Approaches, Problems, Successes and significantly lower in all polymers studied, bringing Failures the efficiencies down to less than 1%. This may David W. Johnson. Department of Chemistry, demonstrate that it is the specific combination of the University of Dayton, Dayton, OH, United States. benzodithiophene and the thienothiophene units that results in highly efficient polymers rather than the The incorporation of civic engagement in science, thienothiophene unit alone. technology, engineering and mathematics (STEM) courses has been a major initiative of the NSF 1 Liang, Y., Xu, Z., Xia, J., Tsai, S., Wu, Y., Li, G., sponsored SENCER program. While there have been Ray, C., Yu, L. Adv. Mater. 2010, 22, Early View. many successful SENCER projects involving non- majors courses, majors courses have been somewhat more difficult. General chemistry is a particularly difficult course in that it is not only a major’s course, but a service course for a wide range of other majors. Our general chemistry course, for example is required for engineering student, premedical students, biology students, nutrition students and exercise science students. In our efforts to improve student learning, we have had to wrestle with questions of content, breath versus depth and a number of other requirements. Our approach has been the development of content modules that allow some of

the “normal” general chemistry content to be a diverse approach to the learning process and presented while including modern societal problems outcomes. Students in the intervention sections at the same time. Some of the more successful receive a game-based review for the final approaches to the use of SENCER ideas will be examination as part of their regular coursework; described in addition to some of the approaches that students in the control sections participate in a have been less than successful. traditional lecture-based review as part of the regular coursework. Data included in the study consists of 213. Lights, Camera, Action! Benefits of final exam scores and pre- and post- surveys Game Show Review in Freshman Chemistry regarding interest in subject matter, effectiveness of review, and methods/timing of preparation for final Thomas W. Stringfield, Gene F. Kramer, Pete exams. Bender. Department of Chemical Sciences, University of Cincinnati - Raymond Walters College, Results/Conclusions: Cincinnati, OH, United States. The purpose of this classroom based research study is Data collected thus far supports the hypothesis that to determine the effect of game-oriented review on game show review is an effective way to engage and student performance, study habits, and interest. This prepare students. The average of the final exam research specifically addresses methods and timing of scores in the game show sections is significantly study, performance on final exam, and developing higher than for the traditional lecture review sections. deeper interest in chemistry. While student interest in subject matter has not changed significantly, the game show review has Background: motivated students to prepare for the final exam sooner than in the traditional lecture review sections. Active learning, through which students become active participants in the learning process is an Bowen, H. R., & Eison J. A. (1991). Active important means for the development of student Learning: Creating Excitement in the Classroom skills. Active learning pedagogies include problem- ASHE-Eric Higher Education Report No. 10, based learning, discovery learning, simulations and Washington DC: George Washington University, games. The use of game-based review encourages School of Education and Human Development. active learning and better study habits. It also emphasizes the exploration of their own attitudes and Campbell, S. & Muzyka J. (2002). Chemistry Game values (Bonwell and Eison, 1991) by requiring Shows. J. Chem. Ed. 79 (4), 458. students to reflect on how they study, when they study and the effectiveness of their study strategies. Meyers, C., & Jones, T.B. (1993) Promoting Active Active learning promotes cognitive activities that Learning, Strategies for the College Classroom. San allow students to clarify, question, consolidate and Francisco: Jossey-Bess Publishers. appropriate new knowledge (Meyers and Jones, 1993). Game show review enables students to build a Ruben, B. D., (1999) Simulations, Games, and framework to integrate previous knowledge with new Experienced Based Learning: The Quest for a New material while being invested in the outcome of the Paradigm for Teaching and Learning. Simulation & game. These methods in particular provide a complex Gaming, 30(4), 498-505. and diverse approach to the learning process and outcomes. They allow for peer feedback in 214. Transforming Gen Chem Labs at a collaborative learning, address affective learning Large University from “Cookie Cutter” to issues, and foster active learning (Ruben, 1999). “Guided Inquiry” Game shows have been used to introduce new material or review previous material in chemistry Edith Preciosa Kippenhan. Chemistry, University courses (Campbell and Muzyka, 2002); however, few of Toledo, Toledo, OH, United States. of these studies offer a quantitative measure of It is possible to introduce inquiry-based experiments student performance and interest. into the general chemistry laboratory curriculum for universities with large enrollments and many Methods: teaching assistants. Group work with online components and lab reports are some of the additions This study involves several sections of freshman that have been made to improve students’ critical chemistry for non-majors over a two year period (to thinking and writing skills. be concluded August 2010). The design incorporated

215. Interfacial Synergy between Energy and States; 2Department of Chemistry, University of 3 Nanomaterials Michigan, Ann Arbor, MI, United States; Hydrogen 1 2 Energy Technology Laboratory, University of Randy L. Vander Wal, Gordon M. Berger, Michigan, Ann Arbor, MI, United States. Michael J. Kulis,2 Kenneth W. Street,3 Gary H. Hunter,3 Laura J. Evans.3 1Energy and Mineral Electrochemical capacitors (ECs) offer a unique Engineering, Penn State University, University Park, combination of robustness, high power density and PA, United States; 2The Universities Space Research moderate energy density filling the gap between Association/NCSER, Cleveland, OH, United States; conventional capacitors and batteries. These devices 3The NASA Glenn Research Center, Cleveland, OH, store energy via (1) double layer (i.e. electrostatic United States. mechanism) or (2) pseudo-capacitance mechanisms that involve charge transfer processes. Transition- With energy at the forefront of the national economy metal nitrides and carbides due to their high and security energy-directed applications are of electronic conductivity, surface area (up to 200 m2/g particular interest. Not surprisingly, energy and for Mo2-N) and electrochemical stability are materials are intimately related. Many forms of promising candidates as electrode materials for ECs. energy utilization, conversion and storage and generation are dominated by interfacial reactions. Nanostructured V, Mo and W nitrides and carbides Therein nanomaterials as an interfacial modifier will were synthesized via temperature-programmed- play a critical role in these processes. Though reaction of their oxide precursors with NH3 or 15% synthesis of a host of organic and inorganic CH4/H2 respectively. Their physical structures were nanomaterials has been demonstrated, their characterized using scanning electron microscopy integration into practical applications remains highly and X-ray diffraction. Cyclic voltammetry and challenging. This talk will provide an overview of impedance spectroscopy was performed on these their synthesis, integration and value in energy materials in aqueous electrolytes including KOH and storage, conservation, transfer, efficiency, control and H2SO4 in order to determine stable operating generation. Specific energy applications we have potential windows and to gain insights into the explored include the following: charge storage mechanism. 1) Storage: Increased energy density in Li ion batteries and The results indicate that these materials exploit both supercapacitors using carbon nanotubes the double layer and pseudo-capacitance 2) Efficiency: mechanisms, thus storing substantially greater Reduced friction using nanolubricants between amounts of energy compared to the carbons in moving parts commercially available ECs. 3) Transfer: Improved thermal management using nanofluids in heat transfer applications 4) Conservation: Lightweight polymeric composites incorporating nanotubes, nanoclays and graphene oxide for vehicle composites 5) Control: Gas sensors based on nanoscale metal oxide semi- conductors for process control and monitoring 6) Generation: Catalysts and photocatalysts using nanostructured oxides for accelerated charge transfer and minimal recombination losses. Highlights in each application will be presented.

216. Transition-Metal Nitrides and Carbides 217. Silicon-Coated Carbon Fibers for as Electrode Materials for Electrochemical Lithium-Ion Battey Anodes Capacitors Gerard K. Simon,1,3 David J. Burton,2 Tarun Priyanka Pande,1 Paul Rasmussen,1,2 Levi T. 3 1 1 1,3 1 Goswami, Benji Maruyama. Materials and Thompson. Department of Chemical Engineering, Manufacturing Directorate, Air Force Research University of Michigan, Ann Arbor, MI, United

Laboratory, Wright-Patterson AFB, Ohio, United reorganization energy barriers. Our experiments States; 2Applied Sciences, Inc, Cedarville, OH, revealed site-to-site variations in the vibrational United States; 3Department of Biomedical, Industrial reorganization energy barriers in the interfacial ET and Human Factors Engineering, Wright State systems. Our recent experiments on combined single- University, Dayton, OH, United States. molecule photon-stamping spectroscopy and femtosecond transient absorption spectroscopy Of all the materials that can be used in lithium-ion studies of interfacial electron transfer dynamics will battery anodes, silicon has the highest theoretical also be discussed. capacity (4,200 mAh/g). However, its tendency to expand 400% when alloying with lithium makes it unusable in bulk or thin film forms for an anode 219. Electron Transfer Dynamics between 9- material. Despite this, a silicon-coated carbon anthracenecarboxylic Acid and TiO2 nanofiber (CNF) may be a viable method of Nanoparticles with Applications for Novel exploiting silicon’s capacity in a battery anode. Photovoltaic Devices Silicon-coated CNFs were fabricated through 1 1 Lynetta M. Mier, Terry L. Gustafson, Arthur J. chemical vapor deposition by Applied Sciences, 1,2 1 Epstein. Department of Chemistry, The Ohio State Incorporated (ASI), and made into their “nanomat” University, Columbus, OH, United States; material. This novel anode material was put through 2 Department of Physics, The Ohio State University, electrochemical testing. The nanomat demonstrated a Columbus, OH, United States. capacity of 954 mA/g in the first cycle, but faded to 766 mA/g after 20 cycles. Structural characterization We present work on the fundamental photophysics of of the samples before and after cycling was carried electron transfer between 9-anthracenecarboxylic out using field-emission scanning electron acid (9-AC) and TiO2 as a first step in understanding microscopy (FESEM) and transmission electron the photophysical properties of ligands in metallo- microscopy (TEM); the results suggest that a portion organic complexes. The complexes have applications of the fade may be due to separation of the silicon in a proposed metallo-organic photovoltaic (MOPV) coating from the CNFs. Enough silicon remains in device consisting of a broad-spectrum absorber that is contact with the conduction network of CNFs to covalently bound through a carboxylic acid on each allow a usable reversible capacity that well exceeds ligand to a nano-porous TiO2 structure. Integral to the that of graphite. improved efficiency of the proposed device is efficient electron transfer between the light absorbing 218. Single-Molecule Interfacial Electron layer and the TiO2. Before investigating the electron transfer from a metallo-organic complex, we work to Transfer Dynamics at Dye-Sensitized TiO2 Nanoparticles understand the electronic structure and the electron transfer dynamics of the ligands. We observe Yuanmin Wang, Yufan He, H. Peter Lu. Department ultrafast electron transfer dynamics from the of Chemistry, Bowling Green State University, photoexcited singlet state of the 9-AC to the TiO2 Bowling Green, Ohio, United States. nanoparticles, resulting in the formation of the radical Interfacial electron transfer dynamics is important for cation. The process of the electron transfer, which environmental and catalytic reactions. Extensive results in the radical cation, is studied with ultrafast ensemble averaged studies have indicated transient absorption spectroscopy. The formation of inhomogeneous and complex dynamics of interfacial the radical cation is found to occur within the first 0.6 ET reaction. To characterize the inhomogeneity and ps after excitation and have a lifetime of 85 ns and is the complex mechanism, we have applied single- formed from the electron transfer from an excited molecule spectroscopy and correlated AFM/STM singlet state of the 9-AC. imaging to study the interfacial ET dynamics of dye 220. Electrolyte-Dependent Photovoltaic molecules adsorbed at the surface of TiO2 nanoparticles. The interfacial ET activity of Responses in Dye-Sensitized Solar Cells individual dye molecules showed fluctuations and Based on an Osmium(II) Dye of Mixed intermittency at time scale of milliseconds to Denticity seconds. The fluctuation dynamics were found to be Anthony C. Onicha, Felix N. Castellano. inhomogeneous from molecule to molecule and from Department of Chemistry and Center for time to time, showing significant static and dynamic Photochemical Sciences, Bowling Green State disorders in the dynamics. Furthermore, we have University, Bowling Green, Ohio, United States. applied site-specific AFM-Raman spectroscopy on analyzing ET associated mode-specific vibrational

The effects of electrolyte composition, specifically nanocrystals to form photosystem-quantum dot the role of Li+ and I- ions, on the resultant hybrid complexes with enhanced optical properties. photovoltaic performance of dye-sensitized solar In this complex, solar photons are absorbed by the cells (DSCs) based on a new Os(II) polypyridine nanomaterial and then transferred to PS-II where complex of mixed denticity, electron-hole pairs become rapidly and efficiently t [Os( Bu3tpy)(dcbpyH2)(NCS)]PF6 (1), were separated. investigated. Photophysical and electrochemical characterization of 1 confirmed the suitability of this 222. Modeling Challenges in Developing New dye to serve as a sensitizer for DSCs. Varying the Thermoelectric Energy Conversion Materials concentration of LiI in the redox electrolyte affects 1 1 1 all photovoltaic properties of the individual devices. Douglas Dudis, Michael Check, John Ferguson, Joel Schmidt,1 Chenggang Chen,2 Bevan Elliott,2 Increasing the concentration of LiI results in 2 3 1 enormous increments in short-circuit photocurrent in Joseph Shumaker, Michael Leamy. AFRL/RXBT, Air Force Research Laboratory, Wright-Patterson Air the Os(II)-based devices accompanied by 2 corresponding decreases in open-circuit voltage. Force Base, OH, United States; University of - by Dayton Research Institute, Dayton, OH, United Independently increasing the concentration of I 3 using either tetrabutylammonium iodide or the ionic States; Department of Mechanical Engineering, liquid 1-n-propyl-3-methylimidazolium iodide was Georgia Institute of Technology, Atlanta, GA, United found to increase short-circuit photocurrent without States. concomitantly lowering the open-circuit voltage. The Thermoelectric materials and devices present combined results suggest that the photovoltaic tremendous opportunities for direct power generation performance of Os(II)-based DSCs can indeed be from a heat source, harvesting waste heat as optimized by simply modifying the composition of electricity, providing heat lift to pump low grade heat redox electrolytes used in the operational sandwich - for rejection from a system, and for cooling and cells. An abundance of I appears to be crucial for the refrigeration in many temperature ranges. For large effective regeneration of oxidized surface-bound scale applications thermoelectric efficiencies are not osmium sensitizers and therefore for the production competitive with other interconversion technologies, of higher photocurrents in these devices. We note that but for small applications thermoelectric are often the select devices based on 1 represent the record power best choice based on system power/mass or system conversion efficiency for an Os(II)-based DSC power/volume considerations. Overall performance measured under simulated AM1.5G one-sun of thermoelectric devices is limited by the Carnot illumination, η = 4.7%. efficiency, but practical materials do not come close to approaching Carnot efficiencies. Much room for 221. Photosynthetic-Nanocrystal Assemblies improvement is available, and the potential impact is Joseph M. Slocik,1 Alexander O. Govorov,2 Rajesh difficult to underestimate. The quest for new 1 1 thermoelectric materials has been receiving R. Naik. Nanostructured and Biologicals Materials increasing attention particularly since seminal work Branch, Air Force Research Lab, WPAFB, OH, 2 by Hicks and Dresselhaus in 1993 suggesting low United States; Department of Physics and Astronomy, Ohio University, Athens, OH, United dimensional materials as possible paths for improved States. thermoelectric performance. This presents significant challenges requiring simultaneous optimization of The production of biofuels using photosynthetic electrical conductivity, thermal conductivity, and algae and bacteria is limited by the strikingly low thermopower (Seebeck coefficient). These are conversion efficiencies of natural photosystems. This generally interlinked in complex ways such that is due to the partial absorption of solar radiation, loss changing one can negatively influence another. of absorbed light as fluorescence and heat, and Moreover, several effects are reported to give rise to multiple independent energy transfer pathways. enhancements in overall thermoelectric performance. Alternatively, one way to improve the limitations of In this talk thermoelectric material design principles natural photosystems is to employ artificial will be discussed along with related modeling nanomaterials (such as nanoparticles or quantum challenges and opportunities. dots). Nanomaterials are expected to enhance the light-harvesting process for the natural 223. Surfactant and Polymer-Induced photosynthetic components by providing a large Modification of Post-Impact Drop Spreading absorption cross section, high quantum yields, and and Heat Transfer tunable optical properties. As a result, we assembled photosystem II from spinach with optically-active

Milind A. Jog. Department of Mechanical rate (high molecular weight) surfactants. The Engineering, University of Cincinnati, Cincinnati, manifestation of the non-Newtonian viscous behavior OH, United States. is seen to change due to the variation in the spreading shear rate at different Weber numbers. Dynamic Computational and experimental investigation of surface tension, surface wettability, droplet Weber post-impact spreading and recoil behaviors and number, and liquid rheology along with the reagent associated heat transfer for droplets of pure liquids bulk properties are seen to govern the transient (water and ethanol) and aqueous surfactant and impact-spreading-recoil phenomena. polymeric solutions has been carried for a range of Weber numbers (20 – 200). The post-impact dynamics of film spreading and its recoil behavior 224. Temperature Dependence of the are captured using high-speed real-time digital Gramicidin Channel Conductance imaging. Hydrophilic (glass) and hydrophobic Thomas L. Beck,1 Hyundeok Song.2 1Department of (Teflon) substrates have been used with water and Chemistry, University of Cincinnati, Cincinnati, OH, aqueous solutions of three different surfactants of United States; 2Department of Physics, University of varying diffusion rates and ionic characteristics – Cincinnati, Cincinnati, OH, United States. SDS (anionic), CTAB (cationic) and Triton X-100 (non ionic). The solutions rheology is modified by The gramicidin channel is the smallest known mixing the water-soluble hydroxyethyl cellulose biological ion channel, and it exhibits cation (HEC) with different degrees of polymerization at selectivity. There are two forms of the gramicidin different concentrations. The solution rheological and channel, the single-stranded helical dimer(HD) interfacial properties are characterized to understand known as channel and the double-stranded double the role of wettability, surface tension, and shear- helix(DH) known as nonchannel. Recently, Dr. John thinning viscosity on the droplet-surface interactions. Cuppolettis group at University of Cincinnati showed The dynamic behavior of drop spreading of surfactant that the gramicidin channel could function at high laden and shear thinning fluids is contrasted with temperatures (360 ∼ 380K) with significant currents. those for Newtonian liquids. The numerical This finding may have significant implications for simulation of the process was carried out to predict fuel cell technology. In this project, we have the transient drop shape evolution and drop-surface examined the experimental system at 300K, 330K, heat transfer. The numerical method is based on a and 360K by computer simulation. Ohio Super finite volume formulation on a structured grid with a Computer was used for the Umbrella sampling volume-of-fluid (VOF) technique for interfacial calculation. We have investigated how the tracking. The numerical model is validated by temperature affects the current and differences in comparing the computational results with magnitude of the currents between HD and DH. Both photographs of droplet shape deformation and recoil the decrease of the free energy barrier and the captured using a high-speed digital video camera at increase of the diffusion of potassium ions inside the 4000 frames per second. The results reveal that the gramicidin channel at high temperatures showed an water droplets spread and then recoil sharply so as to increase of current. The applied external field form a vertical column, which breaks up and ejects 0.2V/nm along the z axis showed that the movement secondary droplets on a hydrophobic surface. The of potassium ion inside HD,DH at 360K is much decrease in surface tension at the liquid-air interface faster than 300K, 330K. and change in the wetting characteristics of the liquid-solid interface facilitate larger initial spreading We found that higher temperatures also affect the and weaker recoil of surfactant solution droplets lifetime of hydrogen bonds, the distribution of the compared to water drops. Correspondingly the bending angle, the distribution of the distance transient heat transfer rate is significantly higher for between dimers, and the size of the pore radius for aqueous surfactant solution droplets compared to the helical dimer structure. These finding may be pure water droplets at the same Weber number. The related to the gating of the gramicidin channel. role of dynamic surface tension is evident in comparisons of impact dynamics of droplets of 225. Atomistic Scale Thermal Transport in different surfactant solutions with identical Amorphous Materials and Its Interfaces equilibrium surface tension and same Weber number. It was observed that higher diffusion and interfacial Ajit K. Roy, Vikas Varshney, Soumya Patnaik, adsorption-rate (low molecular weight) surfactants Barry Farmer. Thermal Sciences and Materials promote higher drop spreading factors and weaker Branch (AFRL/RXBT), Air Force Research oscillations compared to low diffusion/adsorption- Laboratory, Wright Patterson AFB, OH, United States.

The thermal loads (excess heat) in all DoD systems and BR modes is complex in nature, where the (aircrafts and spacecrafts) have steadily been thermal transmission coefficients do not always increasing at an alarming rate. The current practice is correlate with number of CH2 linkages. However, use fuel as the heat sink to dump the excess heat. when the contributions from all the modes are added This operational approach currently is not adequate to together, the overall interface thermal condutance sufficiently cool the electronics and thermal devices, agrees well with NEMD simulations.tudied LA, TA, and thus limiting the system performance and its TW and BR modes is complex in nature, where the system readiness. Amorphous materials system thermal transmission coefficients do not always (polymers, adhesive, etc.), which is known to be correlate with number of CH2 linkages. However, thermally non-conductive material, is prevalent in when the contributions from all the modes are added almost all DoD systems. So, there is a big incentive together, the overall interface thermal condutance in tailoring its thermal transport characteristics to agrees well with NEMD simulations. meet the system requirements. Invent of the conductive nano material constituents (such as, 227. Phonon Transmission in Functionalized carbon nanotubes, graphite platelets, graphene, etc.) Carbon Nanotube: Wave Packet Study and its adaptation in polymers provides us such Jonghoon Lee,1,2 Vikas Varshney,1,2 Ajit K. Roy,1 opportunity. The success of adapting the nano 1 1 constituents in polymers in providing the conductive Barry L. Farmer. Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright pathways through the polymer phase solely lies on 2 the extent how the interface thermal transport Patterson, Ohio, United States; Universal characteristics are tailoring between the polymer and Technology Corporation, Dayton, Ohio, United nano constituent interfaces. In order to understand the States. thermal transport phenomena is amorphous materials Using wave packet simulations, single mode phonon and to design its interface consistent to the nano transmission coefficients are calculated in carbon constituent morphology scale, computational nanotubes side-functionalized with three different methodology using atomistic molecular dynamics functional groups:-methyl, -ethyl, and -carboxyl. In (MD) is developed. Examples for tailoring thermal general, a phonon with a lower group velocity is interface of nano constituents with polymer will be subject to a stronger scattering. Near the Gamma discussed. point, accoustic phonons show ideal transmissions, while the transmissions of the optical phonons are 226. Molecular Dynamics Simulations of strongly suppresses. A phonon with a certain energy Interface Thermal Conductance in and polarization excites a specific functional group Longitudinally Connected Carbon Nanotube selectively. In a separate study of Rayleigh point Junctions mass defects, the mass discrepancy plays crucial role in the transmission. However, there is not a Vikas Varshney,1,2 Jonghoon Lee,1,2 Ajit K. Roy,1 1 1 conclusive deduction relating the transmission Barry L. Farmer. Materials and Manufacturing coefficients with the mass of the functional group. Directorate, Air Force Research Laboratory, Dayton, OH, United States; 2Universal Technology Corporation, Dayton, OH, United States. This study explores the behavior of interface thermal conductance of longitudinally connected (6,6) nanotubes using non-equilibrium molecular dynamics (NEMD) and wave-packet simulations. Here, we study the effect of number of connected CH2 linkers on the interface thermal conductance and thermal transmission coefficients of several phonon modes. Our simulation results suggest that interface thermal conductance between nanotubes is a strong function of the number of CH2 linkers. The more the number of CH2 linkers, the higher the conductance. Further insights into thermal transmission of several phonon modes through CH2 linkages are provided from wave-packet simulations. Here, we find that behavior of transmission for each of the studied LA, TA, TW

228. Diamonds Made of Graphite: A new type of iron pincer complexes (1, 2) have been Calculations on Novel High-Symmetry synthesized using zero valent iron pincer complex Carbon Cages Fe(PMe3)4 and diphosphinite pincer ligands through a selective C-H bond activation process. The PMe3 Roderick M. Macrae. School of Mathematics and ligand that is trans to H undergoes ligand substitution Sciences, Marian University, Indianapolis, IN, United reaction when exposed to CO. 1-CO isomerizes in States. solution upon heating. NMR experiments have shown The term fullerene is now generally used to refer to that this process is not inhibited by PMe3 and CO. any molecular form of carbon containing only hexagonal and pentagonal faces and exhibiting a 230. New Methodology for the Synthesis of cage-like structure. However, these are not the only Periodic Mesoporous Organosilicas (PMO’s) types of face from which a closed cage can be with Bridging Phenyl Groups constructed; in the topology of polyhedra, the Euler T. Kenneth McBride,1 Wendy L. Burns,1 characteristic χ = F + V - E is always equal to two 2 1 Christopher T. Burns. Department of Chemistry and for any convex polyhedron (where F, V, and E are Physics, Bellarmine University, Louisville, respectively the number of faces, vertices, and 2 Kentucky, United States; Department of Chemistry, edges). A graphenic carbon sheet consisting of sp2 University of Louisville, Louisville, Kentucky, carbons arranged in 6-rings can be closed into a cage United States. by the addition of twelve 5-rings, six 4-rings, or four 3-rings, to limit consideration only to the most Periodic mesoporous organosilicas, PMO’s, were symmetric arrangements of non-hexagonal faces. The discovered in 1999 and are still an under explored first of these classes gives the fullerenes; the others field of organic-inorganic chemistry. The pores give interesting and barely studied classes of non- present within these structures have the ability to fullerene cages which may or may not be realizable separate mixtures, to carry an electrical current, or act in nature. An example of a small C24 cage of as a support for catalysts. The varieties of functions octahedral symmetry is shown in the figure. Higher- are tailored via organic linker molecules that hold order cages in the series can be obtained by replacing together the three-dimensional silica structures. This the six-membered rings by graphenic sheets. research has utilized phenyl as an organic linker within the PMO. Phenyl was used to develop an improved methodology for the PMO’s. This material can be compared to the phenyl based PMO synthesized via the known methodology.

231. Developing a New Methodology for the Synthesis of Periodic Mesoporous Organosilicas Wendy L. Burns,1 Christopher T. Burns.2 1Department of Chemistry and Physics, Bellarmine University, Louisville, Kentucky, United States; An algorithm has been created which is capable of 2Department of Chemistry, University of Louisville, producing high-symmetry cage geometries of Louisville, Kentucky, United States. arbitrary size. These structures are characterized through their adjacency matrices using Hückel The study of periodic mesoporous organosilicas theory, and then used as initial geometries for density (PMO’s) is an important bridge between organic, functional calculations. Trends in electron inorganic, and material science. The development of delocalization, obtained from the results of these this science within the last decade has afforded the calculations through study of the distribution of synthesis of PMO’s with applications as catalysts, single-bond and double-bond character, are reported. electrical conductors, and host frameworks for use in host-guest chemistry. Organic linker molecules act as 229. Synthesis and Reactivity of Iron Pincer bridges within the three dimensional silica backbone to form hexagonal shaped pores that range from 1-50 Complexes nm. Known synthetic techniques for the PMO’s Papri Bhattacharya, Jeanette A. Krause, Hairong drastically limit the size and type of organic linkers Guan. Department of Chemistry, University of that can be incorporated. The Burns group is Cincinnati, Cincinnati, OH, United States. currently developing a new methodology for the

synthesis of PMO’s that will allow additional properties. Capsaicin consists of three regions that structures to be synthesized which are unavailable are important for binding to appropriate receptors, with the current methods. allowing it to serve as an interesting target in the design of lanthanide chelates for sensing capsaicin. A 232. Rich Coordination Chemistry of series of Eu (III) and Tb (III) chelates have been Copper(I) with a Poor Sigma Donor synthesized for luminescent detection of a series of Pyridylpyrrolide capsaicin analogs. These chelating ligands are bis- amide derivatives of ethylenediaminetetraacetic acid Jaime A. Flores, Robert J. Wolfe, Jose G Andino, (EDTA). The design and synthesis of the lanthanide Hyunsoo Park, Kenneth G. Caulton. Department of chelates and capsaicin analogs shall be presented, Chemistry, Indiana University, Bloomington, IN, along with luminescence data from binding studies. United States. A number of copper(I) complexes with a weak sigma 235. Synthesis and Anticancer Properties of donor 2-(2’-pyridyl)-3,5-bistrifluoromethylpyrrolide silver(I)- and gold(I)-N-Heterocyclic Carbene as a supporting ligand have been isolated. Complexes Acetonitrile and carbonyl adducts were easily 1 2 Tammy J. Siciliano, Michael C. Deblock, synthesized and under mild conditions. These 3 3 Khadijah M. Hindi, Semih Durmus, Matthew J. develop a very labile metal-lewis base bond. By 3 3 3 Panzner, Claire A. Tessier, Wiley J. Youngs. applying vacuum to either of these species a 1 Department of Chemistry, The Ohio State University copper(I)-pyridylpyrrolide trimer with unprecedented 1 19 13 at Mansfield, Mansfield, OH, United States; features was obtained. H, F, C NMR, IR, Mass 2 Department of Biology, University of Akron, Akron, spectrometry and crystallographic analyses were used 3 OH, United States; Department of Chemistry, in the full characterization of these new compounds. University of Akron, Akron, OH, United States.

233. Synthesis of FeSb2 Nanorods and The synthesis of several silver(I)- and gold(I)-N- Nanoparticles by Solvothermal Synthesis heterocyclic carbene (NHC) complexes will be Routes presented. These metal NHC complexes differ at the 4- and 5-positions of the imidazolyl ring of which an Joel E. Schmidt, Douglas S. Dudis, Joseph A. example is shown. The anticancer properties of these Shumaker, Harry A. Seibel. Materials and compounds will also be discussed. Manufacturing Directorate AFRL/RXBT, Air Force Research Laboratory, WPAFB, OH, United States.

FeSb2 has recently been considered as a novel thermoelectric material due to a Seebeck coefficient of ∼-45000 µVK-1 and a thermoelectric power factor of ∼2300 µWK-2 cm-1 at low temperatures (Bentien, A. et al. 2007 Europhys. Lett. 80 17008). However, its thermoelectric potential is limited by a high thermal conductivity. To lower the thermal conductivity both nanorods and nanoparticles of FeSb2 were synthesized. Nanorods were synthesized following a previously published solvothermal 236. A Systematic Study of Growth synthesis in ethanol. Nanoparticles were synthesized Conditions on the Composition, Structure using a novel sodium naphthalenide reduction in and Properties of Sr2FeMoO6 Films Grown triglyme at ambient pressure. XRD was used to Via Pulsed Laser Deposition characterize both materials. Tricia L. Meyer,1 Patrick M. Woodward,1 Thomas 2 1 234. Synthesis of Lanthanide Chelates for R. Lemberger. Department of Chemistry, The Ohio Detection of Capsaicin in Solution State University, Columbus, OH, United States; 2Department of Physics, The Ohio State University, Christopher G. Gulgas, L. Wyatt Colvin. Columbus, OH, United States. Department of Chemistry and Physics, Longwood Perfect Sr FeMoO is thought to be a 100% spin University, Farmville, Virginia, United States. 2 6 polarized half metallic ferrimagnet (HMF). This Capsaicin is a natural product found in hot peppers feature coupled with its Curie temperature of 420 K, and has both potent pain-inducing and numbing which is above room temperature, make it an

attractive material for spintronic applications. Thin substrate roughness, not the chemical addends nor the films of Sr2FeMoO6 have been grown by pulsed laser thermal cycling, is the predominant determinant in deposition (PLD) and their properties characterized the graphene corrugation. This conclusion is using X-ray diffraction, Rutherford Backscattering, supported by depositing large graphene oxide flakes and SQUID magnetometry. Films have been grown on freshly cleaved mica. Such flakes were shown to at substrate temperatures ranging from 800-850 °C have low corrugation (rms ∼ 70 pm), as dictated by and pressures ranging from 30-150 mTorr in both the atomically flat surface of mica. This experimental inert (Ar) and reducing (Ar+H2) atmospheres. The observation is in accord with the results of our role of substrate lattice match and post-annealing has molecular dynamics simulations, which show that also been explored. The post-annealing results interaction with the substrate greatly suppresses the indicate an increase in the magnetic saturation as well intrinsic corrugation of graphene materials. as a relaxation of the film lattice parameters towards the bulk value. Analysis of the phase purity, We also discuss different chemical approaches to stoichiometry, Fe/Mo ordering and low-temperature modify the electronic properties of GNRs. In magnetic properties of both pre- and post-annealed particular, we demonstrate that chemical films will be discussed. functionalization of GNRs using diazonium salts could be a promising way to alter the electrical 237. Electronic Properties of Graphene properties of graphene devices.3 The kinetics of the Nanoribbons Produced by Chemical functionalization can be monitored by probing the Unzipping of Carbon Nanotubes electrical properties of GNRs, either in vacuum after the grafting, or in situ in the solution. We derive a Alexander Sinitskii, Dmitry V. Kosynkin, Ayrat simple kinetics model that describes the change in the Dimiev, James M. Tour. Department of Chemistry, electrical properties of GNRs. Rice University, Houston, TX, United States. Described in this talk is the large-scale fabrication of [1] Kosynkin, D.V.; Higginbotham, A.L.; Sinitskii, electronic devices based on graphene nanoribbons A.; Lomeda, J.R.; Dimiev, A.; Price, B.K.; Tour, J.M. (GNRs) produced by unzipping of carbon nanotubes.1 Nature 2009, 458, 872-876. We show that GNRs have numerous advantages for device fabrication: they can be produced in large [2] Sinitskii, A.; Fursina, A.A.; Kosynkin, D.V.; quantities with 100% yield, their thickness can be Higginbotham, A.L.; Natelson, D.; Tour, J.M. Appl. estimated by conventional SEM, they all have similar Phys. Lett. 2009, 95, 253108. dimensions, they rarely exhibit wrinkles on Si/SiO2 substrates and can be easily aligned in a parallel [3] Sinitskii, A.; Dimiev, A.; Corley, D.A.; Fursina, fashion. The conductivity of as-prepared GNRs can A.A.; Kosynkin, D.V.; Tour, J.M. ACS Nano 2010, 4, be enhanced through reduction by hydrazine and 1949-1954. further annealing in Ar/H2 at high temperature. With the available alignment techniques, hundreds of 238. Multi-Layer Graphene Petals Grown on graphene-based devices can be fabricated on a single Flat Substrates by Plasma CVD 2 chip. We discuss possible applications of the GNR 1 1 2 Chandra S. Rout, Anurag Kumar, Chris Muratore, devices as field-effect transistors, 2 1,2 1 Roger Gerzeski, Timothy S. Fisher. Birck nanoelectromechanical switches, ultracompact gas Nanotechnology Center, Purdue University, West sensors and nonvolatile memories. 2 Lafayette, IN, United States; RXBT, Air Force

Research Laboratory, WPAFB, OH, United States. Additionally we demonstrate that the interaction of GNRs with the Si/SiO2 substrate strongly affects their Microwave plasma CVD method has been employed electronic properties. The interplay of different to synthesize few-to-many-layer graphene petals on factors such as (a) substrate roughness, (b) thermal various substrates including Si, Ti/Si, quartz and treatments, and (c) oxygen-containing addends on the bucky paper without using catalyst. Growth nanoscopic corrugation of the GNRs has been conditions have been varied by changing temperature studied. Our experiments demonstrate that despite the and plasma power with an aim of achieving control temperature treatment (annealing in Ar/H2 at 300 ºC) of layer thickness graphene. Raman spectroscopy has and the associated removal of the oxygen-containing been used to estimate the number of graphene layers addends from the basal plane of the GNRs, the of the petals. Raman modes are observed at 1352 cm- corrugation pattern of the ribbons exhibits almost no 1 (D-mode), 1589 cm-1 (G- mode), 2701 cm-1 (2D change upon annealing. This suggests that the mode), 2946 cm-1 (D+G mode), 3255 cm-1 (2D’ mode) and 4296 cm-1(2D+G mode). Changes in the

D/G and 2D/G ratios for the petals grown in different formation of metal precursor complexes of different growth environments has been analysed to estimate reduction potential and the combination of the facets the number of layers. By varying temperature at a expressed on the core nanocrystal and the degree of constant plasma power, the D/G and 2D/G ratio each lattice mismatch with shell elements, we have change by a factor of approximately 2. The intensity developed a general framework for understanding of the D-band decreases at lower growth temperature and thus controlling nanoparticle growth mode to suggesting less defective petals. By changing plasma yield architecturally complex noble metal nanorods. power at constant temperature similar growth The effect of the structural and compositional behavior has been observed. Hence it should be complexity on the optical and catalytic properties is possible to develop new applications and physical discussed with regards to the different heterojuctions properties associated with the petal structures grown formed on the nanoparticles. on catalyst-free substrates. 240. Isolation and Characterization of Magic- Numbered Silver Clusters Terry P. Bigioni. Department of Chemistry, The University of Toledo, Toledo, OH, United States. Metal clusters lie at the boundary between molecular species and nanoparticles and can provide insights into the origins of the optical, electronic and chemical properties of nanomaterials. A better understanding of these protomaterials could provide insights into the fundamental rules that govern the stability of nanomaterials. For example, the atomic and electronic structures of gas-phase metal clusters have been shown to lead to the anomalous stability of certain discrete particles sizes, known as magic- number clusters.[1] Although strong evidence existed for magic numbers in the condensed phase,[2] only recently was a family of Au clusters shown to exist with discrete structures and chemical formulae.[3] 239. How To Embellish Au NRs: Controlling We have discovered that Ag clusters can also be the Growth Mode of Ag, Pd and Pt on the Au synthesized as a family of more than 20 discrete sizes and structures, using glutathione as the ligand. We Kyoungweon Park, Richard A. Vaia. will describe the synthesis and separation strategy Nanostructured and Biological Materials Branch, Air used to study the members of this family of clusters. Force Research Laboratory, Wright-Patterson AFB, Chemical synthesis experiments have given insights OH, United States. into the control parameters for the nucleation and growth of smaller versus larger clusters, allowing the Multicomponent nanostructures have great potential tuning of product. These results have also been in a wide range of applications due to their unique applied to Au clusters, again allowing tuning of the chemical, optical, and magnetic properties that arise product. Absorbance and fluorescence spectroscopy from the structural and compositional complexity and showed that the electronic structure of the Ag clusters associated heterojuctions. Colloidal approach is quite different than the Au clusters. The Ag provides synthetic routes to fabricate finely-tailored clusters have more pronounced features that appear to and narrowly-dispersed complex metal be a consequence of the lower density of states for nanostructures; however the complexity of Ag, due to the larger energy difference between the processing parameters limits reproducibility of the d-band and Fermi level relative to that of Au. These nanostructures. Subtle difference in the concentration results will be interpreted in the context of magic- of reactants and particles, temperature and pH can number clusters. result in totally different morphology of the final nanostructures. In this study, secondary chemical [1] T. P. Martin et al., “Shell structure of clusters”, J. reduction and galvanic exchange reaction are adopted Phys. Chem. 1991, 95, 6421-6429. to introduce additional component at various locations of the surface of Au nanorod template to [2] R. L. Whettenet al., “Nanocrystal gold fabricate core-shell structure. By focusing on the molecules”, Adv. Mater. 1996, 8 (5), 428-433.

Single-wall carbon nanotubes (SWNTs) are known [3] Y. Negishi et al., “Magic-numbered Au-n clusters for their superior physical, chemical and mechanical protected by glutathione monolayers (n=18, 21, 25, properties and can be utilized in a number of 28, 32, 39): Isolation and spectroscopic potentially world-changing applications. There are, characterization”, J. Amer. Chem. Soc. 2004, 126 however, several factors that restrict their application. (21), 6518-6519. A primary constraint is the limited lifetime of catalyst, which results in premature SWNT growth 241. Sonochemical Assisted Synthesis of termination during chemical vapor deposition (CVD) Silver Nanoparticles and the Decoration of process, thus affecting SWNT length (usually on the Single-Walled Carbon Nanotubes and order of millimeters) and yields. Graphene Oxide To address this issue we have performed water- K. A. Shiral Fernando,3 Nicholas D. McNamara,1 assisted CVD growth and annealing experiments with Barbara Harruff,3 Marcus Smith,1 Elena Guliants,1 iron catalytic layer on alumina substrate. Real-time Christopher E. Bunker.2 1University of Dayton, SWNT carpet growth rate measurements as a Dayton, OH, United States; 2Wright Patterson Air function of growth time indicates three distinct Force Base, OH, United States; 3University of regions of growth prior to the termination. Plan-view Dayton Research Institute, Dayton, OH, United and cross-sectional TEM allowed correlation of these States. regimes with changes in the size distribution of the Fe catalysts with annealing time. A correlation Nanoparticle synthesis is currently an area of between in-situ measured SWNT carpet growth rate extremely active research, due in large part to the and particle size distribution reveals that growth wide variety of potential applications. We have termination is driven by two primary factors: Ostwald applied sonochemistry to the synthesis of various ripening and diffusion of the Fe catalysts into the metal nanoparticles. Here, we report the synthesis alumina substrate. Real time growth and annealing of and characterization of silver nanoparticles formed equivalent samples inside the environmental through the reduction of silver acetate with DMF. In transmission electron microscope (E-TEM) in addition, we further investigated the decoration of equivalent environments were used to further validate single-walled carbon nanotubes (SWNTs) and our hypothesis. Based on the results, we suggest graphene oxide (GO) with Ag via a one-pot-synthesis catalyst layer modifications that could yield method. It was found that the sonochemical method improved carpet growth. From our results, it becomes was capable of producing well-decorated SWNTs clear that rational design of catalyst layer and support with particles that were sub-5 nm; however, in the substrate is absolutely crucial to prolong catalyst absence of sonochemistry (i.e., strictly thermal) the lifetime, thus maximizing nanotube yields. nanoparticles are scientifically larger and the SWNTs less decorated. These results will be discussed within the context of possible mechanisms for the 243. Highly Conductive Graphene sonochemical decoration of SWNTs and GO. Nanoribbons by Longitudinal Splitting of Carbon Nanotubes Using Potassium Vapor 242. Connecting Carbon Nanotube Growth Dmitry Kosynkin, Alexander Sinitskii. Smalley Termination to Catalyst Morphology Institute for Nanoscale Science & Technology, Rice Dmitri N. Zakharov,1 Seung Min Kim,1 Cary L. University, Houston, TX, United States. 2 3 2 Pint, Placidus B. B. Amama, Robert H. Hauge, Graphene holds great promise for the fabrication of 4 1 1 Benji Maruyama, Eric A. Stach. School of microelectronic devices. It is a zero-bandgap Materials Engineering and Birck Nanotechnology semiconductor demonstrating ballistic conductance Center, Purdue University, West Lafayette, IN, over distances approaching several micrometers1-5. 2 United States; Department of Physics and We have recently shown that carbon nanotubes Astronomy, and Department of Chemistry, Richard (CNTs) can be selectively unzipped lengthwise by E. Smalley Institute for Nanoscale Science and the action of acidic potassium permanganate to form Technology, Rice University, Houston, TX, United straight-edged oxidized graphene nanoribbons 3 States; University of Dayton Research Institute, (GNRs)6. Here we demonstrate how nanoribbons free University of Dayton, Dayton, OH, United States; of oxidized surfaces can be prepared in large batches 4 Materials and Manufacturing Directorate, Air Force and 100% yield using potassium vapor to Research Laboratory, Wright-Patterson Air Force mechanically split multi-walled carbon nanotubes Base, OH, United States. (MWCNTs). The low defect density of these

nanoribbons is indicated by their electrical (macrocyclic/linear blends). However, self-consistent conductivity, comparable to that of graphene derived field theory1 predicts that macrocyclic chains enrich from mechanically exfoliated graphite. The possible the surface of such a blend, so that the surface origins of directionally selective splitting of concentration is 1.5 times that in the bulk. Theory1 MWCNTs have been explored using computer further predicts that the surface excess should be modeling and plausible explanations for the unique larger for cyclic molecules of higher molecular role of potassium were found. weight. For blends of star-branched and linear chains, the surface excess has been shown experimentally to 244. Towards the Synthesis of Amphiphilic depend critically on the number of chain ends and 2 Nanoparticles Using Crosslinked number of branch points. It remains to discover how Polystyrenes various parameters of macrocyclic chains influence the surface segregation of blends containing James Baker, Nicholas Moon, Andrea Charif, macrocyclics. Coleen Pugh. Department of Polymer Science, The University of Akron, Akron, Ohio, United States. A series of well-defined macrocyclic/linear polymer One of the current focuses in the field of polymer blends has been synthesized by anionic polymerization. Synthesis of macrocyclic polymers synthesis is the preparation of polymers having well- 3 defined architectures. The goal of this project is to was performed by a newly developed method using prepare amphiphilic nanorods so others can study the di-vinylpolystyrene macromonomers as precursors self-assembly of these particles into 2-D and 3-D (linear chains with a vinyl group at each end) of structures. narrow molecular weight distribution, and then the The nanoparticles will be composed of diblock precursors were cyclized using a ring closing copolymers of styrene derivatives, with each block metathesis reaction. The macrocyclic polymers were having a different surface chemistry. For example, characterized by NMR, GPC, and MALDI-TOF mass after crosslinking in a two-step process, spectrometry to confirm the expected structure. The poly(styrene)-block-poly(4- tandem mass spectrometry spectra for the (oligooxyethylene)styrene) will result in a polymer macrocyclic and the linear precursor show different nanoparticle having a hydrophobic lobe and a fragmentation patterns, providing additional evidence hydrophilic lobe. Upon heating above a threshold for the macrocyclic structure. The molecular weight temperature, the crosslinking agent isomerizes and and molecular weight distribution of the rapidly reacts to form dimers and oligomers. By macrocyclics used in the study were 37,000 g/mol changing the substituent on the crosslinking agent, and 1.03, respectively. The surface excess of we are able to adjust the temperature at which macrocyclic chains was quantified using neutron crosslinking occurs. reflectometry (NR). The NR results show that Under ultra-dilute conditions a polymer chain macrocyclic polymer segregates to the surface, but containing these functionalities can undergo the surface excess is lower than predicted by theory. intramolecular chain collapse to give a crosslinked, The opposing preference of the deuterated linear discrete particle. The polymers for this study are species for the surface due to the isotopic effect being prepared via controlled radical polymerization. provides a partial explanation for the modest segregation observed, but probably additional effects need to be incorporated into the theory. 245. Surface Segregation in Blends

Containing Macrocyclic Chains References Shih-Fan Wang, Jonathan Janoski, David E. Dabney, Chrys Wesdemiotis, Roderic P. Qurik, Mark 1. Hu, R; Wu, D.T.; Yang, S.; Foster, M.D. “Surface D. Foster. Department of polymer science, The Segregation in Linear/Pompom and Linear/Cyclic University of Akron, Akron, OH, United States. Polymer Blends”, AIChE national meeting, Nashville, TN, Nov. 2009, Blends containing macrocyclic polymers may http://aiche.confex.com/aiche/2009/webprogrampreli provide opportunities for tailoring surface properties minary/Paper167215.html by the segregation of the macrocyclic component to the surface. The focus of studies done to date on 2. Lee, J. S.; Foster, M. D.; Wu, D. T. systems containing macrocyclics has been synthesis Macromolecules 2006, 39, 5113.3. and computer simulation. No experimental work has been done on the surface segregation behavior of 3. Wang, S. F; Janoski, J.; Quirk, R. P.; Foster, M. D. blends of macrocyclic and linear chains in preparation.

Acknowledgement

We thank Dr. Bulent Akgun for assistance in measurements of neutron reflectometry and Dr. David Wu for insights into the theory. Research support from NSF (CBET-0730692) is gratefully acknowledged. The use of neutron reflectometry was supported by the National Institutes of Standards and Technology, U.S. Department of Commerce.

246. Novel PET/In-Situ Fabricated Sheet- Like Titanium Compound Nanocomposite with Excellent Processing and High Effective Uv Shielding Abilities Bin Sun,1 Kun Zhang,1 Heng Zhang,1 Wei Wang,2 Siwei Leng,3 Meifang Zhu,1 Stephen Z. D. Cheng.3 1State Key Lab for Modification of Chemical Fibers and Polymer Materials, College of Material Science

and Engineering, Donghua University, Shanghai, China; 2Key Laboratory of Science and Technology of Eco-textile, Ministry of Education, College of Chemical Science and Engineering, Donghua University, Shanghai, China; 3The Maurice Morton Institute and Department of Polymer Science, The University of Akron, Akron, OH, United States. In recent twenty years, researchers paid much attention to effectively combine the sol-gel process and polymer synthesis, process and application in order to develop high performance polymer based 247. Poly(arylene Ether)s Via Nucleophilic nanocomposites. In this contrubtion,The titanium Aromatic Substitution Reactions of 3,5- compound nanosheet has been in-situ fabricated and its effect on the PET synthesis has been examined in Difluoro Aromatic Systems detail. Based on this,Series of PET nanocomposites Eric Fossum, Sridevi Kaiti, Daan van Beek, Kevin have been prepared. The basic physical Tienda, Zhenning Yu, Gigi Kusmus, Kim Kern, properties,such as end carboxyl group,DEG, Fadwa Constandinidis. Chemistry, Wright State molecular weight and its distribution, thermal University, Dayton, OH, United States. properties have been examined in detail.The nanocomposites possess interesting rheology A traditional pathway to poly(arylene ether)s, PAE, properties. As nanosheet weight content increases, involves the nucleophilic aromatic substitution, NAS, the nano-composite become easier to flow and the reactions of aryl chlorides or fluorides which are sheering viscosity become lower. By 1D-WAXD activated by the presence of a strong electron patterns, it is indicated that the in-situ formed withdrawing group located in the para position. titanium compound has unique crystalline structure Alternatively, our group has been exploring the NAS with new diffraction peaks between 2-theta 6° and chemistry of a series of 3,5-difluoro aromatic 11°. The nanocomposites have good processing systems, 3,5-difluorodiphenyl sulfone, 1, 3,5- ability to fiber and film, and very excellent Uv difluorobenzophenone, 2, 3,5- sheilding function due to parallelly arrangement of difluorotriphenylphosphine oxide, 3, and 2-(3,5- the nanosheet to the film face as shown by Fig.1 and difluorophenyl)benzoxazole, 4, that are activated via Fig.2. strong electron withdrawing groups located meta to the two fluorine atoms. The successful displacement of both fluorine atoms in 1 - 4 resulted in a new class of poly(arylene ether)s, PAE, which are simply geometric isomers of the more traditional materials. Because the NAS activating group is not present in

the backbone the resulting PAE structures have a William Storms, Coleen Pugh. Polymer Science, backbone similar to poly(phenylene oxide), PPO. University of Akron, Akron, Ohio, United States. However, the new polymers bear truly pendant Polyesters of lactic acid (PLA), glycolic acid (PGA) functional groups that provide an avenue to tailor and their copolymers (PLGA) are currently the best their physical and chemical properties via pre- or post materials for disposable or non-recoverable polymer polymerization modification chemistry. This goods applications because they degrade under presentation will discuss the monomer syntheses, environmental and biological conditions, their NAS reactivity screening, polymerization behavior, degradation products occur naturally in the body and and thermal properties of the polymers derived from the environment, and their monomers are naturally 1 – 4. derived. PLA has been extensively utilized as an

environmentally friendly replacement for traditional commodity polymers, and PLGA has become the de facto soft material for biomedical applications such as drug delivery and as tissue engineering scaffolding. However, these polyesters possess a great shortcoming in that they are non-functional and do not possess a handle by which to functionalize them.

We previously synthesized halogen pendant functionalized PLGA. The halogen provides a site for 248. Synthesis and Study of Resorcinarene- functionalization, either by attachment of a moiety, and Calixarene-Core Polylactide Star e.g. a drug or pigment, or transformation to a different functional group. We will describe a Polymers number of nucleophilic substitution reactions Perry S. Corbin. Chemistry, Ashland University, between brominated PLA or a small molecule model Ashland, OH, United States. of brominated PLA and nucleophiles, to prepare pendant functionalized polyesters. Polylactides (PLAs) have been used in a variety of applications, including their use in drug-delivery 250. Synthesis of Cyclic-b-Linear PEG-b-PCL devices, surgical sutures, and packaging films. However, architectural diversity within this class of Copolymers for Controlled Drug Delivery polymers is limited; which, in turn, somewhat limits Gladys R. Montenegro, Coleen Pugh. Department the applications of the polymers. In an attempt to of Polymer Science, The University of Akron, Akron, counter these problems, we have recently synthesized Ohio, United States. a series of multi-armed, resorcinarene- and calixarene-core star PLAs. Sn(II)-catalyzed, ring- Controlled drug delivery has attracted the attention of opening polymerizations of lactide using both medical and synthetic researchers due to its multifunctional, macrocyclic initiators have yielded therapeutic advantages such as reduction in side four- to eight-armed star polymers with wide-ranging effects, and more favorable pharmacokinetics. The molecular weights. This presentation will focus on main requirements for a drug delivery microparticle the synthesis, characterization, and thermal properties are non-toxicity and degradability or excretability. of these new star polymers. Progress toward the Different polyesters such as polylactide, development of related amphiphilic star block polyglycolide, and polycaprolactone meet these copolymers will also be reported. It should be noted requirements. In order to favor assembly and that development of diverse, multi-functional PLA- formation of microparticles, the polymer used must based materials is of particular interest because the have a narrow polydispersity index (i.e. PDI<1.2). precursor monomer, lactide, may be prepared from These microparticles should also achieve their renewable resources—e.g., corn-starch derived lactic therapeutic effect before they are eliminated from the acid. bloodstream by the immune system. Coating microparticles with hydrophilic coatings has been 249. Main-Chain Functionalized Degradable shown to prevent elimination of microparticles, increasing their circulation times. Polyethylene Polyesters: A Versatile Synthetic Route to glycol (PEG) is one of the most popular materials Functionalization used for microparticle coating. Changing the architecture of the PEG block might affect

microparticle stealth properties. We will present a manufacture our products. Capitalizing on this synthetic approach for the synthesis of PEG-b-PCL potential requires overcoming many technological, copolymers with different PEG block architectures: business and societal hurdles and typically takes cyclic and linear. We will also show the synthesis of many years if not decades to realize. And, if a truly linear and cyclic PEG macroinitiators, and ε- valuable materials-based innovation does make it to caprolactone model polymerizations using a low the marketplace, the payoff is rarely realized by the molecular weight initiator. clever chemist/material scientist or their employer. This presentation will present some of the many 251. Synthesis of Urea Peptoid Oligomers, lessons learned while building Cornerstone Research Their Ability To Self Assemble and Coupling Group, Inc from a “group” of one in 1997 to a group to Polymers Prepared under RAFT Control of over 100 employees in 2010. Challenges at every stage of the technology and business development Neil Ayres. Department of Chemistry, The process will be discussed, focusing on the impact and University of Cincinnati, Cincinnati, Ohio, United unique challenges a truly disruptive materials States. technology can have on an industry and on how an organization must manage the product realization This presentation will detail the synthesis, process. characterization and polymer coupling of novel urea- peptoid oligomers. We have prepared a variety of polymers under RAFT control and used the facile 254. Prior Speakers Panel Discussion: copper catalyzed alkyne-azide cycloaddition reaction Facilitator, Joseph Sabol, PhD to couple these to the urea peptoid oligomers. The Joseph E. Sabol. Sabol Consulting, Sabol Consulting urea peptoids afford a versatile route to complex Services, Racine, WI, United States. molecules with a modular approach to materials chemistry. We will also report our recent Back by popular demand! After brief opening observations that the urea peptoid has the ability to remarks, the panel of experts will answer questions self assemble into well defined aggregates. from the attendees on topics related to starting and running a chemical business, the skill set necessary to 252. Challenges in Building a Small Business be a successful entrepreneur, resources to help you succeed, business plans, capital formation, succession David B. Curliss, Jason E. Lincoln. Performance planning, and other relevant topics of interest in Polymer Solutions Inc., Performance Polymer chemical business community. No question is too Solutions Inc., Moraine, Ohio, United States. tough for this panel of experts. Bring it on! There may be a “How to build a successful small chemical manufacturing business” manual at the 255. Soft Lewis Acid-Catalyzed library, but I haven’t found it. Performance Polymer Cycloisomerization Reactions 2 Solutions Inc. (P SI) has grown from two people in a Zezhou Wang. Department of Chemistry, Michigan garage in 2003 to thirty employees and 25,000SF Technological University, Houghton, MI, United today and occupies a leadership position in a niche States. market. In these first few years we have experienced the many challenges that face a “first time” Some transition metals have been found to act as soft entrepreneur transforming good ideas into successful Lewis acids to activate alkynes toward nucleophilic products in the marketplace. In this presentation I attack. The “soft” character of these large and will discuss early stage technology business issues polarizable cations makes them to display significant such as: funding; IP; business practices; staffing; affinity to the Π electrons of alkynes. For example, Pt marketing; manufacturing and how P2SI is navigating (II), Au(I), Pd(II), and Bi(III) catalysts can catalyze through them. similar reactions to achieve a variety of cycloisomerization reactions. In one of our 253. Sell the Dream: Disruptive Technology publication, PtCl2 was used as the catalyst to catalyze from Concept to Production the intramolecular reaction between an alkyne and an epoxide; in another publication, the cheaper catalyst Patrick J. Hood. Cornerstone Research Group, Inc., BiCl3 was applied to catalyze the enynes to form a Cornerstone Research Group, Inc., Dayton, OH, five membered ring with high yield, and in the third United States. project, we found bismuth catalysts can be used to New and revolutionary materials have the potential to replace the expensive metal catalysts with the high fundamentally change the way we live our lives and

yield. Those methodologies may find application in Y/DODCI system is acting as a model of the central the synthesis of bioactive natural products. process involved in photodynamic therapy. DODCI in solution at the same concentration is 256. Synthesis of Medium-Sized Azacycles stable under 532 nm laser irradiation, although it is Via Metallocarbenoid-Derived Ammonium susceptible to decomposition in the presence of UV Ylide Rearrangements irradiation. Oksana M. Pavlyuk, Mark C. McMills. 258. Validation of an Ibuprofen Impurity Department of Chemistry and Biochemistry, Ohio Method To Meet Current ICH Guidelines University, Athens, Ohio, United States. David B. Shepherd, Dorothy J. Ogden. R&D Facile synthesis of six- and eight-membered Analytical, Eurand, Inc., Vandalia, Ohio, United azacycloalkenes can be accomplished via the States. Rhodium-catalyzed diazocarbonyl decomposition and subsequent rearrangement of the newly formed The USP method for ibuprofen chromatographic ammonium ylides. Similarly, bicyclic nitrogen purity does not meet current FDA and ICH heterocycles can be accessed by utilizing the guidelines. The methodology utilizes an internal Rhodium carbenoid-derived ylide formation- standard and only identifies one degradation product rearrangement. (4-isobutylacetophenone). Internal standards can interfere with these degradation products and are not typically used in impurity methods. Ibuprofen has 15 known related substances and impurities. Eight of the fifteen related substances and impurities were identified to be significant degradation products: ((2RS)-2-[4-(2-methylpropanoyl)-phenyl] propanoic acid, (2RS)-2-(4-formylphenyl) propanoic acid, 2-[4- (1-hydroxy-2-methylpropyl)-phenyl] propanoic acid, (2RS)-2-hydroxy-2-[4-(2-methylpropyl)phenyl]

propanoic acid, 4-isobutylbenzoic acid, 4- 257. Photoinduced Reaction between Eosin Y acetylbenzoic acid, 4-isobutyrylacetophenone,4- and DODCI: A Model System for the isobutylacetophenone). A reversed phase HPLC method employing a Waters Nova-Pak C18 column Photodynamic Effect was developed to resolve and quantitate all eight Roderick M. Macrae, Carrie Upchurch. School of compounds. The method was validated to current Mathematics and Sciences, Marian University, FDA and ICH guidelines. Indianapolis, IN, United States. 259. Synthesis and Characterization of We have observed time-dependent changes in the visible fluorescence spectrum of a solution Nanoparticulated Rifampicin containing the dyes 3,3’-diethyloxadicabocyanine Lakshmi Sai Priyanka Guttikonda, Patty K.-L. Fu. iodide (DODCI) and Eosin Y Department of Chemistry, Governors State (tetrabromofluorescein). Solutions of the isolated University, University Park, IL, United States. dyes show maximum fluorescence intensity at 575 nm and 625 nm respectively. The spectrum of a Rifampicin is a naturally made, non-peptide solution equimolar in the two dyes illuminated by a antibiotic. It is bactericidal, killing by disabling the 532 nm DPSS laser initially exhibits predominantly protein expression system universally conserved by the red fluorescence characteristic of DODCI, but all bacteria. The reason Rifampicin works so well is over a period of minutes this fluorescence disappears that it is a rigid molecule, and sits tightly in the and only the (hitherto masked) yellow-green pocket where it binds, allowing the bonds to be fluorescence of Eosin Y remains, with increased strong. However, this also means that if an amino intensity. We attribute these changes to resonant acid on the edge of the channel with a small side energy transfer between the dyes leading to a reaction chain is replaced by an amino acid with a large side which quenches the DODCI’s fluorophoric activity. chain, Rifampicin may not be able to bind, simply Evidence from studies on deoxygenated samples because it cannot fit in the space. Furthermore, suggests that the reaction is an indirect process rifampicin shows polymorphism and therefore, it is mediated by singlet oxygen, in which case the Eosin necessary to select a suitable crystal form to ensure optimum solubility and dissolution rates. An increase

in amorphous content significantly reduces the Novel metal complexes, metalloporphyrins will be dissolution rate of the powders in water. Because of synthesized using expanded porphyrins - the disadvantages both in physical properties and texaporphyrin as ligand for its capability of strong biologically, Rifampicin has to be synthesized in the absorbance in the far-red spectral region (700nm – form of nanoparticles which have low surface area 1000nm). The first generation porphyrins tested for and show good solubility and dissolution properties. the PDT were based on chemically modified natural Nanoparticles can also be designed to allow sustained hematoporphyrins. They possessed certain limitations drug release from the matrix which improves drug such as weak absorption in the phototherapeutic bioavailability and reduction of the dosing frequency, window as well as poor specificity toward malignant and may resolve the problem of drug resistance. and healthy tissues (high toxicity at ground state). The second generation PDT photosensitizers are Our methodology for encapsulating rifampicin is to mainly based on the engineered, synthetic, and use equal amounts of PEG 200 and tween 60 semisynthetic porphyrins with various expanded (polysorbate 60) as micelle delivery vehicles. After substituent at the pyrrol rings and the methylene dissolving the compound completely in the micelle bridges. Metalloporphyrins belong to the second solution, water was added drop wise while stirred generation of the PDT agents with an inserted metal with the magnetic stirrer. The nanoparticles were in the middle of expanded porphyrin ring in order to then formed. If the nanoparticles are not formed after generate high yield production of long-lived triplet this procedure, homogenizer can be used. After the state. Trivalent lanthanides such as europium, formation of nanoparticles, characterization using terbium, and gadolinium will be the metals of our scanning electron microscope is done to confirm the choice due to their extremely long-lived and highly surface properties of the nanoparticles. emissive triplet excite states. According to the literature, lanthanide metals could form eight to ten- 260. Novel Metalloporphyrins as Potential coordinate when complexed to the prophyrins with Photodynamic Therapeutic Agents ligation sphere completely symmetric. This enhanced structural stability suggests the lanthanide Alex Blinder, Sheetal Gangula, Patty K.-L. Fu. metalloporphyrin complexes could be utilized in a Department of Chemistry, Governors State range of applications including PDT. University, University Park, IL, United States. The objective of the proposed study is to test existing 261. Solid-Phase Synthesis of N-Carboxyalkyl compounds as well as synthesize and characterize Unnatural Amino Acids new compounds to be potential photodynamic Lindsey G. Fischer, Martin J. O’Donnell, William therapeutic drugs to treat different stages of skin L. Scott. Chemistry & Chemical Biology, Indiana carcinomas. Skin cancer is the most prevalent of all University Purdue University Indianapolis, types of cancers. It is estimated that more than 1 Indianapolis, IN, United States. million Americans develop skin cancer every year. According to recent estimates from the Skin Cancer A novel route has been developed for the solid-phase Foundation and the National Cancer Institute, forty to synthesis of N-carboxyalkyl unnatural amino acids 4 fifty percent of Americans who live to age 65 will as potential metalloprotease inhibitors. The key step have skin cancer at least once. Traditionally, surgical involves a nitrogen-carbon alkylation of resin-bound removal of cancerous tissue is the typical treatment amino acids with α-bromoesters (2 to 3). Reaction for skin carcinoma. However, this method is invasive conditions for alkylation of the benzophenone imine and depends on the size, stage, and location of the of glycine on Wang resin (1 to 2) had already been tumor. Complete removal of the cancerous cells can established to introduce unnatural amino acid side be intricate and the removal time can be lengthy. chains onto the resin-bound glycine. The benzyl α- 2 Radiotherapy and Chemotherapy are the two major bromoesters [BrCH(R )CO2Bn] were prepared in non-invasive procedures used for treatment if a skin solution by diazotization of naturally-occurring biopsy reveals cancer. Both methods can induce amino acids to form the α-bromoacids, followed by disabling and life threatening side effects as both benzylation of the carboxylic acid to give the benzyl techniques can indiscriminately destroy normal tissue α-bromoesters. Alkylation of the resin-bound, as well as tumor tissue. Recently photodynamic unnatural amino acids with the benzyl α-bromoesters therapy (PDT) has received a great deal of attention and subsequent cleavage from resin gave the benzyl owing to the ability of this innovation technique to ester monoacid intermediates 3. Reverse-phase target tumor tissues selectively; therefore, cyano-silica gel chromatography and reverse-phase minimizing adverse side effects. preparatory liquid chromatography provided effective

purification of the benzyl ester intermediates. of action. Moreover, 2 inhibits the Ki-67 marker of Hydrogenation of the analytically-pure benzyl ester cell proliferation in SK-BR-3 cells at 24 h and the monoacids afforded clean products as the diacids 4. rate of DNA synthesis in L1210 cells at 2 h. Since 1 The two points of variation introduced through the and 3 are less effective than 2, the presence of a para two alkylation steps of C-alkylation of the methoxyphenyl substituent on the N3 of 2 appears to benzophenone imine of glycine on Wang resin and enhance the antiproliferative properties of the N-alkylation with the benzyl α-bromoesters allow for quinazoliniminium scaffold. The molecular targets the combinatorial synthesis of a library of target and mechanisms of action of this new synthetic class compounds. of antitumor compounds remain to be investigated.

263. Mechanical Stability of the C2A Domain from Human Synaptotagmin 1 262. Synthetic 2-Chloro-3-aryl-4(3H)- Li Duan, Ruxandra Dima. Department of Chemistry, Quinazoliniminium Salts That Are Effective University of Cincinnati, Cincinnati, Ohio, United States. Against Leukemic and Mammary Tumor Cell Proliferation In Vitro Synaptotagmin 1 (Syt1) induces the buckling of 1 1 plasma membrane during neurotransmitter release at Jean-Pierre H. Perchellet, Elisabeth M. Perchellet, the synapse. Therefore, elucidating the mechanical Andrew M. Waters,1 Kusum L. Chandra,2 John 2 2 1 properties of Syt1 is essential for understanding its Desper, Sundeep Rayat. Division of Biology, Anti- biological function in synaptic response. Syt1 Cancer Drug Laboratory, Kansas State University, 2 contains two homologous domains, C2A and C2B. Manhattan, Kansas, United States; Department of Starting from the experimental data [3], we focused Chemistry, Kansas State University, Manhattan, on the analysis of the mechanical properties of the Kansas, United States. C2A domain using molecular simulations. Employing a minimalist model that can access the experimental timescales [1], we found two competing unfolding pathways for C2A. We also carried out simulations using an implicit solvent model as implemented in the CHARMM package [2]. This allowed us to follow the unfolding of C2A on a 6 orders of magnitude faster timescale than in experiments. We found a dramatic switch in the distribution of pathways: the minor pathway became dominant, while the major pathway appeared less

frequent. In addition, we detected a novel pathway Aza-Wittig reaction of aminobenzonitrile yielded not present on the experimental timescales. We will iminophosphorane that upon treatment with phenyl present the connection between the underlying free isocyanates yielded benzannulated 1,3,7-(aza)enyne- energy landscape of C2A and its mechanical behavior allenes. The latter underwent facile acid-catalyzed that gives rise to the above unfolding patterns. intramolecular cyclization to 2-chloro-3-aryl-4(3H)- quinazoliniminium chlorides 1-3. Based on their 1. Zhmurov, A., H. Joshi, V. Barsegov, and R. I. comparative ability to decrease the metabolic activity Dima. 2010. Origins of the mechanical stability of of L1210 and SK-BR-3 tumor cells at days 2 and 4, the C2 domains in Human Synaptotagmin 1: the 2-chloro-3-(4-methoxyphenyl)quinazolin-4(3H)- Simulations of forced unfolding on graphics iminium chloride 2 is a more potent antitumor processors. Biophysical Journal. In revision. compound than the 2-chloro-3-phenylquinazolin- 4(3H)-iminium chloride 1 and the 2-chloro-3-(4- 2. Lazaridis, T., and M. Karplus. 1999. Effective chlorophenyl)quinazolin-4(3H)-iminium chloride 3. Energy Function for Proteins in Solution. The antiproliferative effects of these PROTEINS: Structure, Function, and Genetics. quinazoliniminium salts are concentration dependent 35:133-152. and more pronounced after 4 (IC50 values in the 0.9- 8.4 µM range) than 2 days in culture, suggesting that 3. Fuson, K., L. Ma, R. B. Sutton, and A. F. their antitumor effects in L1210 and SK-BR-3 cells Oberhauser. 2009. The C2 Domains of Human are a combination of drug concentration and duration Synaptotagmin 1 Have Distinct Mechanical Properties. Biophysical Journal. 96:1083-1090.

264. Synthesis of a Series of Multi-Dentate, Hugo Mendoza, Joaquin Palacios. Universidad Aromatic Ligands Utilizing 3,5-Difluoro-2,6- Nacional Autónoma de México, Mexico. Diaminopyridine Polyimides (PIs) are usually prepared by the so- John Williams, Natalie Datien, Mark A. Benvenuto. called two-step method in which a dianhydride and a Department of Chemistry & Biochemistry, diamine are allowed to undergo condensation University of Detroit Mercy, Detroit, MI, United polymerization to form poly(amic acid) precursor, States. and subsequently the precursor is converted thermally or chemically into the final polyimide. Two ligands have been synthesized, both However, this method suffers from some enormous incorporating 3,5-difluoro-2,6-diaminopyridine and drawbacks, such as the use of very toxic carcinogenic an aldehyde incorporating a further Lewis base. The solvents and a long reaction time, typically over 18 h. ligands were then reduced using sodium borohydride, The use of microwave energy for the obtention of PIs 2+ 3+ 2+ 2+ and complexed with Ca , Fe , Ni and Cu . has had great acceptance. In this way, We report the Characterization of both ligands and complexes was synthesis and characterization of aromatic primarily through multi-nuclear NMR. poly(imides) obtained from PMDA and 6FDA monomers under microwave irradiation. Our goal is 265. Isolation and Characterization of to study the microwave power, reaction time, and Peptides That Interact with Graphene solvent effects on the kinetics of the reaction 1 1 parameters KpMw and the changes produced on PIs Laurie L. Wissler, Sharon E. Jones, Sang Nyon properties. Kim,1 Yue Cui,2 Seva Khambadkone,1 Michael C. 2 1 1 McAlpine, Rajesh R. Naik. Materials & The structure and performance of polymers were Manufacturing Directorate, Air Force Research characterized by Fourier Transform Infrared Laboratory, Wright-Patterson AFB, Ohio, United 2 Spectroscopy (FTIR), viscosity, density, and States; Department of Mechanical and Aerospace Thermogravimetric Analysis(TGA). The results show Engineering, Princeton University, Princeton, New that the polyimides can be obtained in a short Jersey, United States. reaction time with high intrinsic viscosity and yield. Graphene has recently been recognized as a The effect of the presence of a bridging group, - promising nanomaterial for a variety of applications, C(CF3)2-, in the monomer structure is apparent in the such as in electronics and sensing. However, permeability parameters of the macromolecules. effective and controlled functionalization of this material has been limited to few physicochemical 267. Can Rhodamine-123 Analogs Be Used methods. Peptides that interact with nanomaterials, To Overcome Multidrug Resistance in including carbon nanotubes (CNTs), can be used in Photodynamic Therapy? the surface functionalization and in controlled chemical reactions on nanoparticle surfaces. Herein, Christopher J. Halbrook, Guilherme L. Indig. we screen for peptides that bind to various graphene- Department of Chemistry and Biochemistry, based materials. Using a combinatorial phage library, University of Wisconsin Milwaukee, Milwaukee, WI, we identify peptides that bind to graphene/graphite. United States. Additionally, atomic force microscopy (AFM) and Photodynamic Therapy (PDT) is rapidly emerging as quartz crystal microbalance (QCM) were used to a promising tumor selective technique in cancer characterize the binding activity of the putative treatment. Photodynamic reactions result in the peptides. Peptides identified in this study could have generation of short lived reactive oxygen species potential for the surface functionalization of graphene (ROS), limiting the radius of action. Thus the and its impact on electronic and mechanical intracellular location of ROS generation can properties. determine the area of photodamage in the cell. Mitochondrial targeting is of specific interest, as 266. Microwave Assisted Polycondensation of mitochondrial destruction has been implicated in the Polyimides by [4, 4´- activation of the apoptotic pathway. Rhodamine-123 (Hexafluoroisopropylidene) Diphthalic (Rh-123) is known both to preferentially accumulate Anhydride, Pyromellitic Dianhydride] and [2, and be retained for longer periods in the 4, 6-Trimethyl-m-Phenylenediamine]. Power, mitochondria of cancer tumor cells as compared to Time and Solvent Effect normal cells. However, Rh-123 has also been found to be a substrate for the drug efflux pump p- glycoprotein (p-gp), a protein that is typically over-

expressed in multi-drug resistant tumors. In this study hexakisphosphate, InsP6). Some monogastric animals we compare the uptake of Rh-123 and its n-octyl like swine lack phytase and therefore cannot digest ester analog by a human uterine sarcoma cell line InsP6 and utilize phosphate. The unabsorbed phytate (MES-SA) and its respective multidrug resistant is excreted from animal and results in soil and water mutant (MES-SA/Dx5). We have found that the n- phosphate pollution. Therefore phytases are octyl ester accumulates in larger quantities in both important to address environmental and nutritional cell lines, as compared to Rh-123. These results problems. An alkaline phytase was extracted from suggest that new phototoxic drug candidates lily pollen and purified in our lab. developed over the molecular template of the n-octyl Heterologous expression in the methylotrophic yeast analog have better chances of inducing the Pichia pastoris was developed. Initial studies destruction of MDR tumor cells than Rh-123 employing the cDNA coding for wild type alkaline derivatives. phytase (wtLlAlp2) was expressed in Pichia pastoris. However, low levels of enzyme was produced. 268. Identification of Sea Turtle Leeches Heterologous expression level is influenced by Using DNA Barcoding transcriptional and translational efficiencies. The gene was optimized with respect to aspects such as Triet M. Truong, Audrey E. McGowin, Adrian M. codon bias, chi-sites and RNA secondary structure. In Corbett. Department of Chemistry, Wright State this poster, the expression of wtLlAlp2 and optimized University, Dayton, OH, United States. gene in Pichia pastoris are compared. Fibropapillomatosis (FP) is a panzootic plaguing all species of sea turtles. In order to assess the potential 270. Design and Synthesis of Unsymmetrical of an environmental cofactor involved in the spread π-Extended Push-Pull Porphyrins through β- of FP, disease rates were compared to water quality Position data for turtle populations at Florida. Parasitic marine leeches (Ozobranchus spp.) could also be a potential Yongming Deng, Hong Wang, Rohit Deshpande. mechanical vector behind the emergence of this Department of Chemistry and Biochemistry, Miami panzootic, although it is uncertain if it is species University, Oxford, Ohio, United States. specific. DNA barcoding using mitochondrial Elongating the π-system and breaking the structural cytochrome c oxidase I (COI) gene as a molecular symmetry of the porphyrins are the effective ways to marker is a useful tool for identifying small red-shift and broaden the absorption bands of organisms, such as Ozobranchus spp. Two species of porphyrins. Push-pull structure, containing an leeches present along the Florida Atlantic coast are electron withdrawing group on one side of porphyrin Ozobranchus branchiatus and Ozobranchus margoi. acting as a “pull” and electron-donating group on the DNA barcoding was applied to samples of both other side acting as a “push”, can facilitate intra/inter species of leeches obtained from sea turtles captured molecular electron/energy transfer. To synthesize at Indian River Lagoon and the St. Lucie Nuclear unsymmetrical push-pull extended porphyrins, the Power Plant in Florida. The O. branchiatus leech was unique set of reactivity of 2-nitro porphyrins is added as a new species to the National Center for explored here. Antipodal bromination of 2-nitro Biotechnology Information (NCBI) GenBank using porphyrins gives β,β’-brominated porphyrins. This two different DNA sequences: GU985465 and regioselective bromination of nitro porphyrins serves GU985466. O. margoi is already present in GenBank as an ideal starting point to prepare unsymmetrical (AF003268), but a new genetic sequence was added push-pull porphyrins through b-position using the (GU985467) due to the fact sampled leeches were methodologies developed in our laboratory. The found on loggerheads (Caretta caretta) at a different Heck reaction on porphyrin 1 and 2 using methyl location. acrylate gives benzoporphyrins 3 and 4. Subsequent acetylation, benzoylation, and denitration of 269. Optimizing the Expression of Alkaline porphyrin 3 and 4 give unsymmetrical π-extended Phytase in Pichia pastoris push-pull porphyrins 5-8. Mimi Yang, Pushpalatha Murthy, Steven C. Johnson. Department of chemistry, Michigan Technological University, Houghton, Michigan, United States. Phytases are a family of enzymes that catalyze the hydrolysis of phytic acid (myo-inositol

271. Synthesis and Structural Characterization of Terphenyl Scaffolded S- C-S Palladium Pincer Complexes and Studies 272. Interactions of Hsp70 Chaperones with of Their Catalytic Activity in the Suzuki Fe-S Cluster Scaffold Proteins ISU/IscU Coupling Reaction Wen-I. Luo,1 James A. Cowan.1,2 1Ohio State Paul R. Challen,1 Man Lung Desmond Kwan,1 Biochemistry Program, The Ohio State University, John D. Protasiewicz,2 Wilson Luu,1 Mark J. Columbus, OH, United States; 2Department of Johnson,1 Amy R. Krystosik,1 David W. Beach,1 Chemistry, The Ohio State University, Columbus, David F. Essi,1 Sean P. Steenberg.1 1Department of OH, United States. Chemistry, John Carroll University, University 2 Iron-sulfur (Fe-S) clusters are crucial cofactors in Heights, Ohio, United States; Department of biological systems. A complicated machinery Chemistry, Case Western Reserve University, composed of multiple proteins is required to Cleveland, Ohio, United States. synthesize Fe-S clusters in vivo. Details regarding the

The pincer ligand precursor 2,6-(p-tolylSCH2C6H4)2- mechanism and the regulation of this machinery are 4-I-C6H3 reacts with Pd2(dba)3 to give the new still unclear. It has been acknowledged that an Hsp70 palladium pincer complex 4. Compound 4 has been chaperone is involved in this machinery through fully charaterized, including structural interaction with the Fe-S cluster scaffold protein ISU characterization by single crystal X-ray diffraction (eukaryotic) or IscU (prokaryotic). To identity the methods. The results of the crystallographic work on driving force and to probe the underlying mechanism 4 reveal a twisted type pincer complex not unlike behind this interaction, we have examined the related terphneyl pincer complexes. We have interaction of chaperones with scaffold proteins investigated the catalytic activity ot this compound in through biophysical approaches. Characteristics of the Suzuki coupling reaction. this interaction were analyzed by isothermal titration calorimetry (ITC) and fluorescence anisotropy. In addition, to distinguish similarities and differences in eukaryotic and prokaryotic systems, a cross-system comparison was conducted. Chaperone pairs: human mortalin and Thermotoga maritima DnaK (Tm DnaK), as well as scaffold protein pairs: human ISU and Tm IscU were used as models for the cross- system comparison. These findings provide mechanistic insights concerning the role of chaperones in Fe-S cluster biogenesis, and demonstrate diversity regarding Fe-S cluster biogenesis among species.

273. Quantification of CH-π Interactions: A Cautionary Note to Simplified Models for Aromatic Interactions

Bright U. Emenike, Benjamin W. Gung. Department The 1,4-substituted 1,2,3-triazole addition product of Chemistry & Biochemistry, Miami University, was synthesized in nearly equal yields when left open Oxford, OH, United States. to air or when sealed in an oxygen atmosphere. In contrast, sealed or sealed in an inert atmosphere (N2) A 1,9-disubstituted triptycene system was used to resulted in much lower yields. reveal an attractive interaction between a substituted α benzene ring and an -substituted acetate group in 275. Tailoring Carbohydrates To Capture solution. The free energy of interactions was measured by variable temperature 1H-NMR Shiga Toxin Variants experiments to distinguish between the two possible Hailemichael O. Yosief, Suri S. Iyer. Chemistry, conformations: syn and anti. The interaction energies University of Cincinnati, Cincinnati, Ohio, United show a linear relationship with Hammett constants States. (R2=0.90). While this could imply direct benzene- substituent interactions, the free energy correlates Shiga toxin 1 and 2 are the major virulence factors of E.coli O157:H7. This particular strain of E.coli is better with the acidity of the α-protons of the acetate known to cause bloody diarrhea which proceed to group (R2= 0.98), revealing a predominant CH-π hemolytic uremic syndrome in 10-15% of the interaction. X-ray structure shows that the syn 110,000 annual cases of E.coli infection in the USA. conformation is preferred in the solid state with the Shiga toxins (Stxs) use globotrioacylceramide (Gb3), α ∼ nearest CH-benzene distance as 3.0 Å, while the a glycolipid, as a receptor to bind and invade body α ∼ Br (substituent)-benzene is 4.0 Å. cells. Studies have indicated that Stx2 is more toxic than Stx1 and it has been associated with severe forms of E.coli infections. Using the glycolipid receptor (Gb3) as a starting point and applying biotin-streptavidin chemistry, it has been possible to develop Gb3 analogs which can detect and differentiate Shiga toxins. These Gb3 analogs are robust at ambient temperature, sensitive and selective to be used in diagnostics. Here, our target molecules and their synthesis is presented.

276. Manipulations with Fused-Ring Sydnones 274. Investigations into the Aerobic Synthesis Erik Dihrkop, Kenneth Turnbull. Department of of Triazoles Via Copper Catalyst Chemistry, Wright State University, Dayton, OH, United States. Anthony Lam, Daniel T. Esterline. Department of Chemistry, Thomas More College, Crestview Hills, 3-(2-aminophenyl)sydnone and 3-(2-amino-5- KY, United States. bromophenyl)sydnone (cf. 1) have been converted to the corresponding triphenylphosphine imides (cf. 3) The copper catalyzed reaction of phenylboronic acid by two methods. Various fused-ring sydnones (cf. 4) with sodium azide immediately followed by addition have been prepared in good yields by treatment of the of various alkyne compounds in a one-pot reaction phosphine imides with aryl isocyanates or was reported by Tao et al (Tet. Lett., 48,20, 2007, isothiocyanates in an aza-Wittig process. Extension 3525-3529). Since these one-pot “click” reactions to alkyl congeners, and subsequent deprotection only work in an open vessel, various aerobic vs strategies, have been explored. The scope and anaerobic conditions for the reaction of limitations will be discussed. phenylboronic acid, sodium azide, and propargyl acetate were investigated.

action of silver in the body is unknown. We hypothesize that argyrophilic proteins are involved in the anticancer capabilities of recently developed silver carbene complexes (SCCs). To determine which proteins were interacting with silver in the body several methods were used. Optimal buffering conditions for both biological samples and silver were developed to prevent precipitation of the silver or the protein. Immobilized metal affinity chromatography (IMAC) was used to develop a procedure to separate out proteins isolated from lung cancer cell line NCI-H460 with an affinity for silver. Two different columns were used to immobilize silver a polystyrene based resin with thiourea functionality and a HisTrap FF column, were modified to bind silver. The interaction of silver with common biological buffers was characterized using x-ray crystallography. The results of the silver IMAC 277. Observation of Reversible Block in comparison with alternative methods will be Copolymer Micellization by NMR Relaxation presented. Gregg M. Wilmes, David J. Arnold, Kevin S. 279. Poly(arylene Ether)s Bearing Pendant Kawchak. Chemistry, Eastern Michigan University, Benzoxazoles Ypsilanti, MI, United States. Disraeli Kusmus, Eric Fossum. Department of Block copolymers are composed of regions Chemistry, Wright State University, Dayton, OH, exhibiting different chemical properties. They can United States. show self-assembly into regular structures on the order of tens of nanometers; for example, in solution Poly(arylene ether)s, PAEs are renowned for their block copolymers can self assemble into micelles. thermal and chemical stability making them suitable Amphiphilic diblock copolymers were synthesized by for a wide variety of end uses. A long sought after microwave-assisted reactive atom-fragment chain goal in PAE chemistry is the facile introduction of transfer (RAFT) techniques. The hydrophobic blocks functional groups in order to modify their properties, consisted of either a high glass transition temperature without sacrificing the integrity of the backbone. (Tg) material (poly[methyl methacrylate]) or a low Tg Recent advances in the syntheses of PAEs via (poly[methyl acrylate]) material. The hydrophilic nucleophilic aromatic substitution, NAS, reactions of blocks were either poly(methacrylic acid) (high Tg) or activated 3,5-difluoro aromatic systems has provided poly(acrylic acid) (low Tg). The reversible self- access to materials that can serve as a versatile assembly of the polymers was monitored as a platform to introduce a wide variety of functional function of temperature and solvent polarity by groups. This presentation will describe the synthesis, measurement of their longitudinal (T1) and transverse characterization, and polymerization behavior of 2- (T2) NMR relaxation time constants. T1 and T2 (3,5-difluorophenyl)benzoxazole, 1, as well as the behave differently as functions of molecular size. The properties of the resulting polymers. The synthesis of onset of micellization may be identified by a 1 was achieved by the reaction of 3,5-difluorobenzoic divergence in the T1 and T2 values of nuclei in the acid with 2-aminophenol in polyphosphoric acid. The core of the micelle. NAS behavior of 1 was probed by a combination of 13C NMR spectroscopy and model reactions and was 278. Development of an Argyrophilic Protein shown to be sufficiently high to allow the synthesis Profile of high molecular weight PAEs, bearing a pendant benzoxazole ring, via reaction of 1 with a variety of Stephanie M. Bilinovich, Michael C. Deblock, bisphenols under typical NAS conditions. The Matthew J. Panzner, Wiley J. Youngs, Thomas C. resulting PAEs were fully characterized by 1H and Leeper. Department of Chemistry, University of 13C NMR spectroscopy, GPC, TGA, and DSC Akron, Akron, OH, United States. analysis. Silver based drugs have been shown to be effective antineoplastic agents but the exact mechanism of

Aaron T. Setterdahl, Kacee Lett, George A. Huth, Samantha Strom, Megan Lamb, John W. Halfacre. Department of Chemistry, Indiana University Southeast, New Albany, IN, United States. Genome sequencing of thousands of organisms has resulted in databases of gene sequences that code for many previously unknown proteins. A number of 280. Site-Directed Mutagenesis of the Protein- these proteins are highly conserved between diverse Protein Contacts in the Yeast mRNA organisms. Sequence analysis of the photosynthetic Processing Complex bacterium Rhodobacter sphaeroides reveals several Jillian A. Parker, Thomas C. Leeper. Chemistry, uncharacterized proteins that are highly conserved University of Akron, Akron, OH, United States. among many bacteria. Individual gene studies have been done for several of the conserved genes found in Hrp1 and Rna15 are two complex stabilizing proteins this bacterium. The genes studied here have been which have been shown to interact during formation [1] shown to be transcribed in response to a transition of the yeast 3’-end processing complex. Along with from light to dark conditions. The gene sequence of their cognate RNA, these two scaffolding proteins RSP2796 closely resembles an amidohydrolase stabilize and direct correct 3’-end mRNA cleavage enzyme by sequence similarity searches. This gene and polyadenylation in Saccharomyces cerevisiae. has been cloned and will be expressed to verify the These mechanisms of mRNA synthesis compensate enzymatic function. RSP2415 encodes a previously for the highly complicated and less conserved yeast uncharacterized protein, and this gene has also been genome. The positioning element (PE) and the cloned for further analysis. RSP2234 has also been efficiency element (EE), two conserved regions of cloned, and sequence analysis has predicted a wide the mRNA, are recognized by Rna15 and Hrp1, range of function, from a DNA-binding protein, to an respectively, and direct precise ternary complex [2] SAM-domain protein, or a glycosylase enzyme. formation. However, mutations in the primary These three genes are among about 20% of the total sequence of these proteins have been shown to number of genes in R. sphaeroides that have no disrupt their protein-protein contact and consequently known function. Individual gene studies such as this inhibit formation of the RNP (ribonucleoprotein) [1] are necessary to determine the functions of the complex. The cleavage and polyadenylation unknown gene products to move research forward. complex formed by the Hrp1 and Rna15 interaction will be studied using cognate RNA and various 282. Hemoglobin: A Reliable Indicator of combinations of both mutant and wild-type proteins. 15 Blood in Archaeological Materials? A N HSQC NMR spectroscopy experiment focused on the Rna15 domain will be used to detect Daniel Fraser,1 Ruth Ann Armitage.2 1Department of disruption by mutant Hrp1 in the overall formation of Chemistry and Physical Science, Lourdes College, the RNP complex. Sylvania, OH, United States; 2Department of Chemistry, Eastern Michigan University, Ypsilanti, 1. Leeper, T. C.; Qu, X.; Lu, C.; Moore, C.; Varani, MI, United States. G. Novel protein-protein contacts facilitate mRNA Using clinical test strips for field testing rock 3’-processing signal recognition by Rna15 and Hrp1. paintings for the presence of blood yields negative The Journal of Molecular Biology (accepted results after just a few weeks or months of February 2010). environmental exposure. The utility of such strips in

detecting blood over archaeological time scales, then, 2. Zhao, J.; Hyman, L.; Moore, C. Formation of is unlikely. Understanding the chemical changes that mRNA 39 Ends in Eukaryotes: Mechanism, the heme undergoes will aid in determining whether Regulation,and Interrelationships with Other Steps in or not it is possible to identify blood on surfaces mRNA Synthesis. Microbiology and Molecular through other, more reliable, means. We have Biology Reveiws [Online] 1999, 63, 405-445. undertaken thin layer chromatography to separate the different heme compounds extracted from blood- 281. Identification and Characterization of based paints applied to stone and glass surfaces and Highly Conserved Proteins from the stored for up to eight years under both laboratory and Photosynthetic Bacterium Rhodobacter field conditions. The fractions and direct samples sphaeroides were characterized by UV-visible spectroscopy to determine the structural changes to the heme that

would lead to decreased reactivity in the The [4 + 3] cycloaddition reaction is a powerful tetramethylbenzidine reaction used in the clinical test method for the creation of seven-membered rings. strips. Characterization by direct analysis in real time Many natural products contain polycyclic systems mass spectrometry shows that heme does persist, with seven-membered rings. We have been albeit at extremely low levels. These studies will help developing a gold catalyzed intramolecular [4 + 3] us to develop a more reliable protocol for identifying cycloaddition reaction. We have utilized furan as the blood in archaeological samples. 4C component and propargyl acetates as the 3C component with various Au(I) or Au(III) catalysts for 283. A Two Method Comparison of Acylation the intramolecular [4 + 3] cycloaddition. The Techniques for Sydnones, Using synthesis of precursors and results of the gold Montmorillonite K-10 Clay or Bismuth catalyzed intramolecular [4 + 3] cycloaddition Triflate/Lithium Perchlorate under Thermal reactions will be discussed further.

or Microwave Conditions Amber Rumple, Kenneth Turnbull, Jennifer Fischer. Department of Chemistry, Wright State University, Dayton, OH, United States. 285. Identification of Polycystin 1 on A variety of 3-phenyl-4-acylsydnones were Erythrocytes Using a Cell Surface synthesized using Montmorillonite K-10 clay or Immunofluorescence Staining Protocol bismuth triflate/lithium perchlorate as catalysts and a variety of anhydrides (Scheme 1). The efficiency of Timothy T. Dick, Sarah W. Abuonk, Nancy J. one catalyst versus the other in microwave and Pettibone, Angela M. Shouse. Department of thermal settings was explored. Thermally, the Biology, Owensboro Community and Technical acylated sydnones were synthesized in good yields College, Owensboro, Kentucky, United States. after a time period of 24 hours, for the simplest Polycystin 1 is a plasma membrane bound anhydrides, and up to many days for the more glycoprotein with probable cell-cell and cell-matrix complicated anhydrides when using Montmorillonite adhesion properties. Polycystin 1 may also interact K-10. Using bismuth triflate and lithium perchlorate with Polycystin 2 which serves as a calcium channel. the sydnones could be synthesized in 6.5 hours. With Polycystin 1 and 2 have been found in various cells the use of microwave irradiation the rate of the throughout the body. Increased membrane fluidity in reaction was significantly increased bringing reaction the erythrocytes of individuals with aberrant times down to mere hours for the Montmorillonite K- Polycystin 1 has been observed. However, there are 10 method and minutes for the bismuth triflate and no reports which definitively demonstrate the lithium perchlorate approach. The scope and presence or absence of Polycystin 1 in the limitations of these processes will be discussed. erythrocyte membrane. This study uses immunofluorescence to determine the expression of Scheme 1: Polycystin 1 on the erythrocyte.

286. Investigation of Carbocations in a Solvent-Free Environment Meghan R. Wagner, James Mack. Department of Chemistry, University of Cincinnati, Cincinnati, Ohio, United States. Carbocations are typically formed in solution during SN1 reactions. Since these reactions are solvent dependent we seek to learn whether carbocations can

be created in a solventless system. Using solvent-free 284. Gold Catalyzed Intramolecular [4 + 3] high speed ball milling we reacted triphenylmethyl Cycloadditons between Furan and Propargyl bromide with potassium iodide and compared these result to what is observed by conventional solution Acetates based methods. Ryan C. Conyers, Ben Gung. Chemistry and Biochemistry, Miami University, Oxford, Ohio, United States.

287. Metallomics: A New Approach To Study intracellular Zn levels. Using SEC-ICPMS we also the Metallome of Macrophages and Its observed that during H. capsulatum infection a Response upon Infection significant difference in the abundance of certain Zn binding species between MΦ depending upon Qilin Chan,1 Michael S. Winters,2 George S. Deepe,3 1 1 cytokine activation. Our results establish a link Joseph A. Caruso. Department of Chemistry, between Zn abundance and H. capsulatum University of Cincinnati, Cincinnati, OH, United 2 intracellular growth while suggesting a role for Zn in States; Department of Infectious Diseases, College host defense. The following LC-ESI-MS/MS study of of Medicine, University of Cincinnati, Cincinnati, 3 the SEC fractions revealed the presence of some Zn- OH, United States; Veterans Affairs Hospital, binding proteins which may be involved in the Zn College of Medicine, University of Cincinnati, regulation. Cincinnati, OH, United States. Macrophages function as ‘pathogen sensors’ and play In summary, we have shown that Zn species, in an important role in the initiation of inflammatory addition to Fe, are involved in the host defense responses, elimination of pathogens, manipulation of mechanism. With chromatography like SEC, ICPMS the adaptive immune response. Nutrient deprivation is able to qualitatively and quantitatively measure is a defense mechanism utilized by the host when a metals in host cells before and after infection with the pathogen is ingested by macrophages. For example, intracellular pathogen H. capsulatum. This Fe sequestration has been identified as a defense methodology could provide invaluable insights into strategy utilized by macrophages against pathogens metal regulation of a number of other diseases as well like Mycobacterium tuberculosis, Salmonella intracellular pathogen infections including M. enterica, and Histoplasma capsulatum. However, no tuberculosis, Salmonella enterica, Listeria accurate measurement of metals has been reported in monocytogenes, and Chlamydia. macrophages. 288. Formation of a Sydno[3,4-a]indolone and Using inductively coupled plasma mass spectrometry Reactions Thereof (ICPMS) we have measured concentrations of 10 Daniel Brown, Ryan Vikan, Kenneth Turnbull. metals, simultaneously, in murine peritoneal and Department of Chemistry, Wright State University, bone marrow derived macrophages. Significant Dayton, Ohio, United States. concentration differences of Mg, K, Ca, Fe and Zn were observed between the two types of An attempt was made to prepare and isolate a macrophages. Size-exclusion chromatography (SEC) sydnoindolone 2 from treatment of 3 (2- analysis with element specific detection, provided by carbomethoxy-phenyl)sydnone 1 with base. While, ICP-MS, was used to separate specific metal species, apparently, the sydnoindolone was too unstable for producing both qualitative and quantitative results of isolation, evidence for its existence was obtained metal binding sugars, proteins, and/or peptides in the from trapping experiments with organolithium and cells. organomagnesium reagents. The resultant hydroxysydnoindoles 3a-d were obtained in modest In addition we investigated the metal regulation yield. Reaction of the vinyl hydroxysydnoindole during infection of macrophages with the fungal species 3d with acids gave novel fused ring vinyl pathogen Histoplasma capsulatum. H. capsulatum congeners 4a-c of, as yet, unspecified evades the innate and adaptive immune responses and stereochemistry. Other novel avenues to the thrives within resting macrophages (MΦ) in vitro. hydroxysydnoindole 3d are under exploration. The Cytokines that induce antimicrobial activity of MΦ scope and limitations will be discussed. such as interferon gamma (IFN-γ) or granulocyte monocyte colony stimulating factor (GM-CSF) are necessary to control H. capsulatum infection in mice. Conversely interleukin-4 (IL-4) inhibits the killing of intracellular pathogens. We examined alterations in metal homeostasis of murine MΦ exposed to activating cytokines infected with H. capsulatum. Restriction of Zn was observed in IFN-γ and GM- CSF treated MΦ versus resting MΦ infected with H. 289. Novel Synthetic Approach to an capsulatum. IL-4 reversed anti-fungal activity of Antifouling Furoic Acid GM-CSF bone marrow derived MΦ while increasing

Benjamin R. Eyer, S. Shaun Murphree. Department and 2 (n), along with bisphenolates in NMP at 180 of Chemistry, Allegheny College, Meadville, PA, °C, provided the corresponding linear sulfonated United States. poly(arylene ether)s, sPAEs with number average molecular weights (M ) ranging from 16,000 to Progress on a novel sulfone-based synthetic approach n 81,000 Daltons as determined by gel permeation to the naturally occurring furoic acid 4 is reported. chromatography (GPC). The ion exchange capacities The synthesis launches from commercially available (IEC) were tuned and ranged from 2.09 for the citronellyl acetate (1), which is converted to the 1,3- homopolymer, m=1 and n=0, to 0.9 for the copolymer diketone 2. Subsequent conversion to the sulfonyl with a ratio of m=1.9 and n=3. All of the polymers furan 3 and oxidative desulfonylation provides access 1 13 were characterized using H and C NMR to the target compound. spectroscopy, thermogravimetric analysis (TGA), and

differential scanning calorimetry (DSC). All of the copolymer samples also formed tough peelable films when cast from DMSO solutions and were tested for conductivity measurements and water uptake (WU).

290. Microwave-Assisted Benzylic Bromination Jeremy D. Mason, S. Shaun Murphree. Department of Chemistry, Allegheny College, Meadville, PA, United States. The NBS-mediated bromination of benzylic substrates has been adapted to sealed-tube microwave-assisted conditions. For example, methyl p-toluate (1) is converted to the corresponding benzyl bromide (2) in high yield by heating at 140°C for 10 min in methylene chloride using AIBN as a radical initiator. Solvent, substrate, and stoichiometry parameters are discussed.

292. Metabolic Effects on Mitochondrial Trans-Membrane Potential and Cellular Morphology in CV-1 Cells Melissa Pergande, Guilherme Indig. Department of 291. Copoly(arylene Ether)s Carrying Chemistry and Biochemistry, UW-Milwaukee, Pendant (3-Sulfonated) Phenyl Sulfonyl Milwaukee, Wisconsin, United States. Groups The growth of mammalian cells is primarily fueled Kimberly Kern, Fadwa Constandinidis, Eric through the catabolism of two energy substrates: Fossum. Department of Chemistry, Wright State glucose and glutamine. Various tumor cell lines have University, Dayton, Ohio, United States. been reported to consume large quantities of glutamine through glutaminolysis in order to A series of new sulfonated copoly(arylene ether)s facilitate increased nucleotide biosynthesis and containing the sulfonic acid group, located on a subsequently aid in cellular proliferation. This pendant phenyl sulfonyl moiety, at every repeat unit process results in an enhanced mitochondrial trans- was synthesized using 3-sulfonated-3’,5’- membrane potential, a common tumor cell difluorophenyl sulfone, 1, 4,4’-difluorophenyl phenotype, which enables cationic dyes to localize sulfone, 2, and a variety of bisphenols. In addition, a more efficiently in the mitochondria of tumor cells comparison of pendant versus backbone placement of compared to normal cells. Rhodamine-123, a cationic the sulfonic acid group was carried out using model mitochondrial dye, has been shown to be retained in compounds. A conventional nucleophilic aromatic CV-1 cells with relatively no observed toxicity. In substitution (NAS) process was utilized for the model this study, the effect of energy substrate availability reactions as well as on mitochondrial trans-membrane potential and homopolymerization/copolymerization. cellular morphology was investigated in CV-1 cells. Polymerization reactions of various ratios of 1 (m),

Changes in mitochondrial trans-membrane potential across the three CSF sample types. Six protein and cellular morphology were observed by epi- families with possible protein markers were further fluorescence microscopy. Our experimental results identified, and may be considered as possible focus suggest that energy substrate availability modulates areas for discovering valuable biomarkers to preclude both mitochondrial trans-membrane potential and cell the debilitating or deadly vasospasm. morphology. This study may shed some light on the reasons why tumor cells typically show an enhanced 294. Towards the Total Synthesis of mitochondrial trans-membrane potential compared to Haplomyrtin normal cells. Nora E. Hunter, William A. Feld. Chemistry, 293. Investigation of Metalloproteins as Wright State University, Dayton, Ohio, United Putative Biomarkers in Cerebrospinal Fluid States. To Predict Cerebral Vasospasm Haplomyrtin, a 1-aryl-2-3-naphthalide lignan obtained from Turkish Haplophyllum myrtifolium Yaofang Zhang,1 Joseph F. Clark,2 Gail Pyne- 3 1 1 offers a number of synthetic challenges with the Geithman, Joseph Caruso. Department of incorporation of two aromatic hydroxyl groups at Chemistry, University of Cincinnati, Cincinnati, OH, positions 4 and 7 on the naphthalene ring system and United States; 2Department of Neurology, University regiospecific condensation of the γ-lactone ring. The of Cincinnati, Cincinnati, OH, United States; total synthesis of haplomyrtin is currently being 3Department of Neurosurgery, University of pursued with commercially available vanillin and Cincinnati, Cincinnati, OH, United States. piperonal in a total of 10 separate steps. All steps Cerebral vasospasm (CV) refers to physical have excellent reproducibility with good yields. This narrowing of brain cerebral arteries due to over- strategy includes halogenations of protected vanillin contraction of the arterial wall, which often arises and incorporation of the fully functionalized pendant following a subarachnoid hemorrhage (SAH). aryl ring through a lithium-halogen exchange Between the ictus of SAH and its CV complication, followed by coupling with piperonal. The C-7 there is a 3-7 days delay, which provides a time hydroxyl group is placed by the in-situ formation of a window to predict and possibly prevent the onset CV. benzofuran subsequent Diels-Alder reaction with Since the precise pathomechanism of CV is still dimethyl acetylenedicarboxylate (DMAD), unclear and approaches for predicting it are deprotection and regiospecific reduction of the o- inefficient, more effective ways of predicting CV hydroxyester followed by transesterification to close need to be developed. As a protective nourishing the g-lactone ring. Investigating the use of 4-methoxy fluid flows through the subarachnoid space, benzyl bromide instead of benzyl chloride as a cerebrospinal fluid (CSF) closely relates to the health protecting group, addressing the instability of the states of central nervous system (CNS). Analysis of secondary alcohol from the coupling reaction with CSF can provide invaluable information to diagnose, piperonal as well as the poor yields and difficult treat and prevent diseases of the CNS because of its isolation of the Diels-Alder reaction product are the relatively direct representation of events in the brain. goals of this project. Therefore, we assume that the components in CSF and their alterations may reflect the state of 295. A Comparison of Atmospheric Polycyclic aneurismal SAH and the development of vasospasm. Aromatic Hydrocarbons Profiles from Pine In this study, three types of CSF from healthy Needles and High-Volume Samplers To control, and patients who suffered SAH and its Determine Pine Needles’s Useability as a complication, CV, were separated using size Sampler exclusion chromatography with selective metal detection by ICPMS for characterizing size Timothy A. Tomashuk, Audrey McGowin. distribution of metal species. Various molecular Department of Chemistry, Wright State University, distribution patterns were exhibited at different metal Dayton, Oh, United States. detection points (Fe, Cu, Ni, Zn and Pb). Further Samples of filters from High-volume (HiVol) identification on possible metallopeptides and samplers of particulate matter (PM) with a size of 10 metalloprotein fractions from the three sample types micrometers or less were deployed in Moraine and were made via electrospray MS in combination with Yellow Springs, OH, by the Regional Air Protection the Spectrum Mill data base search engine accessing Control Agency and analyzed for five months for the appropriate data bases. Comparisons were generated Environmental Pollution Agency (EPA) 16 to show suggested protein similarities or differences polycyclic aromatic hydrocarbons (PAHs). Pine

needles on trees near the HiVol samplers were also (vasoconstriction). This in turn leads to systemic collected and analyzed for a comparison with the hypertension. Fortunately, the hypertensive effect can active samplers to estimate atmospheric PAH be alleviated/prevented by removing free Hb and low concentrations. Pine needles were found to collect MW PolyHbs from the PolyHb mixture. Free Hb and lower molecular weight (LMW) compounds far more low MW PolyHbs can be reduced/removed two than HiVol sampler and thus their profiles shown to ways: 1) by synthesizing large MW PolyHbs and 2) compliment the HiVol sampler profile which collect by thoroughly separating free Hb and low MW higher molecular weight (HMW) compounds. PolyHbs from PolyHb solutions. In this work, Concentrations for filters and Yellow Springs pine glutaraldehyde was used to non-site specifically needles, except for Moraine pine needles, increased cross-link/polymerize human Hb to yield high MW as the average temperature decreased. The human PolyHb (PolyhHb) solutions that were frozen atmospheric concentrations (∑PAHatm) were in either the tense or relaxed quaternary states. calculated for the last ten PAHs that overlapped in PolyhHb solutions were subjected to extensive the pine needle and filter profiles (Fluoranthene- diafiltration to remove free Hb and low MW Benzo(ghi)perylene). The ∑PAHatm calculated for PolyhHbs. The PolyhHbs synthesized in this study Moraine ranged from 0.32 ng/m3 to 1.69 ng/m3 while possess: high MW, distinct quaternary state, distinct 3 Yellow Springs ranged from 0.32 ng/m to 4.16 reactivities with O2 and CO, similar NO ng/m3. These values are lower than expected dioxygenation rate constants, distinct autoxidation especially for Moraine since there is industry nearby. rate constants, high viscosity and low colloid osmotic PAH compounds from the pine needles were mostly pressure. We also evaluated the ability of PolyhHbs associated with the vapor phase while the filters to transport O2 in a mathematical model of a hepatic collected PAHs in the PM10 phase. Pine needles hollow fiber bioreactor. PolyhHbs with low O2 have been shown to be useful in showing the affinities were more effective in oxygenating cultured additional LMW PAHs present in the atmosphere hepatocytes inside the bioreactor compared to high which HiVol samplers fails to collect. O2 affinity PolyhHbs. Taken together, our results show that it is possible to synthesize high MW 296. Biophysical Properties and Oxygenation PolyhHbs with no free Hb and low MW PolyhHb Potential of High Molecular Weight components that are capable of transporting O2 to Glutaraldehyde Polymerized Human cultured cells. Hemoglobins Maintained in the Tense and 297. Primary Amine-Metal Lewis Acid Relaxed Quaternary States Derived Bifunctional Catalysts for Ning Zhang,1 Yiping Jia,2 Guo Chen,1 Pedro Enantioselective Reactions Cabrales,3 David R. Harris,1 Andre F. Palmer.1 1William G. Lowrie Department of Chemical and Philias Daka, Zhenghu Xu, Alex Alexandru, Hong Biomolecular Engineering, The Ohio State Wang. DEPARTMENT OF CHEMISTRY AND University, Columbus, OH, United States; BIOCHEMISTRY, MIAMI UNIVERSITY, 2Laboratory of Biochemistry and Vascular Biology, OXFORD, OHIO, United States. Division of Hematology, Center for Biologics The discovery of bi/multiple catalysts has attracted Evaluation and Research (CBER), Food and Drug intense attention in recent years due to their 3 Administration (FDA), United States; Department of effectiveness. This successfulness can be attributed to Bioengineering, University of California, San Diego, a cooperative effect between organo and transitional United States. metal entities. One of the biggest challenges in Recent clinical evaluations of glutaraldehyde constructing Lewis acid-Lewis base bifunctional polymerized hemoglobins (PolyHbs) have catalysts is the obligatory coexisting of a basic and demonstrated adverse effects. A popular hypothesis acidic functional group on the same moiety. This to explain these effects is that vasoconstriction is cooperation can be beneficial or detrimental to caused by the presence of free hemoglobin (Hb) and catalyst activity depending on the design. It follows low molecular weight (MW) PolyHbs in the PolyHb that, strength of the acid/base, the distance between mixture. These molecules can either pass through them and their orientation play a cardinal role to the pores in the wall of blood vessels or get very close to design of bifunctional catalysts. the blood vessel wall. There, they are able to readily scavenge nitric oxide (NO) from the surrounding Here, a Lewis base and an acid are tethered within endothelial cell layer. In response to NO scavenging, the same catalytic moiety. Chiral primary amine the surrounding smooth muscle layer constricts bidentate ligands were used as the Lewis bases, while

transition metals serve as the Lewis acids; they serve injected into chick embryos as Pt (IV), Rh (III), and Pd to assemble the structure and provide the rigidity on (II) salt solutions or PGMs mixtures at 0.1, 1.0, 5.0, or the scaffold; a much needed property for asymmetric 10.0 ppm. The LD100 was established at 10 ppm. catalysis (Figure 1). These systems exhibited good Micro-Raman maps were recorded on the paraffin activity (3h), lower catalytic loading (5%) and water embedded tibiotarsus cross-sections. Anomolous tolerance towards direct asymmetric aldol reaction calcium inclusions were detected at PGM between cyclohexanone and aldehydes in good yield concentrations as low as 1 ppm, which is sufficient to (up to 94%) and excellent stereoselectivity, >99% ee. impede circulation within the cartilage matrix and to (Sceme 1). cause bone deformities. The following bone properties were analyzed and quantified: a) age of Figure 1 mineral crystals and carbonate content, b) degree of mineralization of the collagen matrix and possible losses in the organic/inorganic bone components, and c) mineral crystallinity. Additional tissue samples were chemically digested and examined by FAAS to determine the average calcium content. X-ray fluorescence meausrements were performed to show the calcium distribution along the inner and outer cross-sections of tibiotarsi. All three techniques show corroborating results that the PGMs exposures led to a premature aging process of bone tissue and heterogenous calcium inclusions.

Undergraduate poster session: CHED.

Scheme 1 299. Functionalized, Semicrystalline Poly(ether Ketone)s Via In Situ Modification Chemistry Raghavendhar Reddy Kotha, Eric Fossum. Department of Chemistry, Wright State University,

Dayton, Ohio, United States. 298. Toxicity of Platinum Group Metals in Functionalized, semicrystalline, soluble, linear Chick Embryo Tibiotarsi poly(ether ketone)s, PEKs were synthesized using an AB monomer, 3,4,5-Trifluoro-4’- Jessica Dagher,1 Tai Lam,1 Jennifer Monahan,1 3 hydroxybenzophenone. ‘Pre’ and ‘post’ Kent Weaver,1 Allie Meyerhoefer,1 Marjorie polymerization functionalization of the PEK system Markopoulos,1 Britney NeJame,2 Jacob Cowley,2 was done using phenol, 4-bromophenol, and 3- Robert Slaughter,3 Larry Burggraf,3 Zofia Gagnon,2 aminophenol. Ioana Pavel.1 1Department of Chemistry, Wright Initially, 10 and 25 mol % ‘pre’ and 10 mole % ‘post’ State University, Dayton, OH, United States; modifications were done using the three 2Department of Environmental Science and Policy, functionalizing agents. The solubility and molecular Marist College, Poughkeepsie, NY, United States; weights of the functionalized polymers were 3Department of Engineering Physics, Air Force increased significantly compared to the Institute of Technology, Wright Patterson, OH, corresponding unfunctionalized homopolymer. The United States. 1 13 polymers were characterized by H and C NMR Platinum group metals (PGMs) have been shown to spectroscopy, Gel Permeation Chromatography accumulate in various tissues of organisms, but their (GPC), Thermogravimetric Analysis (TGA), and toxicity is not well-known. A chick embryo model Differential Scanning Calorimetry (DSC). DSC was chosen for qualitative and quantitative analysis results showed that the crystallinity of the polymer of the changes in the chemical composition of was tuned by the amount of functionalizing agent tibiotarsi caused by PGMs exposure. The following used. The homopolymer was highly crystalline and spectroscopic techniques were employed to address the crystallinity decreased as the amount of the these aspects: micro-Raman, flame atomic functionalizing agent increased. When 50 mol % or absorption, and X-ray fluorescence. PGMs were

greater of the functionalizing agent was utilized the PolybHb, suggesting a more complex oxidative materials became completely amorphous. processes in vivo. Our findings also demonstrate that T-state PolybHb exhibited a longer circulating half- life, slower clearance and longer systemic exposure time compared to R-state PolybHb.

301. Structural-Based Computational Drug Design: Potential Inhibitors for Influenza Virus Neuraminidase Lishan Liu, Jason W. Ribblett. Department of Chemistry, Ball State University, Muncie, IN, United States. Group one viruses of type A influenza, including avian flu and swine flu, are generally considered to 300. Synthesis, Biophysical Properties and be the more prevalent and dangerous type, as they are Pharmacokinetics of Ultrahigh Molecular usually associated with epidemics and are resistant to Weight Tense and Relaxed State Polymerized all current inhibitors. Slight differences between 151 Bovine Hemoglobins cavities of group one and group two virus’ neuraminidase point a way to design a novel potential Yipin Zhou,1 Paul W. Buehler,2 Pedro Cabrales,3 2 1 1 inhibitor for group one viruses. Yiping Jia, Guoyong Sun, David R. Harris, Amy Tsai,4 Marcos Intaglietta,4 Andre F. Palmer.1 1 Structural-based computational drug design methods Department of Chemical and Biomolecular were employed to explore new potential inhibitors for Engineering, The Ohio State University, columbus, the target protein. Several trials of ligands were ohio, United States; 2Food and Drug Administration, 3 designed based on derivatives of neuraminic acid and Bethesda, Maryland, United States; La Jolla evaluated as inhibitors of influenza neuraminidase. Bioengineering Institute, La Jolla, California, United 4 Optimized geometries of those ligands were States; Department of Bioengineering, University of determined using HF/6-311++G** and/or B3LYP/6- California, San Diego, La Jolla, California, United 311++G** techniques. Binding energies of the States. ligands bound to the N4 subtype of the Hemoglobin-based oxygen carriers (HBOCs) are neuraminidase protein were determined using currently being developed as red blood cell (RBC) AutoDock 4.0. Some known inhibitors for influenza substitutes for use in transfusion medicine. Despite viruses also were analyzed in the same way to be significant commercial development, late stage used for comparison. Comparing the binding clinical results of polymerized hemoglobin (PolyHb) information of those candidates and current ligands solutions hamper development. We synthesized two can give useful data about the potential ligands. types of PolyHbs with ultrahigh molecular weights: tense (T) state PolyHb (MW = 16.59 MDa and P50 = 302. Microwave-Assisted N-Alkylations of 41 mm Hg) and relaxed (R) state PolyHb (MW = Isatins 26.33 MDa and P = 0.66 mm Hg). By maintaining 50 Charles M. Clay. Department of Chemistry, Wright Hb in either the T- or R-state during the State University, Fairborn, OHIO, United States. polymerization reaction, we were able to synthesize novel ultrahigh molecular weight PolyHbs in distinct In light of the fact that oxindoles undergo alkylation quaternary states with no tetrameric Hb, high at both the nitrogen and the C-3 position, one route to viscosity, low colloid osmotic pressure and the ability regioisomerically produced N-alkyl oxindoles to maintain O2 dissociation, CO association and NO involves a two step process involving N-alkylation of dioxygenation reactions. PolyHbs elicited some in the corresponding isatin followed by reductive vitro RBC aggregation that was less than 6% dextran deoxygenation of the isatin. We report that isatins can (500 kDa) but more than 5% human serum albumin. be efficiently N-alkylated using a variety of bases In vitro, T-state PolybHb autoxidized faster than R- under microwave conditions. These isatins then seve state PolybHb as expected from previously reported as precursors to oxindoles using Wolff-Kishner studies, conversely, when administered to guinea pigs conditions. as a 20% exchange transfusion, R-state PolybHb oxidized faster and to a greater extent than T-state

303. Synthesis and Activity of a Novel Chiral an energy barrier ≤ 8.5 kcal/mol. This value is N-Heterocyclic Carbene-Gold Catalyst comparable to the one previously computed for the alternative SN2 reaction pathway (10.5 kcal/mol). Michael R. Holmes, Benjamin Gung. Department of However, the ET-based reductive cleavage pathway Chemistry and Biochemistry, Miami University, does not impose specific geometrical and distance Oxford, Ohio, United States. constraints with respect to substrate and cofactor as N-heterocyclic carbenes have gained popularity does SN2 pathway. This might be advantageous from recently as ligands for transition-metal catalysis. This the enzymatic point of view. poster presents a novel chiral N-heterocyclic carbene gold catalyst based on an imidazo[1, 5a]pyridine 306. Azidodeoxysugars: Synthesis and skeleton, describing the synthesis, catalytic activity, Application in Heterocycle Formation and enantioselectivity of [4+3] cycloadditions. Peter Norris, Traci Clymer, Krista Cunningham, Antony Okumu. Chemistry, Youngstown State 304. Reduction of Dibenzoyl Disulfide: A University, Youngstown, Ohio, United States. Convenient Strategy for the Synthesis of Thiols Azidodeoxysugars are essential building blocks in the synthesis of aminosugars and complex Hilary Richards, Steven Worden, Douglas J. oligosaccharides. We have observed the unexpected Schauer. Chemical Technology, Ivy Tech formation of azido derivatives during attempted Community College, Lafayette, IN, United States. diazotransfer reactions using a mannofuranose We report a convenient strategy for the synthesis of platform and have expanded this to a useful synthesis thiols. Alkyl halides are typically reacted with of azidodeoxysugars. The azide functionality then thiolates to produce thioesters that can be hydrolyzed serves as a versatile intermediate en route to to give thiols. The thiolates are generally formed by heterocycles such as triazoles and tetrazoles, some of deprotonation of foul-smelling thiocarboxylic acids. which have interesting preliminary biological We have found that sodium thiobenzoate can be activity. generated in situ from the reduction of dibenzoyl disulfide, thus providing an odor-free alternative to 307. Inhibitors of Mycobacterium tuberculosis traditional sulfur sources. This protocol obviates the Antigen 85 need for handling malodorous reagents such as Diaa A. Ibrahim, Kevin R. Trabbic, Samuel S. thiobenzoic acid and thioacetic acid by employing Adams, Aditya K. Sanki, Julie Boucau, Donald R. crystalline dibenzoyl disulfide. Ronning, Steven J. Sucheck. Department of Chemistry, The University of Toledo, Toledo, OH, 305. Reductive Cleavage Mechanism of Co-C United States. Bond in Cobalamin-Dependent Methionine Synthase Background: Currently, TB is a global health threat with nearly 500,000 new cases of multidrug- 2 2 Mercedes Alfonso-Prieto, Xevi Biarnés, Manoj resistance TB estimated to occur every year. A 1 2 1 Kumar, Carme Rovira, Pawel M. Kozlowski. number of antimycobacterial drugs work by 1 Department of Chemistry, University of Louisville, interfering with the biosynthesis of key components 2 Louisville, Kentucky, United States; Computer of the mycolylarabinogalactan (mAG). In light of this Simulation Group, University of Barcelona, observation, other enzymes involved in the synthesis Barcelona, Barcelona, Spain. of the mAG should also serve as targets for The key step in the catalytic cycle of methionine antimycobacterial drug development. One potential synthase (MetH) is the transfer of a methyl group target is the Antigen 85 (Ag85) complex, a family from the methylcobalamin (MeCbl) cofactor to the mycolyltransferases that are responsible for the homocysteine substrate (Hcy). In this work, we transfer mycolic acids from trehalose monomycolate analyze whether this mechanism is plausible from a to the arabinogalactan. Methods: Virtual thiophene- theoretical point of view. By means of a combination arbinoside conjugates were docked to antigen Ag85C of gas-phase and QM/MM DFT calculations, we (PDB code: 1va5) using Glide. Compounds with show that cleavage of the Co-C bond in a MeCbl···S good docking scores were synthesized. Target complex (S = methylthiolate substrate) takes place thiophenes were prepared by a Gewald synthesis III ·- · followed by linking to 5-thioarabinofuranosides. via a [Co (corrin )]-CH3···· Sdiradical * Select compounds were assayed for configuration, involving a change from a p corrin-type * mycoyltransferase activity using a beta-glucosidase- state from a σ Co-C one, and methyl transfer displays

coupled Ag85 activity assay. One compounds United States; 4AFRL/RXBT, Air Force Research showing inhibitory activity was soaked with crystals Lab, Wright-Patterson AFB, OH, United States. of Mycobacterium tuberculosis antigen 85C and the Due to the widespread production and use of carbon structure determined by X-ray crystallography. nanotubes in almost every area of science (ie. drug Results: The Gewald synthesis was performed by delivery, biosensors, fuel cells, dry adhesives, and treating cyclohexanone with malononitrile or ethyl thermal management systems), they are receiving cyanoacetate and sulfur in the presence of N- considerable attention for their novel mechanical, ethylmorpholine to yield a 2-amino-3-carboxylate- electrical and chemical properties. At this time of and 2-amino-3-carbonitrile-based thiophenes high exposure potential, it is critical to ascertain the respectively. The thiophenes reacted with either biological impact of these materials on likely target chloroacetyl chloride or 4-chlorobutyrl chloride and organs, tissues and cells, such as those of the lung. resulted in a series of alkyl chloro-linked thiophenes. The aim of this study was to evaluate the degree of In addition, 2-amino-3-carboxylate was reacted with cytotoxicity to human lung macrophage (U937) cells 2-chloroethyl isocyanate to form a urea in 53% yield. after exposure to unpurified or acid-purified multi- With key intermediates in hand we then explore two walled carbon nanotubes. Cells were incubated with different approaches to form a thioether linkage 5-50 µg/ml concentrations of the two different multi- between the thiophenes and the C-5 position of a walled carbon nanotubes and were assessed for methyl a-D-arabinofuranoside. In first approach, the cytotoxicity, generation of reactive oxygen species, chloro substituent of the chloro-linked thiophenes morphological changes and uptake. The results was displaced with potassium thioacetate in demonstrate that although multi-walled carbon anhydrous DMF to afford thioesters in variable nanotubes can accumulate in human lung yields. The resulting thiophenes were treated with macrophage cells to different degrees based on their NaOEt and reacted with methyl 5-Ο-p- surface chemistry, they do not lead to substantial α toluenesulfonyl- -D-arabinofuranoside. cytotoxicity when considering the average data of Unfortunately, we failed to isolate an identifiable large sets of cells. However, images of individual product using this protocol. We converting the cells demonstrate morphological changes at low tosylate to a sulfhydryl. This required peracetylation concentrations and short time points suggesting that of the arabinofuranoside with acetic anhydride to further scrutiny of nanomaterial toxicity and afford a triacetylated compound in 73% yield. The biological responses warrant additional investigation. acetylated tosylate was treated with potassium thioacetate to afford a thioester in 60% yield. The thioester was then treated with NaOMe at 50 ºC for 2 309. pH-Dependent Release Kinetics of a h. The resulting methyl 5-thio-a-D-arabinofuranoside PEGylated Protein from a Nano was reacted with the chloro-linked thiophenes to Hydroxyapatite-Coated Poly(caprolactone afford thiophene-arbinosides. One of the conjugates Fumarate) 2D Film was shown to inhibit antigen 85 and the X-ray Daniel H. Kwak,1 Ha H. Pham,1 Saumya Saurabh,1 structure of its complex with Ag85C was solved. Jinku Kim,2 Jeffrey O. Hollinger.2 1Department of Conclusions: Some of the thiopenes-arbinoside Chemistry, Carnegie Mellon University, Pittsburgh, prepared have shown inhibitory activity against Pennsylvania, United States; 2Bone Tissue Mycobacterium tuberculosis Antigen 85. The X-ray Engineering Center, Department of Biomedical structure shows the compounds are bound to the Engineering, Carnegie Mellon University, Pittsburgh, active site of the enzyme and are expected to be Pennsylvania, United States. competitive inhibitors. The need for controlled spatiotemporal release of a 308. Cytotoxicity Assessment to Human Lung drug (i.e., nucleic acid, peptide, or protein) has been a Macrophages after Exposure to Multi-Walled critical parameter in drug delivery; the delivery of Carbon Nanotubes such molecules synchronized with the physiological state of the target area can lead to increased Lin Zhu,1,3 Amanda M. Schrand,1 Andrey A. bioactivity and efficacy as well as decreased toxicity. Voevodin,4 Dong W. Chang,3 Liming Dai,2 Saber M. The pH-dependent release kinetics are analyzed for a Hussain.1 1AFRL/711 HPW/RHPB, Air Force PEGylated model protein, bovine serum albumin Research Lab, Wright-Patterson AFB, OH, United (BSA), from a hydroxyapatite nanocrystal-coated States; 2Department of Chemical Engineering, Case poly(caprolactone fumarate) (PCLF) 2D film. Western Reserve University, Cleveland, OH, United Methods include gel electrophoresis (SDS-PAGE), States; 3Department of Chemical and Material spectrophotometry (Bradford assay), and circular Engineering, University of Dayton, Dayton, OH, dichroism (CD) for protein molecular weight,

concentration and secondary structure analysis, Their Electrocatalytic Ability towards the respectively. Previous studies of PEGylated proteins Reduction of Molecular Oxygen in Acidic have shown mediated release profiles and enhanced Media structural integrity of the protein releasate. Implications of the study will elucidate a method for Gregory L. Richards, Shawn M. Swavey. protein delivery in pH-dependent physiological Department of Chemistry, University of Dayton, processes (i.e., the acidic environment of the initial Dayton, Ohio, United States. stages in the wound healing cascade). Edge plane pyrolytic graphite (EPG) electrodes coated with 5,10,15,20-tetra-(3-methoxy-4- 310. Synthesis and Characterization of a hydroxyphenyl)porphyrin [H2T3M4HPP] and its Series of Highly Multi-Dentate Ligands All Fe(II), Co(II), Ni(II), and Cu(II) analogs undergo an Incorporating Tris-(2-Aminoethylene)-Amine electrochemical-chemical-electrochemical (ECE) and Metal Complexes Thereof reaction when anodically scanned in 0.5 M H2SO4. The new redox couple formed from this anodic Benjamin Czierniawski, Malinda Killu, Mark A. conditioning of the coated electrode is dependent Benvenuto. Department of Chemistry & upon the pH of the solution. Roughened EPG Biochemistry, University of Detroit Mercy, Detroit, electrodes coated with the metalloporphyrins show a MI, United States. catalytic shift for the reduction of O2 when compared Several ligands were synthesized from a Schiff’s base to the reduction of O2 at the bare electrode. An condensation reaction between tris-(2- additional catalytic shift of roughly 100 mV is aminoethylene)-amine aldehydes such as: 2- observed for O2 reduction for the EPG electrode furaldehyde and 2-thiophene carboxaldehyde. coated with the Co(II) porphyrin complex which has Reduction of the imine double bond in each ligand is been oxidized in 0.5 M H2SO4. In addition to the accomplished using sodium borohydride. Complexes added electrocatalysis, approximately 15% of the O2 were formed using the target ligands and various reduced at the oxidized Co(II) porphyrin EPG transition metals. These complexes were then electrode is converted to H2O as determined by analyzed to determine the ligands’ metal binding rotating disk electrode measurements. characteristics. All analyses were performed using multi-nuclear NMR spectroscopy.

311. Synthesis and Characterization of a Series of Multi-Dentate Ligands Incorporating Bis(2- Hydroxyphenyl)ethylenediamine, and Some of Their Lanthanide Metal Complexes Jennifer Kubert, Meghann Mouyianis, Mark A. Benvenuto. Department of Chemistry & Biochemistry, University of Detroit Mercy, Detroit, MI, United States. A series of novel ligands, all incorporating (1R,2R) 1,2-bis(2-hydroxyphenyl)-ethylenediamine and a functional, aromatic aldehyde has been constructed via Schiff’s base condensations, and has been characterized by multi-nuclear NMR and, in select cases, by single crystal diffractometry. The ligands have the potential to be both tri- or tetra-dentate. Structural characterizations, as well as indications of 313. Incorporation of SENCER Principles the ligands’ metal binding abilities, will be presented into an Environmental Chemistry Course and discussed. David W. Johnson. Department of Chemistry, 312. Electrooxidation of Iron, Cobalt, Nickel University of Dayton, Dayton, OH, United States. and Copper Metalloporphyrins on Edge The environmental chemistry course at the University Plane Pyrolytic Graphite Electrodes and of Dayton has been transformed from a linear science

course that deals with aquatic chemistry, atmospheric 315. Reduction of Perchlorate from chemistry and geochemistry to one which Contaminated Waters Using Zero Valent investigates environmental problems in a highly Iron, Palladium as a Catalyst, and UV Light branched manner including aspects of science, economics, ethics and public policy. Topics Qiuming A. Zhao. Department of Civil addressed include water usage acid rain, global Environmental Engineering, University of Cincinnati, warming, sustainability and alternative energies. As a Cincinnati, OH, United States. capstone, the course requires either a presentation or With advanced sensitive of modern analytical paper addressing an environmental problem techniques such as ion chromatography(IC), involving chemistry including a scientific solution - perchlorate(ClO4 ) contamination in drinking system that includes economics and public policy has been revealed as a widespread problem in United consequences. As a result, the course contains States, typically at 0.005-0.020 mg/L(5-20 ppb). substantially more student discussion, less time is Man-made perchlorate is a major contribution to the spent lecturing. Fewer topics are discussed, but each contamination in the environment due to the of the topics are treated in greater depth. Students exceptional oxidizer properties of perchlorate. gain a greater appreciation for the nonscientific Although various perchlorate treatment technologies aspects of solving environmental problems. Projects have been shown to be effective, chemical deal with a range of topics and include more than the destruction can be the optimal way to remove science and engineering approaches to a problem. perchlorate to a complete degree from water system. Students appreciate the importance of political, In this study perchlorate reduction by zero valence social, ethical and economic implications of any iron fillings enhanced by UV light and palladium was issue. As a result of the changes, student enrollment studied. Up to 50 % of perchlorate reduction from the has increased from 5-14 in one year and student original 1 mg/L (1ppm) was achieved using iron attendance has improved by 15% in the past 3 years. fillings alone in a batch study. However, using UV light (0.24mW/cm2, 12KW ) with zero valent iron 314. Studies on Dyanmics, Mechanism and perchlorate reduction was enhanced to 65%. A 90% Characterization of the Thermal Degradation of the perchlorate reduction was achieved by adding Products of Beta-Carotene by GC-MS palladium chloride with iron fillings and UVlight. During the initial stages of the process adsorption of Yuan Zhao, David W. Johnson, Mark Masthay. perchlorate to the catalyst surface was for the first 6 Department of Chemistry, University of Dayton, hour of the batch runs. In order to evaluate the Dayton, OH, United States. effectiveness of iron dosage, four different iron The thermal degradation kinetics of beta-carotene, as dosages, 0.25g/ml, 0.50g/ml, 0.75g/ml and 1.0g/ml, a function of temperature, were determined and the were used in the batch study. 1.0 g/ml of iron dosage influence of oxygen on the rate of its degradation has the most capacity for the perchlorate reduction were assessed. Solid Beta-Carotene was heated in among the other three iron dosages. A mathematical Pyrex ampoules sealed under vacuum to ensure correlation was established for the reduction kinetics minimal oxygen and open tubes to evaluate oxygen of perchlorate based on the batch study. A recycle influences. Analysis of kinetic data suggested a first- column study was done to evaluate the prediction of order reaction for the thermal degradation of beta- kinetic rate from the batch study mathematical carotene by UV-Vis spectroscopy. The kinetics correlation. Reduction rate was correlated reasonably parameters, rate constant k, activation energy Ea, and well by pseudo first order reaction kinetics in the pre-exponential factor A have been calculated. column study. Isomerization from trans to energetically favored cis conformation of beta-carotene was observed in gas 316. Quantitative Analysis of Non-Steroidal chromatography-mass spectrometry (GC-MS) Anti-Inflammatory Drugs in the River Raisin analysis. The degradation products, retinol, ionone by GC-MS etc are confirmed by GC-MS, most of them are believed to be apocarotenoids and epoxy compounds. Jennifer Bates, Ruth Ann Armitage. Department of These findings will help give hints to its biosynthetic Chemistry, Eastern Michigan University, Ypsilanti, pathway and determine optimal processing conditions MI, United States. to minimize the degradation of beta-Carotene in food Non-steroidal anti-inflammatory drugs (NSAIDs) are sources. widely used in the United States; these drugs leave our bodies mostly unmetabolized. As they do not get removed during the water treatment process, NSAIDs

– along with other pharmaceuticals and personal care decreased relative abundances, the calculated formula products – can then find their way into aquatic errors increase with increasing mass. ecosystems. Preliminary sampling and testing of Additionally, higher masses have the more water samples from the River Raisin in Monroe mathematical possibilities for calculated chemical County, Michigan was carried out by the Creative formulas. Thus homologous series relationships were Scientific Inquiry Experience Quantitative Analysis used to link lower masses with lower error to higher class this winter. Their results showed the presence of masses with greater error. The depth of the series was acetylsalicylic acid, naproxen, and ibuprofen in the about ten CH2 units, corresponding to the size of the samples. This work will quantify the amounts of each precursor, α-pinene. The bulk of the monomers had of these NSAIDs present in the samples, and unsaturation numbers centralized between 2 and 5. determine how population affects the concentrations. The dimer group had numbers between 4 and 8 and Samples were collected from several locations along the trimer group had numbers between 6 and 10. The the River Raisin, from near the source and to the river O:C ratios and H:C ratios showed evidence of mouth at Lake Erie. The analytes of interest were condensation oligomerization, as the amount concentrated using polymeric reversed phase solid hydrogen and oxygen relative to carbon decreased as phase extraction. Samples were then derivitized mass increased. online to their methyl esters for GCMS analysis, with mecoprop as an internal standard. The results of our 318. Toward Rapid Detection of Methionine analysis will be presented, and compared to the initial Sulfoxide in Proteins study. Morwena Jane V. Solivio, Edward J. Merino. 317. Characterization of Secondary Organic Department of Chemistry, University of Cincinnati, Aerosols from the Ozonolysis of α-Pinene Cincinnati, Ohio, United States. Cancer is a major public health concern with about Lynn Mazzoleni, Annie Putman. Department of 500,000 individuals in the United States dying Chemistry, Michigan Technological University, annually from the disease. Evidence from recent Houghton, Michigan, United States. studies suggests that cancer cells are under an The current challenge in predicting the magnitude of increased level of oxidative stress associated with global climate change is in understanding the oncogenic transformations, increased metabolic magnitude of the effects of aerosol particles. The activity and increased generation of reactive oxygen composition of aerosol particles varies widely, species (ROS). Our lab is interested in developing depending on their origin and their atmospheric methods utilizing oxidative stress products for early processing. Secondary organic aerosols (SOA) result cancer detection. Protein side chains of cysteine, from complex, multi-step reactions between volatile tyrosine, tryptophan, histidine and methionine are organic carbons (VOC), oxidative atmospheric prevalent targets of ROS. Methionine is preferentially gasses, and any of the aerosol constituents already oxidized to methionine sulfoxide in biological present in the atmosphere. In this work, we studied systems. Methionine sulfoxide has been recognized the composition of the biogenic aerosol created by as a biomarker for oxidative stress but is difficult to the reaction α-pinene with ozone, an oxidizing visualize in a rapid and robust manner. To combat atmospheric gas. The SOA resulting from the this challenge, we have identified a selective binding reaction were characterized by ultra-high resolution nucleic acid termed an aptamer. The aptamer was Fourier-Transform Ion Cyclotron Resonance Mass identified by selectively partitioning oligonucleotide Spectrometry (FT-ICR MS). Three samples, labeled sequences that bind methionine sulfoxide containing IR459, IR460 and IR463, as well as chamber blanks, peptides from those that bind closely related were analyzed. methionine peptides. Oligonucleotides that bind The experiments were conducted with varied methionine sulfoxide peptides were amplified, hydroxyl radical concentrations. In all samples, cloned, and sequenced after ten rounds of selection. hundreds of masses (400 < n < 700) were detected Analysis of binding sequences showed high guanine representing monomers, dimers and trimers of base content. The calculated structures were largely oxidized α-pinene species. All of the identified peaks single stranded in nature. We then showed selective of the accepted chemical formulas had corresponding binding via a fluorescence assay. 13C peaks present, reasonably low error (< 2ppm) and were related by homologous series. Because of 319. Chemistry in Water: Coupling Reactions shortened ion cyclotron resonance lifetimes, lower Using Fenton’s Reagent ion resolution at higher mass-to-charge ratios and

Jennifer L. Meyer,1 Mark D. Naber,1 Christopher material is proposed to contain a number of cross- Sears-Dundes,1 Richard P. Hotz,1 Allan R. Pinhas.2 links that reduce the polymer’s solubility, however, 1Department of Chemistry, College of Mount St. the chemical structure of the putative cross-links and Joseph, Cincinnati, OH, United States; 2Department their density are poorly understood. The focus of this of Chemistry, University of Cincinnati, Cincinnati, work is the characterization of the soluble and OH, United States. insoluble components of polyphosphazene to determine their structure and morphology. The Fenton’s Reagent (FeSO and H O in water) is well 4 2 2 primary technique being used in these studies is known for its ability to remove a hydrogen atom from solid-state NMR, where chemical shifts and dipolar DNA and cause the double helix to unravel. It also couplings are used to determine the structure, and causes the degradation of other biological systems, relaxation values are used to characterize the such as proteins and lipids. In contrast, we have polymers dynamics as a function of cross-link studied the use of Fenton chemistry not to destroy a density. Models for the structure of the insoluble molecule, but rather to create new carbon-carbon polymer material will be presented. bonds. Specifically, we have investigated the radical

coupling of acetonitrile, acetone, and acetophenone. Symposium Title: (CeRMACS013) Polymer

Chemistry. Two molecules of acetonitrile couple to give succinonitrile in good yield. However, the coupling of two molecules of acetone only occurs in very low 321. Prediction of LSER r1 Coefficient Using yield. Surprisingly, when acetone and acetonitrile are QSSR mixed, the acetone coupling product predominates. Priyank Shah, David S. Ballantine. Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL, United States. Linear solvation energy relationships (LSER) can be used to predict solubility related properties of solvent phases. The following LSER has been used extensive to evaluate the properties of a set of liquid ionic solvent (LIS)and non-ionic GC stationary phases Acetophenone forms two types of products derived H H H 16 from hydrogen atom abstraction from the aromatic log SP=c1+r1R2+s1π 2+a1∑α 2+b1∑β 2+l1 log L ring and not from the methyl group. In one, OH• adds to the ring to give hydroxyacetophenone derivatives. The r1 coefficient represents the ability of the solvent In the other, two acetophenone radicals couple to phase to engage in electronic interactions. give diacetyl biphenyl derivatives. Quantitative structure-solubility relationships (QSSR) can be used to correlate solubility-based properties 320. NMR Characterization of the Structure with molecular descriptors. Non-ionic phases and Morphology of Polyphosphazene included amine, cyano, and phosphorus-containing functional groups. Ionic phases consisted of sulfonate Jessi A. Baughman, Matthew P. Espe. Department anion salts with phosphonium and ammonium of Chemistry, University of Akron, Akron, OH, cations. Molecular descriptors related to electronic United States. structure, including molecular connectivity indices (χ v Phosphazene polymers are known for their chemical, and χ ) HOMO/ LUMO levels were calculated using thermal, and radiological stabilities. These stabilities CAChe computational software and used to estimate along with the ease to add various sidechains to the the r1 value of the solvent phase set. The best polymer backbone give phosphazene high potential predictive equations consisted of HOMO/LUMO levels normalized by molar surface area, and in optical, high-temperature, and chemical separation 2 applications. The desired phosphazene material is the normalized χ values, with a R value of > 0.4. linear chain polymer, as this material is easily processable since it has high solubility in a variety of 322. Chemists and Other Scientists as Senior solvents. However, if the generation of Athletes polyphosphazene through the polymerization of the Wendell L. Dilling. Department of Chemistry, cyclic phosphazene trimer and/or tetramer is carried Central Michigan University, Mt. Pleasant, Michigan, out at too high a temperature or for too long a time, United States. an insoluble component is produced. The insoluble

Some senior athletes, age 50 and older, are scientists. found at the microscopic level, evidence that such A group of these athletes who are scientists were crystals could effectively block a kidney ureter. identified, and an attempt was made to determine if there was any correlation of the field of science in 324. Hosting a Science Day for Homeschooled which these scientists worked and the sports or Children events in which they competed. Although in this preliminary report the number (23) of scientists Jacob P. R. Deitsch, Edith P. Kippenhan. identified is too small to have any statistical Department of Chemistry, University of Toledo, significance, some interesting stories were received Toledo, OH, United States. from these scientist-athletes. These stories make up Many parents who decide to home school their the major part of this presentation. The scientists children find teaching laboratory science to be a included in this preliminary study were either challenge. This may be due to the cost and access to personal acquaintances or were people who supplies or the lack of laboratory science experience responded to notes in two publications. The fields of of the parents. science included biochemistry, biology, chemical Our organization decided to create an event to engineering, chemistry, civil engineering, ecology, introduce laboratory science learning to educational administration, engineering, homeschooled students and educate parents on how environmental science, geology, human physiology, to implement this crucial piece of science education kinesiology, mathematics, mechanical engineering, in their children’s curriculum. The event began with a medicine, metallurgy, and plant pathology. The demonstration show performed by members of the sports included archery, badminton, basketball, University of Toledo Student American Chemical boxing, canoeing, cycling, race walk, rope jumping, Society. The theme of the show was centered around swimming, softball, table tennis, tennis, track and the fire triangle and combustion. Following the field, triathlon, volleyball, and weight lifting. A more demonstration show, students were broken into detailed analysis of the events within track and field smaller groups of eight or nine students. Each group also did not lead to statistically significant would go to one of six stations. Each station correlations of field of science and events. introduced students to a new concept in chemistry. After fifteen minutes, the groups would rotate to a 323. Chemical Analysis of Melamine in Milk new station. These rotations would continue until Jessica Arnett, Katherine Stickney. Department of each group has visited all six stations. The event Chemistry, University of Indianapolis, Indianapolis, concluded with light refreshments including IN, United States. homemade ice cream using liquid nitrogen to freeze the ice cream. In the fall of 2008, the nitrogen-rich compound melamine cyanurate was found to be intentionally 325. Activation Energy and Collision added to dairy products in Asia, apparently to raise Frequency through the Rate Law for an the calculated crude protein percentage of watered- Iodine Clock Reaction down products to a standard level. The adulterated milk sickened 300,000 children, and six infants died Nick Sharma, Simon Fraser, Myung Han. due to renal failure. In this study, the commercial, Department of Physical Sciences, Columbus State automated Kjeldahl method (commonly used to Community College, Columubs, Ohio, United States. indirectly determine crude protein levels in food The rate law for an iodine clock reaction and its products by nitrogen content analysis) was adapted to activation energy were determined by incorporating a hands-on laboratory method. This adapted mathematical calculations with computer graphing. procedure was used to determine crude protein We obtained the set of reaction rates concurrent to content of various concentrations of reconstituted varying temperature as well as the concentrations of milk. Next, the amount of melamine cyanurate the two reactants: potassium persulfate (K S O ) and needed to raise the nitrogen content of a known 2 2 8 sodium iodide (NaI.) The rate data was used to volume of 25 % milk to the same level as that of 100 determine the rate law which led to calculating the set % milk was calculated, and this amount was added to of rate constants. The rate law of the iodine clock that volume of watered-down milk. It was concluded reaction was determined to be second order: that the Kjeldahl analysis fails when a non-protein, nitrogen-containing contaminant is present in the rate = k [ S O 2- ][ I- ] sample. Finally, melamine cyanurate was dissolved 2 8 in a pH 7 buffer to mimic physiological conditions in a kidney. Various sizes and shapes of crystals were

The activation energy of this reaction was John F. Beck, Joseph A. R. Schmidt. Department of determined by applying the obtained data set of Chemistry, The University of Toledo, Toledo, OH, rate constants and of respective temperatures to United States. computer graphing of the Arrhenius equation. Aluminum, zirconium and hafnium ortho-metalated The activation energy determined ranged from imines were synthesized via the reaction of an ortho- 13.4 kJ (at 23 oC) to 19.2 kJ (at 50 oC). Computer lithiated imine (Li-L) with the corresponding metal graphing of the Arrhenius equation also allowed chlorides. Both bis and mono-ligated aluminum us to calculate the collision frequency of the complexes were made; the complex L AlCl was reaction, which was determined to be 0.005. Most 2 found to be of a distorted square pyramidal geometry iodine clock reactions focus on the aspect of with a C rotation axis though the aluminum-chlorine determining rate law through wet laboratory 2 bond. A mono-ligated complex was prepared in good experiments. We have expanded the scope of this yield via the reaction of Et AlCl and Li-L. Zirconium experiment to incorporate computerized graphing 2 amido complexes were synthesized via the treatment which provided insightful data on reaction of (Et N)ZrCl with 2 Li-L, yielding L ZrCl(NEt ). kinetics as presented by activation energy and 2 3 2 2 mono-Ligated hafnium complexes were prepared via collision frequency. the reaction of Li-L with (Ind)HfCl3 yielding (Ind)Hf(L)Cl2 (Ind = indenyl). The reaction of HfCl4 326. Urinary Analysis of Cyclophosphamide: with Li-L in warm DME/toluene yielded the five- Development and Comparison of Methods coordinate anionic hafnium complexes LHfCl4 Dale A. Shoemaker, Jeffrey L. McLaurin. National together with DME solvated lithium cations. The Institute for Occupational Safety and Health, complexes were characterized by single crystal X-ray Cincinnati, Ohio, United States. diffraction and NMR spectroscopy. These Lewis acidic metal complexes were further functionalized Cyclophosphamide is an antineoplastic drug used in and their catalytic and organometallic reactivity the treatment of many types of cancer. This ascertained. compound possesses carcinogenic, mutagenic, and teratogenic properties. Workers in the health care 328. Reduction of Perchlorate from field, such as oncology pharmacists and nurses, Contaminated Waters Using Zero Valent prepare, deliver, and dispose of this drug and thus have the potential to be exposed. A large field study Iron, Palladium as a Catalyst, and UV Light was undertaken to determine the exposure of several Qiuming Amy Zhao. Department of Civil antineoplastic drugs and evaluate and assess the risks Environmental Engneering, University of Cincinnati, to health care workers. An accurate and precise Cincinnati, OH, United States. urinary biological monitoring method was needed to determine the level of internal dose of this drug. A With advanced sensitive of modern analytical techniques such as ion chromatography(IC), method utilizing solid phase extraction, followed by - derivatization with trifluoroacetic anhydride and perchlorate(ClO4 ) contamination in drinking system analysis by gas chromatography/mass spectrometry has been revealed as a widespread problem in United was developed. Deuterated cyclophosphamide was States, typically at 0.005-0.020 mg/L(5-20 ppb). used as an internal standard. Limits of detection were Man-made perchlorate is a major contribution to the contamination in the environment due to the ∼1.5 ppb for cyclophosphamide. Results will be exceptional oxidizer properties of perchlorate. presented on recovery experiments performed at Although various perchlorate treatment technologies three levels on pooled urine and at one level for 21 have been shown to be effective, chemical individual urines. Quality control values from 34 destruction can be the optimal way to remove batches of healthcare worker samples will also be perchlorate to a complete degree from water system. presented. Results will also be presented on a liquid- In this study perchlorate reduction by zero valence liquid extraction method developed in our iron fillings enhanced by UV light and palladium was laboratories with emphasis on comparison of studied. Up to 50 % of perchlorate reduction from the analytical figures of merit, labor and solvent original 1 mg/L (1ppm) was achieved using iron consumption, and sample throughput. fillings alone in a batch study. However, using UV light (0.24mW/cm2, 12KW ) with zero valent iron 327. Lewis Acidic Metal Complexes Utilizing perchlorate reduction was enhanced to 65%. A 90% Ortho-Metalated Imines of the perchlorate reduction was achieved by adding palladium chloride with iron fillings and UVlight. During the initial stages of the process adsorption of

perchlorate to the catalyst surface was for the first 6 columns possess opposite retention characteristics. hour of the batch runs. In order to evaluate the The oxidized aromatic compounds were weakly effectiveness of iron dosage, four different iron retained on the ZIC-HILIC, but strongly retained by dosages, 0.25g/ml, 0.50g/ml, 0.75g/ml and 1.0g/ml, the PFP and the oxidized aliphatic compounds were were used in the batch study. 1.0 g/ml of iron dosage strongly retained on the ZIC-HILIC, but weakly has the most capacity for the perchlorate reduction retained on the PFP. This separation enhances among the other three iron dosages. A mathematical identification and detection sensitivity capabilities correlation was established for the reduction kinetics through the use of an electrospray ionization mass of perchlorate based on the batch study. A recycle spectrometer. column study was done to evaluate the prediction of kinetic rate from the batch study mathematical 330. Biopolymers To Modify Permeability for correlation. Reduction rate was correlated reasonably In Situ Alcohol Flushing of TCE well by pseudo first order reaction kinetics in the column study. Sangchul Hwang, Nelson Anaya, Katherine Benn, Ingrid Padilla. Department of Civil Engineering, 329. Advanced Liquid Chromatography University of Puerto Rico, Mayaguez, PR, Puerto Method Development for Separation of Rico. Atmospheric Water-Soluble Organic In situ flushing for remediation of dense non-aqueous Compounds phase liquids (DNAPLs) contaminated soil and groundwater is done by the injection of a solvent Sandra S. Orlowski, Lynn R. Mazzoleni. solution into the contaminated zone. The system is Department of Chemistry, Michigan Technological followed by downstream extraction of a mixture of University, Houghton, MI, United States. groundwater, flushing solution and the contaminants Aerosol particles contain products from a variety of for an aboveground treatment. Permeability is the natural chemical reactions. Many of these products principal cause which the flushing solution moves include water-soluble organic compounds. These through a porous medium and, therefore, determines compounds may influence the size and production how effective the remediation is. DNAPLs entrapped rate of cloud droplets, yielding an effect upon Earth’s in low permeable zone are not easily flushed out radiative balance, hydrologic cycle as well as air diminishing overall treatment efficiency. Moreover, quality and climate change. In our research, we focus they release residual DNAPLs concentration over a on implementing chromatographic retention to long period time, which makes our health and safety improve identification and quantification of water- risky. soluble organic compounds. In this work, we chose several aliphatic and aromatic model compounds The objective of the research is to evaluate which include carboxyl, hydroxyl, and nitro effectiveness of biopolymers to modify permeability functional groups. Thus, the creation of a single for in situ flushing of DNAPLs in the heterogeneous liquid chromatography separation method is very subsurface setting. Trichloroethylene (TCE) was challenging. We compared separations on three tested as the target DNAPL compound and 5% columns: a polar endcapped C18 column, a methanol was used as the flushing solution. Both pentafluorophenyl (PFP) column and a zwitterionic biopolymers and synthetic polymers were utilized. hydrophilic interaction (ZIC-HILIC) column. All The parameters measured were the pressure three columns possess different stationary phase developed due to polymer injection and the time for functional groups. Experimental data provided flushing, transport extent and concentration of the information on how the functional group influenced DNAPLs. Different methanol concentrations and retention time by their interactive capabilities with contact times were also evaluated. Results indicated the mobile phase and the analytes. The PFP column that the biopolymer injection could reverse is a reverse phase column with a fluorinated ring, permeability contrast and thereby increase overall while the ZIC-HILIC is a hydrophilic interaction TCE removal. column with a terminal negatively charged SO3 group balanced by a positively charged quaternary amine. 331. Climate Change and Atmospheric In addition to stationary phase type, this project also Chemistry in the Arctic investigated the effect of various experimental factors Paul Shepson. Departments of Chemistry and Earth such as column temperature, injection volume, mobile phase flow rate, salt type and concentration and Atmospheric Sciences and Purdue Climate and solvent composition. The ZIC-HILIC and PFP Change Research Center, Purdue University, West Lafayette, IN, United States.

Climate science is increasingly focused on experimental design or assumptions derived from a development of Earth System models that provide motional model that depends on various conditions useful output regarding response of the natural Earth such as molecular size, time-scale of the motion, systems to human perturbations. This is a huge static magnetic field strength, NMR pulse sequence, challenge, as our global experiment in climate change and observed nuclei. Thus, we conduct experiments has no experimental control, and the planet is and simulations to estimate, or if possible to reduce, outrageously complex. Thus we must pursue deep errors involved in the NMR relaxation experiments understanding of the complex array of connections that are often used to characterize protein dynamics. between system components, and shed our The work is supported by NSF MCB/0814905 and disciplinary bounds. No where is climate change so NIH 1R01AI077424. apparent as it is in the Arctic. Sea ice is retreating rapidly, and this will lead to a range of impacts and 333. Directing the Binding of Potential feedbacks, most of which are poorly understood. Activating Agents into the Active Site of Aged Among them is the impact on cloud cover. Clouds Acetylcholinesterase after Exposure to depend both on the availability of water vapor, and Organophosphorus Nerve Agents: A on aerosols upon which the water vapor condenses. There is a large need to understand how changes at Computational Investigation the surface of the Arctic will lead to changes in Jeremy M. Beck, Siva Muthukrishnan, Jason D. aerosols and thus cloud cover and the ice albedo Brown, David A. Critser, Christopher M. Hadad. feedback. A part of these changes is a range of Department of Chemistry, The Ohio State University, chemical processes related to the presence of sea ice, Columbus, OH, United States. and its role in liberating sea salt, molecular halogens, and halogen radicals into the atmosphere, that in turn Upon inhibition of the acetylcholinesterase (AChE) impact atmospheric composition. In this talk, I will active site by organophosphorus (OP) nerve agents, review these processes and the rich array of the phosphoryl center can undergo a secondary chemistry that occurs in this environment, how that reaction termed aging, wherein dealkylation of the chemistry is probed with ground based and space OP’s O-alkyl group occurs. In this aged state, the based instruments, and what the future may hold. I native activity of AChE is completely lost; moreover, will close with a discussion of the lack of connection to date, aged AChE has been found to be un- between the chemistry community and the climate reactivateable. However, re-alkylation of the change research and solutions development phosphonate center could allow for cleavage of the communities, what the nature of the opportunities OP-AChE bond via the attack of potent nucleophiles. are, and how chemists can play an important role in Currently, oximes are the most commonly used connecting science to a sustainable future. therapeutic for OP nerve agent poisoning, albeit with poor success rates. In order to aid the design and development of re-alkylating agents for the 332. Practical Aspects of NMR Relaxation phosphylated serine residue of AChE, we have Experiments To Study Protein Dynamics in investigated a class of alkylating compounds, Solution quinone methides, and tuned their selectivity for the Wazo Myint, Lakshmi Menon, Rieko Ishima. Dept active site of AChE. of Structural Biology, University of Pittsburgh Docking and molecular dynamics simulations School of Medicine, Pittsburgh, PA, United States. revealed that induced fit could play an important role in binding at the active site of aged AChE. Further, in Nuclear Magnetic Resonance (NMR) relaxation is a silico results suggest two predominant interactions in powerful technique that provides information about the choline binding pocket with Trp86 and Glu202, internal dynamics associating to configurational which can be utilized to direct the quinone methide energetics in proteins, and about insights in to the precursors into an active orientation. Leveraging site-specific information involved in conformational these interactions, the binding and stability of several equilibriums. For meaningful results to emerge and quinone methide precursors in the active site of aged for reasonable comparison of NMR-derived acetylcholinesterase will be presented. dynamics with those obtained by other methods, accurate evaluation of uncertainties in the NMR- derived parameters is critical. Uncertainties in NMR- derived dynamics parameters may stem from experimental noise errors and systematic experimental errors. Such errors may occur through

334. Role of Force Orientation in the incroporated into the YbaK protein at surface Mechanical Response of Biological Filaments positions to trap binding partners in vivo. Bpa is an photoaffinity unnatural amino acid, which can form Kelly E. Haines, Harshad Joshi, Ruxandra I. Dima. covalent bonds with adjacent protein molecules under Department of Chemistry, University of Cincinnati, UV irradiation. The in vitro and in vivo irradiation Cincinnati, OH, United States. experiment with the YbaK-Bpa mutatant showed that Microtubules (MTs) perform their cellular functions scanning a protein with Bpa may be especially useful through a mechanism known as dynamic for weak or transient protein-protein interaction instability1,2[/sup]. As an essential component of the studies. cytoskeleton in eukaryotic cells, the effect that applied forces have on dynamic instability is crucial 336. Binding of OP Nerve Agents with to MTs role in the cell. We used molecular Butyrylcholinesterase and Its Mutants: A simulations of a self-organized polymer (SOP) Computational Study model3 of the tubulin dimer, the fundamental subunit of MTs, to view its unfolding in response to tension. Shubham Vyas, Christopher M. Hadad. Department Our data shows that not all units in the MT lattice are of Chemistry, The Ohio State University, Columbus, created equal: the beta monomer is the least stable OH, United States. part of an end dimer, while the alpha monomer is the Organophosphorus (OP) compounds are chemical least stable part of an interior dimer. While the warfare agents; thus, they are a potential threat to magnitude of the force is crucial, the orientation of mankind. Butyrylcholinesterase (BuChE) is a the force is also significant in complex structures stoichiometric bioscavenger against OP nerve-agent such as the MT lattice. To probe in detail the effect of poisoning. Significant efforts are in progress to orientation, we applied the force in different design a BuChE variant that is catalytically active for orientations to the tubulin dimer. Our results correlate a variety of OP nerve agents. In this context, we well with experimental data such as the extent of the carried out extensive molecular dynamics (MD) 2 GTP-bound tubulin layers that cap MTs . simulations on wild-type (WT) BuChE to understand the flexibility of different segments of the protein. 1Nogales, Eva, et al., Cell, January 8, 1999, vol. 96, We then docked several different OP nerve agents 79-88 into the active site of BuChE to recognize important interactions between the nerve agents and enzyme. 2Schek III, Henry T., et al., Current Biology, The MD simulations suggested two transient September 4, 2007, vol. 17, 1445-1455 orientations of the active site serine, which interconvert very frequently. Furthermore, the 3Dima, Ruxandra and Joshi, Harshad; PNAS, simulations supported the notion that W82 might play October 14, 2008, vol. 105, no. 41, 15743-15748. a role of gatekeeper for the back door.

335. Convenient Stop Codon Scanning Similar MD simulations were carried out for known Mutagenesis Method for Alanine and BuChE mutants (G116H, G117H, E197Q and Unnatural Amino Acid Scanning G117H/E197Q) and results are compared with the WT-BuChE MD simulations. In light of the structural Lihua Nie, Thomas J. Magliery. Department of differences between WT-BuChE and mutants along Chemistry, The Ohio State University, Columbus, with the docking results on WT-BuChE, we predict Ohio, United States. the differences in binding of OPs with the mutants. A general combinatorial mutagenesis method with Our predictions are in good agreement with the orthoganally protected mononucleotide known experimental data. These computational phosphoramidites and a single trinucleotide results and future insights will be discussed. phosphoramidite was developed to systematically scan a protein gene with the amber stop codon, TAG. 337. Differential Expression of Proteins in In combination with stop codon suppression, a single Response to Arsenic Stress in DNA library can be used to incroporate natural and Chlamydomonas reinhardtii unnatural amino acids for diverse purposes. For Chamari Walliwalagedara,1 Harry van Keulen,2 prove of principle, two TAG mutation libraries were 3 1 1 syntehsized. Alanine was incorporated into the Rop Belinda Willard, Robert Wei. Department of Chemistry, Cleveland State University, Cleveland, protein to scan for determinants of RNA binding 2 activity in vivo. p-Benzoylphenylalanine (Bpa) was Ohio, United States; Department of Biological Geological and Environmental Sciences, Cleveland

State University, Cleveland, Ohio, United States; the destruction of chemical agents. The use of OPH 3Lerner Research Institute, Cleveland Clinic, for decontamination applications would be greatly Cleveland, Ohio, United States. enhanced in a molecular context that increases enzymatic stability. One potential way to increase The aim of this study was to identify proteins that are enzymatic stability would be to combine the enzyme differentially expressed in response to arsenate with a protein chaperone to create an enzyme- [As(V)] in the fresh water unicellular alga chaperone hybrid. The plant chaperone protein, Chlamydomonas reinhardtti. The cells were exposed Stable Protein 1 (SP1) is expressed as a monomeric to different concentrations of As (V) ranging from protein of 12.4 kDa, but forms a higher ordered, 100-400 mM. When they were exposed to 200 mM dodecameric structure through homo- As(V), growth inhibition started at the second day oligomerization. Remarkably, the dodecameric and remained until the experiments were terminated structure of SP1 is resistant to denaturization by heat, on the 6th day. First, extracting soluble proteins with organic solvents and ionic detergents, thus preserving trichloroacetic acid in combination with acetone was its chaperone activity under denaturing conditions for not effective in the removal of chlorophyll and other the re-folding of protein substrates. The stabilizing materials, which contributed to loss of protein and the activity of purified, wild-type SP1 has been tested streakiness of the two dimensional (2D-PAGE) gels. with OPH as a chimera where SP1 was covalently An alternative protocol was developed which attached to OPH in a single reading frame. Compared employs two consecutive precipitation steps of to monomeric OPH, the OPH-SP1 chimera ammonium sulfate ((NH ) SO ) yielding high 4 2 4 demonstrated significant stabilization when assayed resolution mapping for proteomic studies. The 40% at elevated temperatures. The chimeric OPH-SP1 salt treatment removed chlorophyll and other viscous demonstrated higher temperature stability compared materials and the second precipitation step [60% to that of monomeric OPH in the presence of free (NH ) SO ] recovered >90% of the soluble proteins. 4 2 4 SP1, even at higher OPH:SP1 mass ratios. The shapes of protein spots were more discrete and Surprisingly, no evidence of self-healing was the protein distribution patterns were highly observed with the OPH-SP1 chimera, suggesting that reproducible. Seventeen (17) protein spots that were increased heat stability is a result of immobilization expressed in the 200 mM As(V) treated samples were on a protein scaffold. Based on these studies, other selected to determine their identity by Liquid immobilization strategies are being tested, such as Chromatography-Tandem mass spectrometry (LC- OPH binding to titania-based diatoms, which also MS/MS) analysis. The expression of these proteins have the ability to hydrolyze organophosphates, and suggested impairment of photosystem function, encapsulation of OPH by silk. Nonetheless, the energy and carbohydrate metabolism, and also ability of SP1 to form higher-ordered structures and oxidative stress. stabilize covalently associated proteins will be critical in the creation of multi-enzyme complexes as 338. Enhanced Organophosphate Hydrolysis well as organic/inorganic hybrids that are able to with Enzyme-Chaperone Chimeras and catalyze complex reactions under adverse Organic/Inorganic Hybrids environmental conditions. Patrick B. Dennis,1,2 Matthew B. Dickerson,3 Wendy J. Crookes-Goodson,1 Caitlin Knight,1,2 339. Coupling between Sequential Allostery Arnon Heyman,4 Oded Shoseyov,4 Nils Kroeger,5 in a GroEL Mutant and Protein Folding 6 1 1 Kenneth H. Sandhage, Rajesh R. Naik. Materials Nathan Smith, Pooja Shrestha, George Stan. and Manufacturing Directorate, Wright-Patterson Air 2 Department of Chemistry, University of Cincinnati, Force Base, Dayton, Ohio, United States; UES, Cincinnati, Ohio, United States. Dayton, Ohio, United States; 3Research Associateship Program, National Research Council, The bacterial chaperonin GroEL is a double-ring Washington D.C., United States; 4Hebrew University nanomachine which provides critical folding of Jerusalem, Rehovot, Israel; 5Department assistance to misfolded proteins. During ATP-driven Chemistry and Biochemistry, Georgia Institute of cycles, GroEL binds and encapsulates substrate Technology, Atlanta, Georgia, United States; proteins (SPs) inside a dynamic cavity and assists 6Department of Materials Science Engineering, them to reach their native structure. The dramatic Georgia Institute of Technology, Atlanta, Georgia, expansion of the cavity is facilitated by concerted United States. conformational transitions of the seven subunits of each ring. Organophosphate hydrolase (OPH) is a bacterial Complete functionality requires the attendance of a protein that holds promise as an enzymatic agent for single-ring heptameric cochaperonin, GroES, which

acts as a lid to the cavity. In contrast to the and/or surface water and sediments in the selected GroEL/GroES mechanism, sequential conformational parks, and (2) determine the extent of transitions have been proposed to underlie the biomagnification and bioaccumulation of mercury in operation of the eukaryotic chaperonin homologue bats and the bat food chain (specifically benthic CCT. We study the effect of subunit cooperativity on macroinvertebrates, night-flying Lepidoptera and protein folding assistance by comparing the action of Coleoptera). This is one of eight research projects a mutant GroEL ring, which has sequential listed for the NSF REU Site: Summer Research transitions, to the wild-type GroEL. We perform Experience on the Impacts of Land Use and Land molecular dynamics simulations of a coarse-grained Cover in the Upper Green River Watershed of model of mutated GroEL and a four-helix bundle SP. Western Kentucky, USA. This project runs from We compare our results to previous simulations of 2010 to 2013. All research projects are linked to the four-helix bundle protein folding assistance by current environmental issues. the wild-type GroEL. 341. Peer-Reviewed Open Access Publishing: 340. Mercury Bioaccumulation in Bat The Teaching/Learning/Publishing Populations in the Southeastern U.S. National Landscape Park Units Alexander Scheeline. Department of Chemistry, Cathleen J. Webb. Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Western Kentucky University, Bowling Green, KY, IL, United States. United States. The Internet has made generation, storage, and The potential forenvironmental impacts or damage distribution of manuscripts nearly free. Peer review from atmospheric deposition of mercury from is, typically, uncompensated. Yet, regardless of existing and proposed coal-fired power plants and the distribution mode, the cost to publish a peer-reviewed subsequent contributions to mercury loading in article is approximately $2,000. Why? People other surface and ground-water is a national problem. This than the producer and consumer of information are project examines and determines the current extent paid to manage peer review, edit, type-set, proof- and distribution of mercury in four Kentucky read, and maintain content. What happens when the National Parks with karst ecosystems: Abraham producers and consumers are the same people, and Lincoln, Big South Fork, Cumberland Gap, and they volunteer to do the otherwise-paid jobs? The Mammoth Cave. Research into the toxic effects of cost of production and consumption nearly vanishes. mercury bioaccumulation is vital. Methylation is the The Analytical Sciences Digital Library, supported most biologically relevant step in mercury speciation by limited advertising (on the ACS Division of that influences the fate and transport of mercury in Analytical Chemistry website) publishes peer- the environment. Bats are particularly vulnerable to reviewed content useful for teaching and learning in Hg and MeHg bioaccumulation because they are the analytical sciences. Now in its eighth year, small, mobile, long-lived, and generally consume 40- evident trends include: 1) having freely available 100% of their body mass in prey each night. In materials is a boon. 2) Participation has been addition, bats are also exposed to contaminants narrower than anticipated. 3) Inertia mitigates against through the placenta, nursing, breathing, and drinking Open Access, low-budget publishing displacing water. Given the high toxicity of Hg and MeHg and subscription-model publishing. 4) A separate, web- the relative paucity of toxicological data on Hg and centric community makes significant use of the MeHg with respect to bats, our research and material. Examples of what can be done with the monitoring program has found that the range of 1.78 Open Access model for publishing for lab manuals, to 9.7 mg/kg in adult bat hair from over 350 samples individual experiments, and learning modules will be from MCNP. Species, gender, and age are clearly presented. Barriers to wider use of this publishing seen factors in the levels of mercury found. High model, and plausible circumstances in which it may levels of Hg have also been found in guano deposits. flower, are discussed. This research and sampling program is planned for multiple years and parks to enable us to fully evaluate 342. Introducing Students to Quantitative the effects of increased emissions on mercury Measurements in the Chemistry Laboratory bioaccumulation and biomagnification in bats among local southeast region park units. The specific Ted M. Clark. Chemistry, The Ohio State objectives of this work are to: (1) establish the University, Columbus, OH, United States. occurrence and extent of mercury in groundwater

An initial goal of chemistry courses is almost always spiking sand with various oils. Students were initially the “proper” use of lab resources including glassware given the task to identify components in the oil spill and instruments. The proper use of glassware sample using retention times. As students discovered encompasses many topics, such as laboratory safety, that some of the identifications using retention times technical proficiency, and recognition of function. were equivocal, a guided inquiry process led students However, as many chemical educators can attest, at to propose changing the temperature ramp utilized in both the K-12 and university-level students often the GC program to attempt to separate the have a poor understanding of what makes a particular components. Further guidance allowed students to piece of glassware appropriate for a given task. In discover the power of mass spectrometry as a particular, student ignorance of the role and use of detector for GC. Introducing the concepts of GC and volumetric glassware may be quite pronounced. This MS separately was shown to greatly enhance student lack of understanding certainly impairs student understanding of each of the hyphenated techniques. performance in lab, especially when quantitative Details and assessment results of this experiment will measurements are needed. This presentation seeks to be presented. reverse these circumstances by sharing a popular interactive demonstration that has been successfully 345. Homogeneous Catalysis of implemented in diverse educational settings including Hydroperoxide Decomposition in Liquid analytical and general chemistry courses at the Hydrocarbons undergraduate level, and also high school chemistry and introductory physical science courses. Zachary J. West, Ryan K. Adams, Steven Zabarnick. Energy and Environmental Engineering 343. The New ACS Curriculum: Is “Quant” Division, University of Dayton Research Institute, Dead? Dayton, OH, United States. J. Faye Rubinson. Department of Chemistry, Thermal oxidation of hydrocarbons has been a point Georgetown University, Washington, DC, United of study for many decades due to the practical States. implications of these reactions. A specific area of concern is that of jet fuel thermal stability. Since jet If and when schools move to the model of one course fuel is used as an onboard coolant, it is exposed to in each area plus additional “in depth” courses, it is elevated temperatures in the presence of ca. 70 ppm logical that the first analytical course will become dissolved diatomic oxygen. Subsequent autoxidation more instrumental. This does not mean, however, that of the fuel hydrocarbons occurs, which often there is no time to address some of the traditional produces undesirable products such as gums, quantitative analysis techniques in the lecture and/or varnishes, and surface deposits. These bulk and lab. Some approaches that have proven to be surface deposits foul critical fuel system components, successful at our institution will be presented and i.e., valves, filters, and nozzles, which if left suggestions for future implementation welcomed unchecked can lead to catastrophic system failure. from those present. Therefore, a more complete understanding of jet fuel autoxidation is desired to both predict deposition a 344. Headspace Analysis of a Simulated Oil priori and present opportunities for deposit Spill: Demonstration of the Utility and mitigation strategies. Limitations of Retention Times for Qualitative Analysis in a Gas It is known that autoxidation proceeds via a free Chromatographic Experiment radical chain mechanism to produce hydroperoxides as an intermediate molecular species. Since Lois A. Zook-Gerdau. Chemistry, Muskingum hydroperoxides are a thermally labile species, they University, New Concord, OH, United States. tend to decompose and produce radicals which auto accelerates the oxidation process. We intend to Students in the environmental chemistry laboratory present results from a recent study investigating were introduced to the basic principles of various factors affecting this key hydroperoxide chromatography through the analysis of a decomposition reaction. The results show that the contaminated soil sample using GC-MS. The concept decomposition rate is a function of hydroperoxide of headspace analysis of volatile components was structure and organometallic type (both ligand type also introduced. Students built their own library of and metal type). Additionally, a synergistic effect on retention times for a series of hydrocarbons and decomposition rate was discovered when both alcohols that were suspected to be components of the simulated oil spill. Soil samples were prepared by

organometallic and organic acid were added to the acetogenesis, and methanogenesis. These processes hydrocarbon system. catabolize major macromolecules in an anaerobic (oxygen free) environment to produce biogas. The 346. The Use of Gas Chromatography for biogas, when reformed, becomes biomethane, which Biogas Analysis is a renewable, methane rich, clean gas that can easily 1 1 substitute petroleum based natural gas. In a Amanda M. Andersen, Jennifer L. Aurandt, John collaborative effort between Kettering University, 2 1 Seeley. Department of Chemistry & Biochemistry, Swedish Biogas International, and the City of Flint, Kettering University, Flint, MI, United States; efforts have been made to establish the Center for 2 Department of Chemistry & Biochemistry, Oakland Energy Excellence in Flint, focused on the renewable University, Rochester, MI, United States. energy of biogas. Currently, four lab digesters are Energy from natural gas accounts for 24% of total running and producing biogas. To maintain a healthy, energy consumed in the United States. Natural gas is robust environment for the microorganisms in the a robust form of energy which is rich in methane reactors, daily maintenance and weekly testing is content and is low in impurities which are typically performed. On a weekly basis, the pH, alkalinity, much higher in other types of fossil fuels. This volatile fatty acid content, and nitrogen content are quality suggests that it is a very clean and safe gas; it tested and analyzed. For research purposes, the can be used in providing heat for homes, a source for digesters vary slightly from one another. Between the cooking, and even in powering vehicles. The three sludge digesters, the hydraulic retention time downside of petroleum based natural gas is that it is a (HRT) varies. This variation has shown differences in non-renewable resource. On the contrary, methane gas production between the digesters running on 28 rich gas that is produced by the breakdown of organic day HRT and the 40 day HRT. material in an anaerobic environment, called biogas The fourth digester varies greatly because it has been (or biomethane), is a renewable energy source. converted to a co-digestion digester, because the Kettering University, Swedish Biogas International, substrate fed to this digester is composed of mixed and the City of Flint are collaborating in order to food, instead of primary sludge. This digester has create the Center of Energy Excellence in Flint. This shown to be competing well against the all sludge diverse group of scientists, engineers, and business digesters and is producing equal or sometimes greater professionals study numerous different facets of the amounts of biogas. For this project, continuous anaerobic digestion technology. This research research will be done to discover which variations of focuses on the gas analysis portion of the creation of parameters, when combined, will push the methane the anaerobic digestion and verification laboratory (biogas) production to its peak, while still where content analysis and forensic analysis of maintaining a healthy digester. biogas and anaerobic digesters are performed. Gas Chromatography is implemented as the optimal 348. Production of Hydrogen from Aluminum analytical tool for quantifying the components of the Nanoclusters and Water: Simulation Using biogas including methane, carbon dioxide, hydrogen Density Functional Theory sulfide and siloxanes. In addition, the problems Paul N. Day,1,2 Kiet A. Nguyen,1,3 Ruth Pachter.1 associated with the undesirable components are 1Materials & Manufacturing Directorate, Air Force discussed. Standard operating procedures have been Research Laboratory, Wright-Patterson AFB, OH, developed and used for the analysis of the United States; 2General Dynamics Information components. Anaerobic digestion of primary sludge Technology, Dayton, OH, United States; 3UES, Inc., has consistently produced about 55% methane; future Dayton, OH, United States. goals include studying different substrates to increase the methane yield and decrease levels of impurities in Hydrogen production from aluminum cluster anions the gas. and water has been observed under multicollisional conditions in a fast-flow reactor. The reaction can be 347. The Production of Biomethane through written: Anaerobic Fermentation of Biomass -1 -1 Aln + 2H2O → Aln(OH)2 + H2 (1) Tiffany Snow, Jennifer Aurandt. Department of Chemistry and Biochemistry, Kettering University, Previous studies have indicated strong size selectivity Flint, MI, United States. -1 for H2 production by this reaction. In particular, Al12 The fermentation of biomass requires four complex apparently does not release the hydrogen, instead processes categorized as hydrolysis, acidogenesis, following the reaction,

350. Microbial Growth and Biofilm -1 -1 Al12 + 2H2O → Al12(H)2(OH)2 (2) Formation: GC-MS Analysis and Traditional

-1 -1 -1 Culture of Jet A and Alternative Fuels while Al16 , Al17 , Al18 all release H2 by reaction (1). This has been explained by the adjacent Lewis Lori M. Balster, Loryn L. Bowen, Lisa M. Brown, acid – Lewis base pair sites in these compounds, Susan S. Mueller, Linda M. Shafer, Max Tsao, which makes the final step in the mechanism Marlin D. Vangsness. Energy & Environmental energetically accessible. The possible mechanisms, Engineering, Bioenvironmental Group, University of which show site-selectivity, have been investigated Dayton Research Institute, Dayton, OH, United using density functional theory with both GGA and States. hybrid exchange-correlation functionals. For at least fifty years, microbial growth has been a known problem in aviation fuel. Microbial growth 349. Characterization of Metal Oxide can cause degradation of fuel, fuel additives, and/or Additives and Their Role in Cu/ZnO-Based fuel system components. Biofilms, which are Catalysts for Catalytic Reduction of Carbon microbial growth organized into sheets, clumps, or Dioxide to Methanol mats of exopolysaccarides (EPS), are known to be especially harmful to fuel systems. Recently, the U. John P. Baltrus,1 Sittichai Natesakhawat,1,2 Bryan 1 1 S. Air Force has been exploring the use of coal based Morreale. National Energy Technology Laboratory, and renewable fuel sources as a means of enhancing U.S. Department of Energy, Pittsburgh, PA, United 2 and/or replacing traditional jet A and JP-8 aviation States; Department of Chemical and Petroleum fuels. One of the many issues with replacing Engineering, University of Pittsburgh, Pittsburgh, traditional fuels with alternative fuels is the PA, United States. possibility of an increase in microbial growth due to

Catalytic hydrogenation of CO2 to methanol is of the compositional differences of the fuels. In this interest because it produces a valuable fuel and study, microbial growth and biofilm formation in chemical feedstock while offering a practical several Fischer Tropsch (FT), animal, and plant approach to utilizing CO2. Currently, methanol derived fuels are compared to those in traditional jet production using Cu/Zn/Al2O3 catalysts primarily A fuel. GC-MS analysis including hydrocarbon type utilizes CO-rich syngas and the catalysts have been and traditional culture methods are utilized. formulated for that feedstock. Thus they have low activity and stability under CO2-rich conditions. By 351. Hexadecane Hydrotreating as a introducing various combinations of promoters, they Surrogate for Fischer-Tropsch Upgrading to can be tailored to operate under CO2-rich conditions. Aviation Fuel Using a Co/MoO3/Silica- By using various characterization methods to better Alumina Catalyst understand the roles of ZnO and promoters, the nature of the active sites in Cu/ZnO-based catalysts Heinz Robota, Jeremy Jones. University of Dayton can be identified, which in turn will aid in designing Research Institute, Dayton, Ohio, United States. novel catalysts that are suitable for CO2- to-fuel The U.S. Air Force has taken the lead in certifying applications. 50%/50% blends of synthetic fuels with petroleum- derived fuels and will soon be followed by the A set of novel Cu/ZnO-based catalysts have been commercial aviation fleet. synthesized and investigated for methanol synthesis The synthetic component is a Fischer-Tropsch by CO2 hydrogenation. Up to a two-fold increase in derived product obtained by upgrading the broad tunover frequency was observed when compared to a spectrum FT oils and wax. commercial catalyst. Characterization of the catalysts To further this effort, the Air Force is constructing a was accomplished using classical and spectroscopic facility for producing its own samples of both techniques. The role of each component of the specification and off-spec materials for further catalyst was delineated based on the characterization research. As part of that effort, we investigate the results and will be discussed. A combination of in- activity and selectivity of an unsulfided situ and post-reaction characterization has revealed Co/MoO3/Silica-Alumina catalyst using hexadecane the true identity of the active site and possible as a model feed in advance of using this catalyst in reaction pathways for methanol synthesis. the Assured Aerospace Fuels Research Facility to process both simulated and actual FT feeds. In the unsulfided form, this catalyst exhibits a significant non-selective “methanolysis” activity in addition to

modest isomerization and hydrocracking acitivites. of the lives of many in the world are tremendous. We report on hydroisomerization and hydrcracking This talk will highlight progress being made and activities and selectivities under a range of typical suggest some chemical and material opportunities. upgrading process conditions. The results are presented within the context of the metal-acid 354. An Introduction to the Green Energy balance concepts. and Information Center – The Environmental Branch of the Dayton 352. Energy for World Peace International Peace Museum Wade Adams, Richard E. Smalley. The Richard E. Ralph Dull. Green Energy and Information Center, Smalley Institute for Nanoscale Science and Dayton International Peace Museum, Dayton, OH, Technology, Rice University, Houston, TX, United United States. States. The Energy field is vastly broader than renewable After hearing a surprising statement from an oil and alternative energy. Even though conservation of company Fellow in 2002, Rick Smalley embarked on energy and natural resources reduces fossil-fuel a campaign to raise awareness of the rapidly growing consumption, the solution to an impending need for clean, inexpensive, widely available energy. catastrophe takes much more effort from everyone During intense study of the myriad issues, we than merely switching to more efficient light bulbs. organized three groundbreaking nano and energy workshops which showed the way to a new vision for One question for us to consider is: Should our society a worldwide energy system that would send energy or individuals wait until we are forced by wherever needed as electricity, not via mass transport circumstances to change our ways or should we step of fossil fuels. Energy was considered by Rick up to the plate now? We need to ask ourselves if it is Smalley to be both the single most important problem coincidental that the carbon content of the facing humanity today, and a magnificent scientific atmosphere has increased on the same plane for and technical opportunity for a revolution in eighty years as the increase in population and fossil nanotechnology and other physical sciences and fuel consumption. (In 1930, human activity placed 1 engineering. As technical optimists, we can examine, billion tons of carbon into the air; now it’s 7 billion with hope, the links among the major challenges tons per year.) Other questions: Does it matter? Are facing humanity, many of which can foster solutions times a-changin’? What’s the evidence? The Green that will promote the improvement of life and Energy and Information Center attempts to answer extension of prosperity and peace for the world. these questions.

353. Energy and the Future: Opportunities 355. Evolution of Metabolism for Destruction for the World of DoD Pollutants Douglas Dudis. Air Force Research Laboratory, Jim Spain. School of Civil & Environmental Materials & Manufacturing Directorate, Wright- Engineering, Georgia Institute of Technology, Patterson Air Force Base, OH, United States. Atlanta, GA, United States. The energy problem has long been recognized as one This year marks the 40th anniversary of Earth Day of the greatest challenges facing humanity. While not and in that time we have witnessed dramatic shifts in broadly appreciated, solutions to the majority of the attitudes and practices related to pollution. The US energy problems are in sight, with many military has taken a major responsibility for commercially or nearly commercially available. development and implementation of new technology Costs for sustainable living are dropping, and it is not for dealing with hazardous wastes because of the difficult to visualize a world in which sustainable, scope of the industrial complex devoted to military distributed energy is widely available at costs, or activities. The resulting technologies have been even cheaper, than what has traditionally been adopted quickly by the private sector and the available. Just as wood and coal played central roles regulatory community and are now being used in bringing about the industrial revolution, and the worldwide. The major contaminants of concern for ready availability of petroleum enabled the th DoD are fuels, chlorinated solvents, and transportation revolution of the 20 century, explosives/propellants because they are used at switching over to renewable primary energy supplies military installations across the globe. The most will herald civilization sized changes. The remarkable technological advances for destruction of opportunities for economic growth and improvement hazardous wastes have been enabled by

biotechnology and bioremediation. Today, Travis Q. Battiest, Clovis A. Linkous. Department bioremediation is very well established for cleanup of of Chemistry, Youngstown State University, military and industrial contaminated sites. It is the Youngstown, OH, United States. first fundamental advance beyond burning and it is Contaminated ground water is still a large problem inherently green chemistry. The biodegradation of for most of the United States. One contaminant, petroleum based fuels in soil and groundwater is sulfur, is both a natural and a man-made problem in relatively straightforward because the components many sources of drinking water. Sulfur is most are all natural organic compounds and, therefore, notable for the aesthetically displeasing smell of biodegraded readily by soil microorganisms. In rotten eggs, but can also cause intestinal issues. contrast, chlorinated solvents and explosives were not Currently the processes of removing sulfur are either believed to be biodegradable on the first Earth Day. expensive or ineffective. Through the research of Now, as a result of DoD funding we have available a how sulfur reacts to dilution, concentration, pH, growing array of microorganisms and metabolic temperature, and redox chemistry we are hoping to pathways for complete destruction of the majority of create a more cost-effective and environmentally the synthetic solvents and explosives used by DoD. friendly solution to the problem of sulfur Anaerobic bacteria that catalyze reductive contamination. dehalogenation of chlorinated solvents support a major portion of the remediation efforts at DoD sites. We have recently discovered bacteria that mineralize 357. Recent Advances in Femtosecond-CARS vinyl chloride and cis-dichloroethylene and their for High-Bandwidth Diagnostic Applications roles are being investigated at a variety of in Combustion Systems demonstration sites. Waruna D. Kulatilaka,1 Sukesh Roy,1 James R. Gord.2 1Spectral Energies, LLC, Dayton, OH, United Explosives and propellants are military unique States; 2Propulsion Directorate, Air Force Research problems. TNT, RDX, DNT, CL20, nitroglycerine Laboratory, Wright-Patterson AFB, OH, United and ammonium perchlorate can all be biodegraded or States. inactivated by microorganisms and bioremediation is widely used for destruction of such explosives in Femtosecond coherent anti-Stokes Raman scattering contaminated soil and groundwater. The remarkable (fs-CARS) spectroscopy has emerged as a promising scientific discovery is that microbes can evolve the technique for high-speed, collision-free measurement capability to degrade novel synthetic chemicals after of temperature and species concentration in reacting such chemicals are introduced into the environment. flows. In fs-CARS, the broad spectral bandwidths of For example, the metabolic pathway for degradation the pump and Stokes lasers permit the coupling of of DNT was recently assembled by recruitment of each ro-vibrational Raman transition via a large genes from the naphthalene degradation pathway. number of pump-Stokes photon pairs, creating a Once the pathway evolved it provided the basis for strong Raman coherence in the medium and hence several large scale bioremediation projects including resulting in very strong CARS signals. The a major contaminated site at Badger Army temperature is extracted by mapping the initial Ammunition Plant, Wisconsin. The current challenge Raman coherence dephasing rate which is free of is to understand and predict the evolution of collisional effects. By incorporating a chirped probe microbial pathways so that they can be applied to pulse, we have demonstrated single-laser-shot emerging contaminants and new military materials as temperature measurements at a data rate of 1 kHz. A they are developed. The genes seem to be recruited theoretical code has been developed to extract single- from pathways for degradation of the millions of shot temperature from time-resolved data. High- natural organic compounds in the biosphere. An bandwidth temperature measurements have also been understanding of the existing metabolic diversity and performed in a variety of laboratory burners how pathways are assembled will allow the rational operating laminar, driven and turbulent flames. Our design of molecules that can be biodegraded at the measurement capabilities provide invaluable data for end of the life cycle or when they are released into turbulent combustion modelers to validate their large- the environment. scale computer codes. In addition, we have also investigated the interferences caused by 356. Remediation of Sulfide-Contaminated intermolecular polarization beatings in fs-CARS. The Groundwater effects of CO and CO2 interferences in the N2 and O2 fs-CARS respectively will be discussed in detail.

358. High-Speed Hybrid fs/ps Coherent Anti- Our group has been exploring different pulse shaping Stokes Raman Scattering Spectroscopy in strategies for chemical sensing via single-beam Chemically Reacting Flows CARS. Their implementation relies on an ultra- broadband femtosecond) laser source and a calibrated 1 1 Joseph D. Miller, Mikhail N. Slipchenko, Terrence pulse shaper. We use multiphoton intrapulse 1 2 2 R. Meyer, Hans U. Stauffer, James R. Gord. interference phase scan (MIIPS) technique to 1 Department of Mechanical Engineering, Iowa State compensate for ultrashort pulse distortions and apply 2 University, Ames, IA, United States; Propulsion various phase-and-polarization shaping schemes to Directorate, Air Force Research Laboratory, Wright- gain the spectral resolution and suppress the Patterson Air Force Base, OH, United States. nonresonant background. In one approach, we excite impulsively all Raman transitions within the pulse Hybrid femtosecond/picosecond coherent anti-Stokes -1 Raman scattering is employed for time- and bandwidth (up to 2500 cm ). In the others, we frequency-domain spectroscopy in high-temperature exercise selective excitation of a single vibrational chemically-reacting flows. Collisional-free and mode of target molecules using chirp, sinusoidal or nonresonant-background-suppressed kHz-rate binary phase shapes. Selective excitation is of interest thermometry measurements, derived from the for CARS imaging when spectrally-resolved temperature-dependent excited vibrational states of acquisition compromises the data collection speed. Pulse shaping then ensures straightforward Raman N2, are reported with accuracy and precision better than 3% and 2% respectively. frequency tunability and improves the image contrast Additionally, the probe pulse bandwidth and as illustrated in panel (b) of the figure. Here the top lineshape are varied to maximize nonresonant panel displays the CARS image of a 10 µm CO2 jet background suppression while maintaining sufficient using broadband impulsive excitation, while the resonant signal for single-shot measurements. In bottom panel shows the same CO2 jet imaged using combination with a detailed temporally and spectrally selective binary phase shaping. resolved theoretical model, time–frequency dynamics of the N2 molecule are explored with implications for simultaneous temperature and pressure measurements along with the determination of fundamental rovibrational parameters.

359. Pulse Shaping for Single-Beam CARS Spectroscopy and Imaging Paul J. Wrzesinski,1 Dmitry Pestov,1 Vadim Lozovoy,1 Bingwei Xu,2 Sukesh Roy,3 James R. Gord,4 Marcos Dantus.1,2 1Department of Chemistry, Michigan State University, East Lansing, MI, United

States; 2Biophotonic Solutions Inc., East Lansing, The application of these pulse shaping methods to a MI, United States; 3Spectral Energies LLC, Dayton, variety of solid, liquid and gas samples, OH, United States; 4Propulsion Directorate, Air Force demonstrating the capabilities of single-beam CARS, Research Labs, Wright-Patterson AFB, United States. will be highlighted. Recent advances in laser and pulse shaping technologies have made it possible to perform 360. Tunable Diode Laser Absorption coherent anti-Stokes Raman scattering (CARS) Measurements in Supersonic Flows measurements using a single laser beam, and allow Michael S. Brown,1 Dominic L. Barone,1 Todd for acquisition of CARS spectra over the entire 1 2 1 molecular fingerprint range, with no wavelength Barhorst, William F. Terry. Aerospace Propulsion Directorate, Air Force Research Laboratory, Wright- scanning or changes to the experimental parameters. 2 The single-beam method, originally implemented for Patterson AFB, OH, United States; Innovative microscopy, has been extended beyond that to Scientific Solutions, Inc., Dayton, OH, United States. measurements in the condensed and gas phases and By taking advantage of impressive advances in diode has become a convenient, practical alternative to laser and associated technology, tunable diode laser multi-beam approaches. spectroscopy (TDLAS) has become a widespread tool for optical diagnostics in reacting flows. Measurements of target species concentration (e.g.

H2O, O2, and CO2), temperature, pressure and a-ODPA resins. These imide resins were fabricated velocity have been demonstrated in a wide variety of into polyimide/T650-35 carbon fiber composites by a environments by several research groups. RTM process at 280°C. Composites properties Commercialization of niche measurement derived these RTM imide resins, such as open-hole instruments based on TDLAS has been achieved. The compression and short-beam shear strength, will be current maturity of the technique enables close compared to each other at room temperature, 288 ºC scrutiny of collected signals to ascertain expectations and 315 °C. These high temperature RTM resins of accuracy and precision in measurements coupled exhibit outstanding properties beyond the to reacting flows. TDLAS presents one of the few performance of conventional RTM resins, such as means by which in-stream measurements can be epoxy and BMI resins which have use temperatures made in supersonic reacting flows that frequently around 177°C and 232° C for aerospace applications. have limited optical access. We have been using the technique for time-dependent measurements of 362. Addition of Octastyrenyl Polyhedral temperature, pressure, water concentration and Oligomeric Silsesquioxane on Properties of velocity in direct-connect supersonic flow facilities. Bismaleimide Resins Cured with A sample of this data will be presented and discussed Diallybisphenol A in the context of comparison with flow modeling efforts and conventional wall measurements of Jiang Zhu, Andre Lee. Department of Chemical temperature and pressure. Upstream of the Engineering and Materials Science, Michigan State combustor, the fluidic behavior of supersonic flows is University, E. Lansing, MI, United States. quite complex. Currently, no comprehensive model Varying amounts of Octastyrenyl polyhedral can capture all of the observed and inferred oligomeric silsesquioxane (octastyrenyl-POSS) were dynamics. For example, prediction of transient and added in Bismaleimide (BMI) and Diallybisphenol-A unstable aspects of shock-wave-boundary-layer (DABA) thermosetting resin. Up to 10 weight interaction are beyond even numerical approaches. percent of octastyrenyl-POSS can be made soluble in TDLAS measurements coupled with other diagnostic BMI-DABA resin and forms transparent nano- information offer a means to address these o composite after cured at 250 C. Differential Scanning shortcomings. Calorimetry (DSC) was used to study the effect of POSS addition on the cure kinetic of BMI-DABA. It 361. Low-Melt Viscosity Imide Resins Based was found that the addition of POSS did not on Asymmetric Dianhydrides significantly affect the activation energy of cure. This Kathy C. Chuang,1 Jim M. Criss,2 Eric A. Mintz.3 suggests that octastyrenyl-POSS behave more like 1Polymer Branch, NASA Glenn Research Center, nano-particles blended in the BMI-DABA network. Cleveland, OH, United States; 2M & P Technologies, Moisture absorption, thermal and mechanical Marietta, GA, United States; 3Center for Polymers & properties of cured BMI-DABA networks containing Composites, Clark Atlanta University, Atlanta, GA, 0, 2, 5 and 10wt% of octastyrenyl-POSS were also United States. investigated. Moisture uptake kinetics indicate the addition of octastyrenyl-POSS increase the Three series of low-melt viscosity imide resins (5-20 diffusivity of water in cured BMI-DABA network, poise at 260-280°C) were formulated from three which is consistent with swelled network due the different asymmetric dianhydrides, namely, 2,3,3’,4’- inclusion of POSS nano-particles. However, the glass biphenyl dianhydride (a-BPDA), 2,3,3’,4’- transition temperature as determined by Dynamic oxydiphthalic anhydride (a-ODPA) and 2,3,3’,4’- Mechanical Analyzer (DMA) increases as the amount benzophenone anhydride (a-BTDA) with 3,4’- of octastyrenyl-POSS increases. This observation in oxydianiline, 3,3’-methylenedianiline and 3,3’- combination with results form the cure study suggests diaminobenzophenone and terminated with the 4- that the POSS nano-particles hindered the network phenylethynylphthalic endcap, using a solvent-free mobility of cured BMI-DABA. Thermal Gravimetric melt process. These low-melt viscosity imide Analysis (TGA) also showed that thermal and oligomers also displayed long pot-life (1-2 h) that is oxidative stability of the BMI-DABA network was amenable for low-cost resin transfer molding (RTM) significant enhanced with addition of octastyrenyl- for composite fabrication. The cured RTM resins POSS. Overall mechanical and thermal properties of based on a-dianhydrides exhibited high glass cured BMI-DABA network were improved with transition temperatures, for example: Tg’s = 320-370 addition of octastyrenyl-POSS. ºC for a-BPDA resins and Tg’s = 350-400 °C for a- BTDA resins as compared to Tg’s = 265-320 °C for

363. Electrothermal Polymer Nanocomposite LCNs) is observed. Crosslinking density of azo- Actuators LCNs increases with curing time. Glassy and rubbery storage moduli (E’) and tan δ of azo-LCNs also Aaron T. Sellinger,1,2 David H. Wang,3 Loon-Seng 1 1 1 increase with crosslinking density. Interestingly, the Tan, Richard A. Vaia. Materials and bidirectional (forward and reverse) bending angles of Manufacturing Directorate, Air Force Research 2 the polydomain azo-LCN cantilevers at equilibrium Laboratory, WPAFB, OH, United States; National decrease with increasing temperature and Research Council, Washington, DC, United States; 3 crosslinking density. The influence of other variables University of Dayton Research Institute, Dayton, on the photomechanical response of the azo-LCN, OH, United States. such as the nature of the azobenzene monomer, The novel property combinations offered by polymer concentration of the azobenzene in the polymer nanocomposites (PNC) afford unique opportunities sample, and the thickness of the cantilever will also for sensor and actuator-based devices. Carbon be discussed. nanotube (CNT) additives, both below and above percolation, have been shown to reduce the electric- 365. Broadening of a Polymer Stabilized fields required to induce actuation by up to two- Negative Dielectric Anisotropy Cholesteric orders of magnitude in various electrostrictive and Notch by a Low DC Field piezoelectric polymers. This behavior is commonly attributed to local electric field modification and Madeline Duning, Lalgudi V. Natarajan, Vincent charge accumulation within the PNC. Alternatively, Tondiglia, Timothy White, Richard L. Sutherland, the low percolation thresholds that are typical of Timothy J. Bunning. Materials and Manufaturing these material systems can also promote actuation via Directorate, Air Force research laboratory, WPAFB, resistive (Joule) heating at relatively low applied OH, United States. fields. Infrared imaging of polyimide (CP2) A dynamic broadened reflection band was achieved nanocomposites containing single wall nanotubes when a weakly polymer stabilized cholesteric liquid (SWNTs) and carbon nanofibers (CNFs) reveals crystal containing a negative dielectric anisotropy o temperature increases in excess of 225 C at fields no nematic was subjected to a low DC field (< 3V/mm). greater than 0.01 MV/m applied in-plane. Thus, The broadening effect was significant as the notch depending on the mechanical boundary conditions bandwidth enlarged up to 3 times from its original employed, thermal expansion driven buckling or value. The broadening effect is proportional to the o mechanical softening of the polymer at Tg (220 C) strength of the applied DC field and relaxes to the can result in macroscopic strains of up to 5%. original bandwidth when the DC field is removed. Consequently, under the application of an AC Fields, greater than a critical value cause a blue shift voltage, both the temperature and shape of the PNC of the broadened band. The cholesteric mixture were observed to oscillate at frequencies as high as consisted of the chiral dopant S811, the negative 10 Hz. dielectric LC ZLI-2079, 5% LC diacrylate monomer RM257 and 0.05% of UV initiator Irgacure 369. 364. Polarization Controlled Weakly polymer stabilized network was formed by Photomechanical Bidirectional Bending UV curing. The curing was done by illuminating with Behaviors of Polydomain Azo-Liquid a flood lit laser line at 364nm, or an EXFO UV lamp Crystalline Polymer Networks with a 365nm filter. Kyungmin Lee, Timothy J. Bunning, Timothy J. 366. Tunable Hyper-Reflective Filters White. Materials and Manufacturing Directorate, Wright-Patterson Air Force Research Laboratory, Michael E. McConney, Timothy J. White, Jennifer WPAFB, Ohio, United States. Hurtubise, Vince P. Tondiglia, Lalgudi Natarajan, Timothy J. Bunning. Materials and Manufacturing We report the photomechanical behavior of Directorate, Air Force Research Laboratory, azobenzene liquid crystal polymer networks (azo- WPAFB, OH, United States. LCN). High modulus, glassy polydomain azo-LCNs were synthesized by copolymerizing RM257, 4-4’- Optical Bragg reflections are easily formed from bis[6-(acryoloxy)hexyloxy]-azobenzene (2-azo), and cholesteric liquid crystals (CLC), which makes them 1 wt% of the inorganic photoinitiator Irgacure 784 (I- promising for many photonic applications. The CLC 784). The effect of crosslink density on the band-gap is limited to circularly polarized light polarization-controlled bidirectional bending of (CPL), with the handedness of the polarized light azobenzene liquid crystalline polymer networks (azo- matching helical pitch of the cholesteric director.

Therefore, CLCs are limited to reflections of 50% or incomplete combustion of various organic materials less of unpolarized light. Here, we present tunable including tobacco; cigarette smoke is a complex cholesteric systems capable of reflecting both left and mixture of various classes of compounds including right circularly polarized light, so-called tunable numerous PAHs. This experiment is about collecting hyper-reflective CLCs. This tunable high contrast and analyzing the particulate matter that would enter system was realized by combining a left-handed the human lungs both from directly smoking cigarette tunable CLC mixture with a static right-handed and from second hand smoke. Benzo(a)pyrene and polymeric scaffold capable of templating the LC Anthracene are considered among the most molecules. The polymeric scaffold was formed by dangerous classes of PAHs, and are going to be polymerizing in the presence of a right-handed CLC analyzed through this experiment. Marlboro Reds mixture. The polymerization process was localized cigarettes and a cigar are being used for this research. near one surface of the cell by including the photo- The residues of ten cigarettes without filters are initiator in the anchoring film, instead of the collected in filter paper using the vacuum aspirator in conventional approach of including the initiator in the order to be analyzed by GC/MS for identifying the bulk CLC mixture. Then the CLC was leeched out by different levels of PAHs from first hand (FH) and immersing the cell in a solvent, followed by drying second hand (SH) smoke. Then later on to plot all the and refilling with a left-handed CLC. These tunable data to the calibration curve to determine the amount high contrast optical materials are highly promising of PAHs entering the human lungs. for technologies such as active color displays and tunable lasers. 369. Lead Concentration in Urban Garden Soil 367. Photoinduced Broadening of Cholesteric Liquid Crystals Marilynn Barcus, Sherry Cucci. REEL General Chemistry Lab, Cleveland State University, Alex Freer, Timothy J. White, Nelson Tabiryan, Cleveland, OH, United States. Timothy J. Bunning. Materials & Manufacturing Urban gardens have increased in popularity in the Directorate, Air Force Research Laboratory, Wright- Cleveland, Ohio area in the past years in conjunction Patterson Air Force Base, OH, United States. with city funded projects to increase “green” The selective reflection of cholesteric liquid crystals awareness in the community. Cleveland, Ohio has (CLCs) is well-known and has been utilized in a been an industry dense area leading to many deposits number of dynamic optical applications. This work of chemical byproducts in the environment. This presents a novel approach to passively (e.g. all- project’s purpose was to investigate lead levels in optically) cue reflection notch broadening in existing urban gardens in Cleveland. Soil samples photoresponsive CLC formulations based on high were obtained, digested, filtered, and analyzed by helical twisting power (HTP) bis(azo) chiral dopants. means of an Inductively Coupled Plasma Mass The original reflection bandwidth of approximately Spectrometer (ICP-MS), from three existing urban 100 nm is increased to as much as 1700 nm, by gardens and compared to a suburban-rural exposing 36 micron thick cells to UV light. The community garden. Spike and Recovery maximum attainable bandwidth is shown to be a methodology was utilized to determine validity and function of cell thickness, light intensity, and strongly reliability of digestion protocol. Lead levels were related to the HTP of the photoresponsive chiral significantly higher in one urban garden and dopants. An all-optical technique of simultaneous UV insignificantly higher in the other two urban gardens and green light exposure is demonstrated to trap the in comparison with lead levels of the suburban-rural reflection notch at a predetermined position and garden. bandwidth. 370. Heavy Metal Concentrations in Local 368. Determination of PAHs in First and Rivers Second Hand Cigarette Smoke Meaghan Spann, Elizabeth Looney. REEL General Claude Al Fahel, Muneer Jaber, Candice Jones, Chemistry Lab, Cleveland State University, Elizabeth Rosza. REEL Organic Chemistry Lab, Clevelend, OH, United States. Clevelend State University, Clevelend, OH, United The Environmental Protection Agency (EPA) has States. designated a number of rivers as Areas of Concern Polycyclic aromatic hydrocarbons (PAHs) are a class (AOC s). AOCs are bodies of water with dangerously of environmental pollutants created primarily from high pollutants, including heavy metals. The Black

River in Lorain, Ohio has been on the EPA’s AOC 373. Lead (Pb) Concentrations in Gasoline list since 1990. The current study attempted to Emissions identify the presence of heavy metals, and in particular lead, in sediment from the Black River. Igor Deynega, Mark Galay, Maryana Skotsen. REEL The Rocky River, with no EPA classification, was General Chemistry Lab, Cleveland State University, used as a control site. Using inductively coupled Cleveland, OH, United States. plasma (ICP) analysis, it was determined that obth Grade 89 gasoline was obtained from several local the Black River and Rocky River had similar lead gas stations. Each sample was burned in a vacuum content well below the toxic level of 500 – 1000 ppm apparatus which enabled the lead filtrate to be at 4.03 ppm and 2.25 ppm respectively. trapped in an aqueous solution. Inductively Coupled Plasma (ICP) was used to measure the amount of lead 371. Concentrations of Arsenic in CCA- present in each gasoline sample. The quantities Treated Wood detected by the ICP was compared with the standards for allowed lead in gasoline set by the EPA. Emiliya Akhumian, Ahamad Maarouf, Adam Determined lead levels were within the limits set by Salem. REEL General Chemistry Lab, Cleveland the EPA. State University, Cleveland, OH, United States. Chromium copper arsenate is a chemical wood 374. Usage of Coffee Grounds in the Removal preservative used in pressure treated wood to protect of Mercury Ions from Drinking Water it from rotting due to insects and other organisms. As the name implies, CCA wood contains copper, Erik Schepens, Andrew Sadowski, Alyssa Petko. chromium, and arsenic. It has been widely used for REEL General Chemistry Lab, Cleveland State decades in outdoor structures. It was banned from University, Cleveland, OH, United States. residential areas in 2003 by the Environmental The increasing amount of heavy metal contamination Protection Agency (EPA). Wood samples were from coal-burning and industrial processes presents a collected from residential structures that were built growing danger to humans and animals. Mercury before 2003 and tested for arsenic using inductively contamination has been shown to cause serious health coupled plasma (ICP). Soil samples were also problems in humans. Current filtering technology is collected and analyzed for arsenic to determine if expensive and not entirely available in non- arsenic had leached into the soil surrounding the industrialized countries. Phytoremediation is an wooden structures. efficient and cost-effective technique used to rid soil and water from heavy metal contaminants. This 372. Determination of Tetracycline in Beef technique uses the intrinsic molecular mechanisms of Tissues Using High Performance Liquid plants to absorb heavy metal contamination from soil Chromatography (HPLC) and water. Coffee grounds have been shown to absorb lead ions from drinking water. The aim of this Anam Khan, Chantale Salem, William Waters. report is to explore the ability of coffee grounds to REEL Organic Chemistry Lab, Cleveland State absorb mercury ions from drinking water in order to University, Cleveland, OH, United States. provide cost-effective bioremediation. Our results Beef liver samples were obtained from two local show that coffee grounds do indeed have the ability butchers in order to determine and compare the to absorb mercury ions from water under certain amount of tetracycline antibiotics in beef tissues. circumstances. Extraction was used to separate the antibiotics from the meat tissues and then High Performance Liquid 375. Leaching of Bisphenol A into Foods Chromatography (HPLC) was used to analyze the during the Canning Process amount of antibiotics in the samples. Currently, many farm animals are feed antibiotics in order to provide Andrej Gabrovsek. REEL Organic Chemistry Lab, therapeutic treatment. Even though, antibiotics are Cleveland State University, Cleveland, OH, United not toxic, they can cause some harm, such as States. antibiotics resistance, to consumers who eat meat. In Bisphenol A is an organic compound associated with this study, the amount of tetracycline antibiotics in health problems and diseases, including breast and meat from two different locations will be determined prostate cancer and infertility as well as being an and compared. endocrine disruptor. BPA is an intermediate in the production of polycarbonate (PC) plastics and epoxy resins. These epoxy resins are used to coat the inside

of metal food containers. BPA can leach from this financial resources to pay for maintenance. This epoxy resin and into food, especially at increased study therefore surveys lead and copper in the temperatures of heat processed canned foods. This drinking water of central Ward 5. Samples from the study will measure the amount of BPA that leaches single water plant and each of three mains that serve into water from a selection of canned foods at the area, and ten buildings, are tested. Results from elevated temperatures and to compare these amounts copper are conclusive: Copper is present in all to currently acceptable levels. samples, but nowhere is the concentration near to the EPA action limit. A pair of experimental errors 376. Determination of 1,4-Dioxane in drastically widen confidence intervals for lead, yet Mouthwash (after a deal of error-analysis and some educated guessing), the errors are brought back under control Arsela Gishto. REEL Organic Chemistry Lab, and partial results presented for this metal as well: Cleveland State University, Cleveland, OH, United Water from the plant and from the mains almost States. certainly have no detectable amount of lead, and 1,4-Dioxane is a colorless organic compound that is while water from some buildings have lead known to be a carcinogen to animals and possibly to concentrations significantly different than zero, none humans. In addition it may cause damage to CNS, of them reach the EPA action limit. kidneys, and liver. 1,4-dioxane is used as both a foaming agent and stabilizing agent and is an 379. Accumulation of Arsenic and Toxic accidental byproduct of ethoxylation process in Heavy Metals in Chinese Brake Fern (Pteris cosmetic manufacturing. This contaminant has been Vittata) found in shampoos, deodorants, toothpastes, soaps, etc. In this study, mouthwashes were analyzed for Katie Lemmeyer, Jerome McGinty. REEL General 1,4-dioxane by GC/MS. Results indicate low Chemistry Lab, Cleveland State University, concentrations of 1,4-dioxane in some mouthwashes. Cleveland, OH, United States. The purpose of this research is to study the 377. Lead Detection in Potential Community capabilities of the fern Pteris vittata to remove Garden arsenic and commonly found toxic heavy metals from contaminated ground soil via bioremediation. In other Brittany Elmlinger, Rachel Elasser. REEL General studies, this plant has shown considerable ability to Chemistry Lab, Cleveland State University, absorb or metabolize highly toxic levels of forms of Cleveland, OH, United States. arsenic that would have otherwise left the ground soil In this study, lead levels were determined at a site unusable and unlivable by humans or any other where a community garden might be located close to organism. In this work we explore the possibility that the steelyard in Cleveland Ohio. Soil samples were this plant can not only be used to remove arsenic, but collected from two major areas on the Holmden site; also lead and chromium as well. Plants will be one from a yard area and one from where a house exposed to different concentrations of these once stood. Soil samples were dried, digested, chemicals to determine if there is a point where the filtered, and measured for lead concentration using metal would become toxic to the plant so that it could inductively coupled plasma (ICP). The lead no longer remove the contaminants. In addition, we concentrations at both sites were found to be above will expose several of the plants to a mixture of the EPA limits. arsenic, chromium, and lead to investigate whether or not the plant prefers one species over another. 378. Determination of Lead and Copper in the Drinking Water of Cleveland’s Central 380. Dissemination of Environmental Ward Chemistry Research: From the Classroom to the Lab to the Public Alexander Swift. REEL General Chemistry Lab, Clevelnd State University, Cleveland, OH, United Victoria Mason, Ted M. Clark. Chemistry, The Ohio States. State University, Columbus, OH, United States. Lead and copper are too often found in our drinking Environmental chemistry is a popular research water, especially in aging or poorly maintained water module theme at many institutions that contribute to distribution systems. Downtown Cleveland has many the Research Experiences to Enhance Learning older buildings, a water system that in places dates (REEL) program. At the Ohio State University more back to the Civil War, and no superabundance of than 300 general and analytical chemistry students

each year design their own soil or water infants if the concentration levels are too high. investigations to collect and analyze samples from According to the EPA’s national primary drinking the Greater Columbus area. The investigation water standard, the maximum contamination limit described here extends a student-proposed, (MCL) of nitrate-nitrogen is 10 mg/L. Samples from classroom-based research project of analysis of heavy Pickerington, Ohio were taken from ground water, metals in urban community gardens. Soil samples surface water, a natural pond and a manmade pond. from many Columbus gardens were tested by X-ray Using an ion selective electrode and a standard fluorescence spectroscopy and those with excessive addition method, the water samples were analyzed - levels of contaminants, such as lead, identified. for NO3 concentration. Results in the Pickerington - Concurrent to these analyses a website was prepared area show that the NO3 concentrations ranged from 0 in collaboration with OSU’s Digital Union to ppm to 1.2 ppm. These concentration levels are not describe the research context, procedures, data, and harmful according to the EPA’s drinking water overall student experience. This presentation standard. This project was performed in the general describes the design of the website and considers its chemistry laboratory at Capital University as a part of potential or sharing REEL research with classmates, the Research Experience to Enhance Learning future REEL students, and the general public. (REEL) consortium. Three weeks of the course were devoted to quantitative analysis of ions in natural 381. Ambitious Characterization of Heavy water samples. Metals Found in Urban Soil in the Greater Columbus, OH Area 383. Analysis of Maumee River Water for Nitrate Ion Jason Eng, Jason Stybel, Ted M. Clark. Chemistry, The Ohio State University, Columbus, OH, United Marilyn Archambeault. Department of Chemistry, States. Bowling Green State University, Bowling Green, OH, United States. Anthropogenic activities in urban areas have the potential to concentrate potentially toxic materials, The Maumee River is located in both Indiana and like lead and arsenic, in settings often frequented by a Ohio. It originates in Fort Wayne, IN and flows into large number of people. Exposure to these toxins may Lake Erie near Toledo, OH. Its watershed includes pose numerous health risks. The goal of identifying numerous agricultural areas, which makes it areas with increased concentrations of harmful toxins vulnerable to fertilizer runoff. Several large animal should also be joined with efforts to establish farms are located near the river as well. Both baseline values for these same substances at sites fertilizer and animal waste are known to be major with minimal anthropogenic contributions. To this contributors to elevated levels of nitrates in water. end, several hundred surface soil samples were Nitrate exposure through water consumption poses a collected from public urban parks throughout the threat to public health as nitrate ions are easily Greater Columbus, OH area. Analysis was dissolved in water and known to interfere with accomplished by students in the Research biological pathways and processes within the human Experiences to Enhance Learning (REEL) program at body. This project was undertaken to analyze several the Ohio State University using X-ray fluorescence samples of Maumee water along with tap water from spectroscopy. This presentation will discuss the Bowling Green, OH for nitrate concentration. (The experimental design for this ambitious in-class city of Bowling Green receives its tap water from research project, preliminary results, and future aims Maumee River). The nitrate levels in water were for this project. determined using a nitrate ion-selective electrode (ISE), which provides a voltage (in millivolts) that is 382. Analysis of the Nitrate Ion inversely proportional to the nitrate concentration Concentration in Pickerington, Ohio: A present in the water sample. REEL Undergraduate Research Project 384. Analysis of Mixed-Metal Fluoride Kelsey Peer-Bostic, Brianna Mitchell, Jens Perovskites Synthesized by First-Semester Hemmingsen. Department of Chemistry, Capital Chemistry Students at Capital University University, Columbus, OH, United States. - Prince N. Otchere, William J. Clark, Jr. Department Nitrate ion (NO3 ) is a nutrient pollutant found in of Chemistry, Capital University, Columbus, Ohio, waterways near agricultural, industrial, and sewage United States. waste areas. It is caused by agricultural runoff from fields, lawns, and golf courses and can be harmful to

In a general chemistry laboratory setting, students and [Cl-], where the CSO is released into the creek. synthesized fluoride perovskites as part of a research- There were high levels of Cl- (205.6-963.6 ppm) in based laboratory module conducted in the OCUR- all samples, relative to standard concentration limits REEL (Ohio Consortium for Undergraduate Research set by the EPA (250 ppm). These concentrations may - Research Experiences to Enhance Learning) project. be due to road salt runoff. The results of this - Three weeks were designated for the experiment. experiment show [NO3 ] (4.57-7.74 ppm) to be within During the first week, students made a pair of single the limits set by the EPA. Phosphate ion metal fluoride perovskites with the formula KMF3, in concentration was tested in samples taken from the which M was cobalt, copper, or nickel. During the same watershed where a storm drain from Main second week, mixed metal fluoride perovskites with Street flows into Alum Creek. Samples results 3- the formula KMxN1-xF3 were synthesized, in which M showed [PO4 ] of 5.0 ppm near the CSO outlet, and N were two of the three transition metals used in which is higher than EPA standards. the single metal fluoride perovskite synthesis. The values of x were chosen by the student researchers. 386. Effect of Time and Eutrophication on The single and mixed metal fluoride perovskite Nitrate and Nitrite Levels in Stream Samples samples were analyzed by ultraviolet-visible spectroscopy (UV-vis) and X-Ray Fluorescence Heidi M. Buckeye, Isaac Asamoah, John C. (XRF). The student analysis was primarily to Difrancesco, Andrew S. Fellure, Ian A. Freshwater, compare the expected composition of the mixed Pierce M. Freshwater, Shane Z. Guzman, Wesley C. metal fluoride perovskites to the composition Johnson, Heather N. Nauman, Mort Javadi. determined by XRF analysis of the metal (M) Biological Sciences, Columbus State Community content. Additionally, correlation of expected College, Columbus, Ohio, United States. composition with UV-vis absorption spectra was High concentrations of nitrate and nitrite pose health examined. In this presentation, data from a large hazard to humans. Excess nitrogen in streams is also number of the student researchers is compiled to associated with eutrophication and a decline in examine overall trends in expected versus measured dissolved oxygen levels in water. Factors including composition for the perovskite species. In addition to pH, temperature, and biodegradation can change the data analysis as per the student researchers, this concentrations of nitrate and nitrite in a body of compilation compares normalized UV-vis data to water. Water samples from Scioto River were taken, both expected and XRF measured composition. The beginning in 2008 through 2010, and have been data compilation proved to be instructive in both an analyzed to determine the nitrate levels at the time examination of the chemical composition trends and when samples were taken, as well as in 2010. the error analysis of reported student data. Nitrate and nitrite concentrations for 2008 samples 385. Analysis of Water for Nitrate, Chloride were 5.1 mg/L and 0.020 mg/L, respectively. The and Phosphate Ions near the Alum Creek same samples were stored and analyzed in 2010. It - - Combine Sewer Overflow in Bexley, Ohio: A contained 1.2 mg/L NO3 –N, and 0.010 mg/L NO2 REEL Undergraduate Laboratory _N. The reduction of the 2008 nitrate levels may have been due to a reduction in oxygen levels during the Bethany R. Davies, Kathryn Dove, Kori Keeton, storage period. Megan Meinert, Devin Mills, Katie O’Donnell, Jillian Stelmach, Ryan Williams, Jens Hemmingsen, The 2010 samples showed concentrations of 5.650 Margaret E. Ginn-Pease. Department of Chemistry, - - mg/L NO3 -N and 0.025 mg/L NO2 -N respectively. Capital University, Columbus, OH, United States. Both samples will be subject to eutrophication and Alum Creek and the combine sewer overflow (CSO) will be analyzed on weekly basis in order to discharge pipe are located in Bexley, Ohio. Water determine the fate of nitrate and nitrite in the above - near the CSO discharge pipe was analyzed for [NO3 ] samples. and [Cl-]. This research is relevant because the Ohio EPA continues to work towards reducing CSO output 387. Environmental Remediation of of contaminant ions throughout the state. Water Contaminated Groundwater Using Zero- samples from three areas surrounding the discharge Valent Iron Nanoparticles - - pipe were analyzed for [NO3 ] and [Cl ] using an ion selective electrode and the standard addition method. Adam I. Keller, Yassir Sheikhaldeen, Isaac Phosphate ion was measured using a colorimetric Rampersaud. Department of Physical Sciences, - Columbus State Community College, Columbus, determination. An increase was found in both [NO3 ] Ohio, United States.

Chlorinated hydrocarbons, such as trichloroethylene The synthesis of a potentially anti-diabetic (TCE) and dichloropropane (DCP), continue to be a hydrolysable tannin derived from 6-chloro-6-deoxy- common and persistent contaminant of groundwater D-glucose is shown. Key steps are the digalloylation across the United States. Zero-valent iron of the unprotected carbohydrate and the conversion nanoparticles have been reported to reduce these of the remaining two hydroxyl groups with a contaminants to the corresponding gaseous hexahydroxydiphenic acid derivative. hydrocarbons, but the commercial and practical application of this methodology remains elusive. The 390. Qualitative and Quantitative Analyses of delivery of the nanoparticles to a groundwater aquifer Lipidic Binders in Paint of Archaeological is difficult for a number of reasons: delivery of the Samples particles by way of a slurry injected at multiple injection well sites is difficult due to aggregation of Christina Phillips, Ruth Ann Armitage. Deparment the particles at the elution points, many types of iron of Chemistry, Eastern Michigan University, particles oxidize quickly in the presence of air, and Ypsilanti, MI, United States. the nanoparticles are fairly unreactive towards alkyl In order to reliably determine the age of rock chlorocarbons (e.g. DCP). Our studies are aimed at paintings with radiocarbon analysis, it’s important to developing a low-cost and practical method for know as much as possible about the organic delivery of the nanoparticles to a contaminated composition of the paint. One of the limitations in aquifer that circumvents the limitations of current characterizing binders in rock paintings by GC-MS is practices. the amount of sample available for analysis. Different To this end, we have screened several brands of classes of compounds - lipids, proteins, commercially available particles to identify the best carbohydrates - are found together in the natural candidates for reduction of all types of substances used as binders. chlorocarbons, including the stubborn alkyl Some methods, like thermally assisted chlorocarbons. This has been done by treating spiked hydrolysis/methylation-GC-MS, yield qualitative water samples with the particles and analyzing the information about all three classes in a single samples by GCMS. We are also experimenting with analysis. coatings to allow the particles to travel passively Quantitative analysis requires a more targeted through the soil while maintaining their reactive approach. This study focuses on using the residue left integrity, and measuring the results by conducting after extracting the proteins from modern and column studies in the lab. The ultimate goal is to archaeological rock painting binders for GC-MS conduct field studies at contaminated sites in the near analysis of the fatty acids. Modern binders prepared future. Our results obtained to-date and current in the laboratory were treated with ammonia to outlook will be presented in this poster. extract proteins. The remaining residue was saponified in ethanolic KOH (10%) and the resulting 388. Analysis of Nitrate in Portage River free fatty acids were extracted into diethyl ether. An Water aliquot of the ether extract was then derivatized to Adrienne Snyder, Kimberly Verhoff. Department of form trimethylsilyl esters of the extracted fatty acids, Chemistry, Bowling Green State University, Bowling which were then subjected to GC-MS for quantitative Green, OH, United States. analysis. The identities and quantities of the fatty acids present in the modern binders will help to better Portage river, located in Northwestern Ohio near understand the nature of archaeological materials. Bowling Green OH, flows through a heavily agricultural area potentially exposing its water to 391. Analysis of a Series of Ancient Herodian elevated levels of nitrate from fertilizer runoff. The Coins – The Biblical ‘Widow’s Mites’ – Via study was undertaken to analyze several samples of Energy Dispersive X-Ray Fluorescence Portage river water and the surrounding streams for nitrate concentration. Nitrate concentrations were Spectrometry determined using Ion Selective Nitrate Electrode. Danielle Garshott, Elizabeth MacDonald, Meghann Mouyianis, Mark A. Benvenuto. Department of 389. Synthesis of an Ellagitannin Derived Chemistry & Biochemistry, University of Detroit from 6-chloro-6-Deoxyglucose Mercy, Detroit, MI, United States. Jacob A. Venoy, Klaus B. Himmeldirk. Chemistry & A series of small, copper coins issued under the Biochemistry, Ohio University, Athens, OH, United authority of the Herodian kings has been analyzed by States. energy dispersive X-ray fluorescence to determine

their elemental compositions. These small coins are reliably radiocarbon date fragile organic artifacts widely believed to be the widow’s mite coin given to while preserving the whole artifact and even the the Temple treasury by the old woman noticed by fragments for further study. The efficacy of our Jesus, as mentioned in the Gospels. The findings for newly developed pretreatment protocol has been these items are presented. studied using gas chromatography-mass spectrometry to monitor the disappearance of marker compounds. 392. PLTL Games as Aids to Memorization We will discuss the results of a pilot study on cleaning and dating waterlogged and humic- Jillien H. Whiteside, Tracey A. Murray. Department contaminated textiles of known age with this non- of Chemistry, Capital University, Columbus, Ohio, destructive process. United States. The Chemistry Department at Capital University has been using Peer Led Team Learning (PLTL) workshops to provide students the opportunity to gain a further understanding of chemistry through active learning. In order to enhance these workshops, two different games were developed as aids to memorization for two different classes: Chemistry 101 and Chemistry 131. To determine the effectiveness of the games as learning tools and to gauge student opinion, the different games have been assessed using a pre-test and a post-test on the topic covered by the game played, as well as a student opinion survey. Data analysis to date show that over 394. Examination of the Patent Medicines 80% of students who played the games felt that doing and Nostrums Archived at the Henry Ford so contributed to their learning. This suggests that the Museum Via Energy Dispersive X-Ray Chemistry Department should continue using PLTL Fluorescence and Multi-Nuclear NMR games. Danielle Garshott,1 Elizabeth MacDonald,1 Thomas 1 1 2 393. Recent Developments in Nondestructive Sanday, Andrew Diefenbach, Mary Fahey, Mark 1 1 Radiocarbon Dating of Fragile Organic A. Benvenuto. Department of Chemistry & Artifacts and Textiles Biochemistry, University of Detroit Mercy, Detroit, MI, United States; 2The Henry Ford Museum & Ruth Ann Armitage, Deidre Hardemon. Department Greenfield Village, Dearborn, MI, United States. of Chemistry, Eastern Michigan University, Ypsilanti, MI, United States. A series of patent medicines and nostrums, permanently housed in the Henry Ford Museum in Plasma-chemical oxidation is an alternative non- Dearborn, MI, have been analyzed by energy destructive method for preparing fragile organic dispersive X-ray fluorescence (EDXRF) materials like textiles for radiocarbon dating by spectroscopy and multi-nuclear NMR. Such materials accelerator mass spectrometry. We report here on the were created over a century ago in relative secrecy, results of studies on bark and reed artifacts excavated and thus the ingredients and recipes have never been from a cave in Idaho, charcoal from rock paintings in made public. The initial findings for metals and Nicaragua, and a technical study on new cleaning organics in these items are presented. treatments for preparing textiles for dating. It is possible to date entire small artifacts with the plasma 395. Chemists and Artists: Both See Beauty, process. Contamination from the sample environment but Communicate It in Different Ways – such as humic acids from soil – must first be removed to ensure a reliable date. As the standard David W. Johnson,1 Mark Masthay,1 Alan acid-base-acid treatment to remove this Strathmann,2 Nick Voegler.2 1Department of contamination is inherently destructive, we are Chemistry, University of Dayton, Dayton, OH, developing new cleaning protocols for use with the United States; 2Department of Art and Technology plasma-chemical oxidation sample preparation Studies, School of the Art Institute of Chicago, technique. Using the tiny fragments obtained from Chicago, IL, United States. routine handling of larger artifacts, we have shown that it is possible to non-destructively clean and

Chemists and artists can both see an object as currently found in water purification, wound care, beautiful, but the way they would communicat its and fabric additives. beauty can be very different. In the object below: 397. Determination of Composition of Synthetic Lubricating Motor Oils by GC-MS Christopher Frye, David S. Ballantine. Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL, United States. The composition of three motor oils two synthetic motor oils, two of which were full synthetic oils and the other a synthetic blend, were determined by comparison to a series of standards consisting of straight chain alkanes ranging from C12- C34. The full synthetics were Maxima 530RR and Mobil One Racing 4T, the blend was Maxima Synblend. Major

components were tentatively identified by The chemist might describe it as interactions of comparison of retention times with those of n-alkane different wavelengths of laser light with a coiloidal standards. Initial investigations were performed using gold suspension. an Agilent 19091J-413 with a capillary column, HP-5 .32mm*30m*.25µm equipped with a FID. The An artist might describe the same object as The analytical method consisted of a temperature program framing of our intuitive associations with the very with an initial temperature of 40°C, a ramp rate of edge of our technical means gives us cause for self- 10°C/min and a final temperature of 250°C with a reflection. When do we know things? What is built hold time of 40 minutes. The synthetics contained into our physiology and what is learned? We less than 10% n-alkanes (v/v). The additional major continue to achieve, to become new—to redefine components were tentatively identified using a GC- ourselves through the advancement of our thoughts MS system by matching fragmentation patterns with and technologies. We imagine, design, make, and we the compound library. destroy—and we accumulate associations as we do memories: as flickering visions, while we continually 398. Green Energy, Chemiluminescence, and move towards question after question. Fuel Cell Tushar Goswami. Beavercreek High School, 396. Synthesis and Application of Colloidal Beavercreek, Ohio, United States. Silver for Use in an Undergraduate Laboratory The objective of this research was to investigate the potential of various common plants as alternate Kristi L. Liddell, Joseph T. Keiser. Department of energy sources to produce green lighting, electricity, Chemistry, Pennsylvania State University, University and energy. Park, PA, United States. For example, chlorophyll in plants absorbs light Chemistry on the nanometer scale has evolved into a which can be harnessed back to produce energy. prominent field in research and industry. In an effort Therefore, this project has the capacity to serve as an to introduce students to current research topics, the alternate energy source, and a paradigm shift from synthesis of silver nanoparticles has been included in fossil fuel to green energy. A common white light the general chemistry laboratory curriculum. Students source along with the spectrometer and an energy synthesize 10-14 nm silver colloid, determine meter was used to conduct the experiments. The nanoparticle size by UV-Vis spectroscopy and study experiments were performed on four types of plants: the effect of aggregation with and without the Lettuce, Red Lettuce, Pothos, and Spinach. The addition of surfactant. chlorophyll content of each of these plant was Silver has shown the ability to kill and prevent measured. bacterial growth. More recently there has been an When the light photon packets strike the chlorophyll array of products containing nanoparticles which can at a particular wavelength, simulating the absorption impart different properties to a material. This and emission from sun light, it absorbs a fixed experiment opens a variety of projects for students to quantity and the rest is emitted. explore different applications for silver nanoparticles

Spinach has the type a chlorophyll whereas red Ryan M. Griffin. Department of Chemsitry, Capital lettuce and pothos are type b (C55H70O6N4MG). University, Columbus, Ohio, United States. Type a absorbed sixty percent of the light used in this Surface water nitrogen is integral to the influence of experiment while the rest were emitted. On the other nutrients that are received by rivers and streams. hand Type b leaves emitted only 15% of the total Although nitrogen is often attributed to non-point light. Therefore, type a vegetation are a good source source agricultural influence, many point source for energy production. The study showed that darker discharges are also considered as a contributing thicker leaves contained more chlorophyll and more factor. Nitrogen concentrations of two watersheds energy than thinner lighter leaves. This study within the Upper Scioto River Basin were analyzed provides the basis for developing artificial synthetic during the summer sampling season (June-September fuel cells to produce energy. 2009) to determine the influence of two different municipal wastewater facilities. Qualitative testing 399. Multi-Exponential Lifetime Analysis for was conducted to ascertain agricultural influence of Temperature Sensors Based on Luminescent the surrounding area. Quantitative analyses provided Europium Complexes information about point source addition of nitrogen Lukas T. Kromer, Jeffrey A. Gray. Department of by wastewater treatment processes. Effluent from the Chemistry and Biochemistry, Ohio Northern larger wastewater treatment plant (WWTP) showed significant change between upstream and University, Ada, OH, United States. - - downstream [NO3 ] + [NO2 ] (p = 0.0002), whereas Organic polymer films containing luminescent the smaller wastewater plant did not show significant - - lanthanide complexes make interesting photo- [NO3 ] + [NO2 ] attribution (p = 0.57). Analysis functional materials. Europium(III) β-diketonate suggests that major WWTP facilities are a - - complexes, for example, are useful as optical measurable point source for NO3 + NO2 , in contrast temperature sensors. Although total luminescence to smaller WWTP facilities. quantum yield varies predictably with temperature, calibration of intensity-based sensors requires 401. Substituent Effects on a Regioselective corrections for drift in the excitation source, variation Template Reaction in film thickness, and irreversible photo-bleaching of samples. Alternatively, luminescence lifetimes are Travis D. Neimeister, Britni Morand, Richard P. very temperature sensitive and less prone to sampling Hotz. Department of Chemistry, College of Mount errors, but multi-exponential data often complicates St. Joseph, Cincinnati, OH, United States. 3+ analysis. We have synthesized Eu(tta)3Z , a new Dibenzotetraaza[14]annulenes are prepared via a aminoindanol pyridine bisoxazoline (i.e. a py-box “sterically-sensitive” nickel(II) template derivative, labeled here as “Z”) derivative of condensation of 1,2-diaminobenzene and a 1,3- trithenoyltrifluoroacetonato europium(III), deposited diketone. Remarkable regioselectivity is observed this complex in polystyrene and PMMA films, and when an unsymmetrical diketone whose substituents recorded pulsed laser-induced luminescence with are an aromatic ring and a small alkyl group is used. high amplitude resolution, which reveals bi- or tri- It is proposed that pre-association between the exponential time decays. Unlike previous studies that nearly-planar intermediate and the enolic oxygen correlated changes in average lifetime with atom of the diketone’s enol tautomer allows for pi- temperature, we model the luminescence as a stacking between the aromatic rings of each superposition of emissions from partially dissociated component in an alignment that leads to the cis forms of the complex each having a distinct and fixed isomer. lifetime. This more general approach explains how the relative contribution of lifetime components varies and how dissociation equilibrium constants depend on solvent or polymer host environment. Optimization of ligands and control of their temperature stability may lead to improved optical sensor designs.

400. Differentiation in Nitrogen Loading This project focuses on attempts to minimize or between Minor and Major Municipal disrupt pi-stacking interactions by placing Wastewater Treatment Systems in the Upper substituents on the aromatic ring of the diamine. Scioto River Watershed

402. Synthesis and Characterization of the 404. Gas Chromatography of Nail Polish Novel Perovskite Series K(CuXM1-x)F3, for M Removers: A Consumer Product Teaching = Ni, Mn and Co Experiment Ashley Wolf, Timothy Wagner. Chemistry, Thomas N. Loegel, Neil D. Danielson. Chemistry Youngstown State University, United States. and Biochemistry, Miami University, Oxford, OH, United States. Perovskite-related compositions in the K(CuXM1-x)F3 system were investigated where Cu is mixed with The major volatile organic compounds in various either Ni or Mn. The series K(CuXMn1-x)F3 and types of nail polish remover are qualitatively K(CuXNi1-x)F3 (x = 0, 0.1, 0.2, …0.9) were identified and their volume percentages estimated. synthesized and characterized along with their Acetone is the major component of one type and ternary end-members by students in an undergraduate either methyl acetate or ethylacetate is found in non- general chemistry laboratory as part of the Project acetone based products. Isopropanol, found in some REEL implementation at Youngstown State products, can also be identified. Methanol is used as a University during the spring 2010 semester. These reasonable but not ideal measure of an unretained series have not been previously reported to our component to permit the calculation of retention knowledge. factor, k’, for each compound. The effect of The structure, composition and optical properties temperature from 30 – 60 oC on the resolution of were characterized hands-on by students via X-ray peaks is also studied and ln k’ versus 1/T plots are powder diffraction, X-ray fluorescence, and UV-Vis generated. For quantitation, the internal standard spectroscopy, respectively, and this data will be equation is used which introduces an important presented. This data will also be compared to results analytical concept that is used widely in all of a previous study in which the series: K(CuXCo1- chromatography methods. Separations are carried out x)F3 (x = 0 to 0.1) was also synthesized and on a RTX-1701 capillary column with dimensions of characterized by students as part of Project REEL. 30 m length, 0.53 mm internal diameter, and a cyanopropyl-phenyl-polysiloxane stationary phase. 403. Synthesis and Characterization of the An unexpected result was this stationary phase showed an enhanced affinity for carbonyl compounds Novel Perovskite Series (AxB1-x)CoF3, for A = + + + over alcohols. The chromatographic retention order Na , K , and NH4 with boiling point in oC in parentheses is methanol Caleb J. Tatebe, Ashley Wolf, Timothy R. Wagner. (64), acetone (56), isopropanol (82), methyl acetate Department of Chemistry, Youngstown State (58), and ethyl acetate (77). In contrast to the boiling University, Youngstown, OH, United States. point order, the retention times of acetone and methyl Perovskite-related compositions in the (A B )CoF acetate are greater than that for methanol and ethyl x 1-x 3 acetate is retained significantly longer than system were investigated, where A & B are a mixture + + + isopropanol. This demonstrates an important teaching of two of Na , K , or NH ions. Attempts to 4 concept that boiling point can often be used to predict synthesize compositions in the series (K Na )CoF x 1-x 3 retention order of compounds within a class but not (x = 0 to 1.0) were unsuccessful, however (K NH x 4(1- for a mixed set of compounds, even those with a )CoF , where x = 0.1, 0.2…0.9, were synthesized x) 3 slight difference in functional group. This experiment and characterized along with their ternary end- exposes students to a typical quality control method members by students in an undergraduate general found in industry. chemistry laboratory as part of the Project REEL implementation at Youngstown State University during the spring, 2010 semester. This series has not 405. Metal Ion Analysis Using the Water been previously reported to our knowledge, and as Adsorbent Polymer Polyacrylate: An expected, the range of colors in the series is impacted Adaptable Science Experiment less than similar studies in which subsitutions are Ling Zhou, Neil D. Danielson. Chemistry and made at the transition metal site. The structure, Biochemistry, Miami University, Oxford, OH, United composition, and optical properties were States. characterized hands-on by the students via X-ray powder diffraction, X-ray fluorescence, and UV-Vis Polyacrylate is a synthetic polar polymer with spectroscopy, respectively, and this data will be carboxyl groups that gives it a very high affinity for presented. water. Its primary commercial use is in disposable diapers. Water is drawn into the matrix of the polymer chains, forming a gel that can swell several

hundred times its original size. The polymer does not 407. Cellular Automata Model of the swell as much in concentrated salt solutions because Distribution of Gases in the Earth’s cations such as sodium and calcium will readily Atmosphere interact electrostatically with the carboxylate groups hindering the interaction of the water molecules. We Edur Basha Boyini Palli, Paul G. Seybold. have found that the measurement of the water Department of Chemistry, Wright State University, saturation point of a 0.5 g sample of polymer can be Dayton, Ohio, United States. used as a quantitative measurement of metal ions in Almost 200 years ago John Dalton proposed that the solution. As a measure of water purity, distilled water composition of the gases in the Earth’s atmosphere and unsoftened tap water can be adsorbed to about should change with altitude, the heavier gases being about 200 and 95 mL, respectively, before the relatively more abundant at lower elevations and the solution capacity of the polymer is exceeded. The lighter ones relatively more abundant at higher polymer adsorbs softened water similar to unsoftened altitudes. In 2006 this proposal was experimentally water as expected. However, distilled water and confirmed at low altitudes (0-4 meters) by careful distilled, deionized water can be differentiated. A measurements of the ratio of Argon to Nitrogen [Y. linear calibration curve for sodium from 0 to 0.6 g/L Adachi et al., Science 2006, 311, 142] at a desert has been established before the response levels off location. In the present work a dynamic, isothermal from about 2- 9 g/L. Relative standard deviation of cellular automata model for the distributions of such data are remarkable, about 5%. Measurement of nitrogen, oxygen, argon, and carbon dioxide in the sodium in food products should be possible. Finally, atmosphere will be presented and compared with the the ion exchange chromatography retention predictions of the barometric equation. The cellular mechanism can be demonstrated by comparison of automata model employs two rules: a gravitational the difference of adsorption of lithium, sodium, rule based on the masses of the molecular calcium, and aluminum solutions of the same constituents and a motional rule based on their concentration. Polyacrylate chemistry has been used relative average speeds. The model captures the basic as part of a polymer experiment in a first year features of the gas distribution with altitude as well as chemistry college laboratory but because of the the expected relative uncertainties caused by the excellent safety aspects and no need for complicated diffusive motions of the gas molecules. equipment, it should be an excellent experiment for middle and high schools. 408. Investigation of the Direct Synthesis of Polyimide-Organoclay Nanocomposites 406. Organocatalysis in the Sophomore Organic Chemistry Laboratory Thomas Morgan, Isabelle Lagadic. Chemistry, Northern Kentucky University, Highland Heights, Kenneth E. Walsh, Edmir O. Wade. Department of KY, United States. Chemistry, University of Southern Indiana, Evansville, IN, United States. In the field of polymer-layered silicate nanocomposites, research efforts have been directed In the literature in recent years there has been an toward polymers reinforced by nanoscopically explosion of papers concerning the area of dispersed organically modified layered silicates. organocatalysis. We have developed a multi-step Exfoliated structures, with inorganic layers randomly capstone laboratory project that combines key second dispersed in the polymeric matrix, are usually semester organic chemistry reactions with this new preferred, to enhance the nanocomposite properties, field of research. The students synthesize a such as mechanical, thermal and gas impermeability prolinamide catalyst which is used to perform an properties. In this project, we started to investigate enantioselective aldol reaction. In this sequence they the direct synthesis of polyimide-organoclay are exposed to some of the common reactions of acid nanocomposites through the reaction between a derivatives, enamine formation and the aldol poly(amic acid) (PAA) and a one-step prepared reaction. The success of the reaction is measured by amino-functionalized organoclay material (Mg- calculating the enantiomeric excess of the aldol APTES). The reaction between the amine groups of product formed. the organoclay and the dianhydride end groups of PAA resulting in a covalent bonding between the polymer and the organoclay layers was confirmed by infrared spectroscopy. X-ray diffraction analyses show that a certain level of exfoliation of the organoclay layers was obtained.

Significant differences in color, texture and strength Previously, for the atomic absorption (AA) lab between the pristine polymer and the composites experiment at Miami University, we have tested the were also observed. However, the composite suppression effect of phosphate on the response of materials did not show any improved degradation calcium and how lanthanum can preferentially form a temperatures or moisture absorption level compared more stable complex with phosphate and reverse the to the pure polymer. effect of the suppression. This phenomenon has been well documented in the literature. The purpose of this 409. Exploring Synthetic Parameters for the research project is to use this chemical interference to Preparation and Properties of Functional our advantage for the indirect determination of not Organoclays only ortho-phosphate but also other phosphate species such as polyphosphates and Jennifer Hand, Isabelle Lagadic. Chemistry, polyphosphonates. To the best of our knowledge, the Northern Kentucky University, Highland Heights, suppression of the calcium AA signal by various KY, United States. phosphate species other than ortho-phosphate has not A fair amount of interest has been given to been previously investigated. In particular, organosilicate materials due to their unique tripolyphosphate and hexametaphosphate are of combination of organic and inorganic properties and interest since they are two major phosphorus potential in various environmental and industrial containing components in Calgon and applications. Among these hybrid materials, layered fluorophosphates is found in some toothpaste brands. organosilicates have remained rather unexplored. Our In addition, polyphosphonates such as research interests have been on the preparation of ethylenediaminetetra(methylene phosphonic acid) talc-like organoclays by direct alkaline co- found in the Dequest products made by Monsanto are promising candidates. Using a 1.2 mM calcium polymerization between MgCl2 and organosilanes, (RO) Si-X, where R = CH or C H and X = solution, linearity in response from 0.02 to 0.1 mM 3 3 2 5 for hypophosphate, fluorophosphate, (CH2)3SH (MTMS) or X = (CH2)3 NH2 (APTES). In this work, we particularly investigated some tripolyphosphate, and hexapolyphosphate is synthesis parameters that may affect the structure observed. The sensitivity in response is about the and/or the properties of these organoclays. We found same for hypophosphate and fluorophosphate but that substituting fractions of organosilane with a non- higher for both tri- and hexa-polyphosphate. Weak functionalized alkoxysilane (e.g. Tetraethoxysilane, anion exchange solid phase extraction is planned to pre-treat some of the commercial products before TEOS, (C2H5O)4Si) tends to increase the hydrophilicity of the materials, but also resulted in analysis. the loss of the layered structure. No noticeable structural differences were observed in the 411. Probing the Nature of Metal- organoclays prepared at room temperature, under Phosphonate Interactions by FTIR reflux or hydrothermal conditions indicating that the Spectroscopy synthesis temperature has little effects, if any, on the J. Radler, Douglas J. Schauer. Chemical material structures. Varying the hydroxide to Technology, Ivy Tech Community College, magnesium mole ratii led to different results Lafayette, IN, United States. depending on the nature or the organosilane precursor. When MTMS was used as a precursor, the Proposed mechanisms for mild, metal-promoted layer stacking and the order within the layers Horner Wadsworth Emmons reactions often invoke a improved as the OH-/Mg2+ mole ratio increased, chelate model to account for enhanced acidity of the while an opposite trend was observed with a more phosphonate reagent. The nature this type of complex disorganized overall structure when APTES was used has been previously explored in the case of lithium a precursor. salts by FTIR spectroscopy. Since that report, however, several other metals have been shown to 410. Indirect Determination of Phosphate promote Horner Wadsworth Emmons reactions with Compounds Using Calcium Suppression by a variety of phosphonates. This includes diprotic Atomic Absorption Spectroscopy: An Open- phosphonates that are not well-promoted by lithium Ended Inquiry Teaching Experiment salts. We report, herein, a study of various metal/phosphonate complexes, whereby the FTIR Matthew P. Collins, Neil D. Danielson. Chemistry spectra of these complexes were examined to identify and Biochemistry, Miami University, Oxford, OH, changes in the C=O and P=O bonds of the United States. phosphonate.

412. Quantum Chemical Study of the Cynthia A. Schroll, William Heineman. Department Energetics and Directionality of Acid- of Chemistry, University of Cincinnati, Cincinnati, Catalyzed Aromatic Epoxide Ring Openings Ohio, United States. Rory Korzan, Brian Upton, Kenneth Turnbull, Paul Monitoring of Actinides and Lanthanides during the Seybold. Department of Chemistry, Wright State electro-refining process can be difficult using University, Dayton, Ohio, United States. electrochemistry because of the multiple redox active species that are present in the melt. We propose that Epoxide ring openings play important roles in a spectroelectrochemistry can be used to enhance the variety of chemical situations and in addition are detection of these species. The cell will first be believed to be important in the metabolic processes evaluated using model analytes such as Potassium through which some polycyclic aromatic ferricyanide (K3Fe(CN)6) and Fluorescein in ionic hydrocarbons are converted to carcinogenic species. liquids(IL). Spectroelectrochemistry is a technique In the present study the energetics and directionalities where you apply a specified potential to the analyte of acid-catalyzed epoxide ring openings are and it will either be oxidized or reduces, and in doing examined using quantum chemical methods. In so the absorbance or fluorescence spectrum will particular the consequences of local saturations in the change and be monitored. Using an Optically aromatic systems are noted and shown to exert very Transparent Thin Layer Electrode (OTTLE) cell strong influences on the resulting energetics and lowers the path length of the cell helping to minimize product distributions. the time it takes for the analyte to be completely electrolyzed. K3Fe(CN)6 was dissolved in a 1M 1- 413. Cyclic Voltammetry Detection of Lead at butyl-3-methylimidazolium bromide ([BMim]Br) Crown Ether Modified Electrodes solution and -200mV was applied, reducing the analyte and causing its absorption peak at 420nm to Phuong Khanh Quoc Nguyen, Suzanne Lunsford. decrease. Likewise fluorescein was dissolved in a 1M Chemistry, Wright State University, Dayton, Ohio, [BMim]Br solution and 1000mV was applied to United States. oxidize the analyte causing a decrease in the Over a decade, crown ethers have been utilized as fluorescence signal at 515nm. The data obtained for modifiers for the detection of mercury and silver. the analytes dissolved in the IL solutions are They have been known to form complexes with a compared to solutions with the same molarity and the host of cations including alkali, alkaline earth metal same conductivity of a common supporting ions, ammonium ions, lanthanides and transition electrolyte, Sodium nitrate. It was found that the rate metal ions. Thus, the expansion of REEL (Research of change in the spectrum is related to the Experiences to Enhance Undergraduate Learning conductivity and not the molarity of the solution. Experiences) program has brought about the research to determine if the lead ions uptake can be carried out 415. Investigation of Chlorophosphazene with the use of a dibenzo-18-crown-6. Employing Cyclic Oligomers and Byproducts from the chemically modified electrodes with crown ethers Ring-Opening Polymerization of the such as dibenzo-18-crown-6 is of great scientific and Chlorophosphazene Trimer technological interests in developing sensors for the detection of heavy metals such as lead. In this work, David J. Bowers, Jessi Baughman, Matthew J. platinum working electrodes electrochemically Panzner, Vincenzo Scionti, Matthew Espe, Chrys modified with crown ethers were studied in the Wesdimiotis, Wiley J. Youngs, Claire A. Tessier. determination of lead ions by cyclic voltammetry Department of Chemistry, University of Akron, compared to the bare platinum electrodes. The cyclic Akron, OH, United States. voltammograms results will display that the anodic A wide range of applications exist for phosphazene and cathodic peaks are enhanced for the modified polymers, however, the difficulties with the ROP crown ether electrodes compared to the bare synthesis of the parent chlorophosphazene polymers electrodes response to lead ions. Detailed results of has limited their use. The synthesis of high molecular the structural properties of the crown ether (dibenzo- weight chlorophosphazene polymers are often 18-crown-6) modified electrode were investigated completed through the ring-opening polymerization utilizing SEM and X-ray Fluorescence,which will be (ROP) of the chlorophosphazene trimer [PNCl2]3. presented. Our research targets various aspects of the ROP through investigation of fundamental 414. Spectroelecctrochemical Sensing in an chlorophosphazene chemistry. We will present data Ionic Liquid Matrix focusing on ring-ring equilibria of the

chlorophosphazene cyclic oligomers, as well as a Markeata Lee, Roviere Colson, Christopher Lupai, preliminary MAS NMR study of ROP products. Daqing Gao, Suzzane Seleem. Department of Natural Sciences, Central State University, Wilberforce, 416. Photophysical Properties of a Series of Ohio, United States. Octaethyl Tetraphenyl Porphyrins The keto-enol tautomerization of 2,4-pentanedione Jonathan L. Flikkema,1,2 Joy E. Haley,1,3 Weijie and the free energy differences between the E and Z Su,1,4 Jonathan E. Slagle,1,5 Daniel G. McLean,1,5 conformers of formic acid were studied by ab initio Thomas M. Cooper.1 1Materials and Manufacturing molecular orbital and density functional theory Directorate, Air Force Research Laboratory, calculations. All of the 10 unique conformers in the WPAFB, OH, United States; 2SOCHE Student gas phase were located through a variety of high level Research Program, Dayton, OH, United States; 3UES, ab initio and DFT optimizations. Free energy Inc., Dayton, OH, United States; 4General Dynamics differences between different structures of ketone and Information Technology, Dayton, OH, United States; enol and formic acid in the gas phase were obtained 5Science Applications International Corporation, from frequency calculations. The solvation free Dayton, OH, United States. energies of the conformers in different solvents were obtained from the continuum CPCM model. The Interest in both the linear and non-linear properties of computed equilibrium constants in different solutions porphyrins has been large for quite some time were compared to the experimental literature values. because of their use in numerous applications such as cancer therapy, alternative energy, hemoprotein 418. Adsorption of Manufactured models, and electronics. Porphyrins are especially Nanoparticles on Synthetic Biofilm interesting because small changes in their structure lead to large changes in their electronic and Endalkachew Sahle-Demessie, Haragewine photophysical properties making them excellent Tadesse. NRMRL, U.S. Environmental Protection candidates for studying structure-property Agency, Cincinnati, OH, United States. relationships. In this study we look at the effect of Adsorption of anatase TiO nanoparticles on various metals on the photophysical properties of a 2 synthetic biofilm has been investigated. Highly series of octaethyl tetraphenyl porphyrins (shown porous biofilm that consists of spherical beads was below) in toluene. Investigations include Beer’s Law prepared from agarose and well characterized in wet analysis to determine ground state molar absorption and freeze-dried forms. The approach provides a coefficients and nanosecond laser flash photolysis. method of mimicking and a deeper insight in the The latter technique is used to study the triplet nature of nano-particle adsorption to natural biofilm. excited state properties of the chromophores A hydrogel made of polysaccharide found in agar including spectral and kinetic details. The triplet was prepared for the coating of metal surfaces. Self- excited state maximum is found in the 500 – 535 nm assembled monolayer polyoxyethylene containing region for the three chromophores. All three amphiphiles on metal sheets were prepared, with porphyrins have triplet lifetimes under deoxygenated hydrophobic chain moiety extend away from the conditions between 1 – 5 ms and the PtOETPP has a surface. A detailed exploration of biofilm- biexponential decay with a second lifetime of 29 ms. nanoparticle matrices, i.e., adsorption, aggregation,

dispersion, distribution and stability were carried out using surface sensitive analytical techniques including AFM, SEM/EDAX, and TEM. Macroscopic adsorption behavior of the biofilm to nano-scale TiO2 particles has been studied at room temperature in a batch mode. The effect of nanoparticle initial concentration, the pH and ion strength of the solution is being investigated. The experimental data suggests that at solution pH of 10 the effect of ionic strength to the adsorption of TiO2 is significant and it was observed that at 100 mM NaCl, the adsorption capacity of the biofilm (10.9 417. Conformational Studies of 2,4- mg/g) was higher than in 1 mM NaCl (6.5 mg/g), Pentanedione in the Gas Phase and Solution with initial TiO2 solution concentration of 10 mg/L. The adsorption equilibrium was established in 4 h, and the adsorption appears to follow pseudo first-

order kinetic. From desorption data, it was also Smart Materials and Devices Laboratory, Cincinnati, observed that the adsorption is irreversible, which Ohio, United States. could be due to the combination of high porosity of Electroanalytical determination of heavy metals using the adsorbant and the active binding sites on the stripping voltammetry is commonly employed and highly porous biofilm surface. Freundlich isotherm has many advantages over other methods. This work gave the best fit of the adsoption equilibrium data. introduces the sensitive voltammetric detection of trace metals using multi wall carbon nanotube 419. Self-Assembly of Colloidal Metal (MWNT) bundles with good resolution of the four Nanoparticles and Plasmon-Mediated Energy metals. Trace metals ions, Zn2+, Cu2+, Cd2+ and Pb2+ Transfer are analyied by in situ-mercury film electrode (MFE) Anil Desireddy,1 Gardelle Bastien,1 Joshi Chakra,1 using osteryoung square-wave stripping voltammetry Sestak Michelle,2 Little Scott,2 Kumar Santosh,1 (OSWSV). There are two steps in the analysis: Marsillac Sylvain,2 Collins Robert,2 Bigioni Terry.1 deposition and stripping. Longer deposition time 1 leads to lower detection limit. The detection limit can Department of Chemistry, University of Toledo, -7 2 be as low as 10 M when for a deposition time of Toledo, OH, United States; Department of Physics -9 and Astronomy, and the Wright Center for 120s; 10 M when the deposition time is 500s. Photovoltaics Innovation and Commercialization, University of Toledo, Toledo, OH, United States. 421. Synthetic 5-oxo and 5-thio Derivatives of 1,4-Diaryl Tetrazoles That Inhibit Tumor Plasmon-supporting metal nanoparticle thin films are Cell Proliferation and 3-Hydroxy-3- important for optical applications such as sensors or photovoltaic devices. We have used drop casting to Methylglutaryl-Coenzyme A (HMG-CoA) self-assemble a compact and uniform monolayer film Reductase Activity of dodecanethiol-capped metal nanoparticles across Jean-Pierre H. Perchellet,1 Elisabeth M. Perchellet,1 an entire 2” wafer. Typically, the thiol-capped gold Andrew M. Waters,1 Aditya S. Gundugola,2 Kusum and silver nanoparticles act as surfactants and cover L. Chandra,2 Sundeep Rayat.2 1Division of Biology, the toluene-air interface, assembling into a highly- Anti-Cancer Drug Laboratory, Kansas State ordered 2-dimensional array of particles. The fully University, Manhattan, Kansas, United States; assembled monolayer is then set down onto the 2Department of Chemistry, Kansas State University, substrate upon final drying of the liquid drop. The Manhattan, Kansas, United States. films were found to have good wafer-scale uniformity using a variety of microscopy techniques complemented by ellipsometry. The optical properties of the films were also evaluated, in particular the plasmon bands of the films. The absorbance characteristics of these monolayers depend on particle sizes, spacings and materials. The characteristics of the plasmon bands were also found 1,4-Diaryl tetrazol-5-ones 1a-d were prepared by the to depend on the film quality. Well-ordered films had coupling of aryl boronic acids with 1-phenyl-1H- strong and sharp plasmon bands while disordered tetrazol-5(4H)-one. Thionation of 1b-d gave the films had broad and weak plasmon bands. These corresponding tetrazole-5-thiones 2b-d. nanoparticle thin films were then used to study Treatment of 1d and 2d with Lewis acid produced 1e plasmon-mediated energy transfer. Fluorescent dye and 2e. Compounds 2e, 1e and 1a inhibit the molecules were deposited onto these monolayer films proliferation of L1210 and SK-BR-3 tumor cells in to measure metal-enhanced fluorescence, including vitro. The antiproliferative effects of 2e, 1e and 1a in the dependence on the distance between the metal L1210 cells are concentration dependent, more nanoparticle and dye. pronounced after 4 than 2 days, and characterized by IC values of 2.5, 7.1 and 12.9 µM, respectively, at 420. Simultaneously Detection of Trace 50 day 4. Moreover, 2e inhibits the Ki-67 marker of cell Metals by Anodic Stripping Voltammetry proliferation in SK-BR-3 cells at 24 h and the rate of Using Carbon Nanotube Electrodes DNA synthesis in L1210 cells at 2 h. At 156 µM, 1a, Xuefei Guo,1 Mark Schulz,2 Vesselin N. Shanov,2 2c and 2b inhibit the activity of human HMG-CoA William R. Heineman.1 1Department of Chemistry, reductase in a cell-free assay by 91.1, 71.2 and Univerisity of Cincinnati, Cincinnati, Ohio, United 66.2%, respectively, suggesting direct interaction States; 2College of Engineering, Nanoworld and with the rate-limiting enzyme of cholesterol

biosynthesis. The concentration dependent inhibition chromatography, dialysis, sonication, UV-Vis of HMG-CoA reductase by 1a begins at 4 µM and is spectrophotometry, and protein fluorescence. The characterized by an IC50 value of 34.1 µM. But there poster session also increased student engagement in is no correlation between antitumor and statin-like the purification and analysis, since each student was activity and the molecular targets and mechanisms of considered an “expert” in one of the techniques. Pre- action of these bioactive compounds remain to be and post-tests were given to assess student learning elucidated. of the techniques and how they are typically used in the purification and analysis of proteins. Scores 422. Rapid Detection of Influenza Viruses improved markedly, demonstrating an increase in Using Magnetic Nanoparticles student understanding as a result of the lab and poster session. Yun He, Suri S. Iyer. Department of Chemistry, University of Cincinnati, Cincinnati, OH, United 424. 2009 ACS Director-at-Large Election: States. How To Elect Two Candidates with Each Influenza is a widespread infectious disease that Being Elected by a Majority of the Voters remains a constant threat to humans. Rapid and Wendell L. Dilling. Department of Chemistry, accurate detection methods for the detection of Central Michigan University, Mt. Pleasant, Michigan, influenza viruses of specific type (e.g. seasonal United States. versus “swine” or “bird” strain), are in urgent need. My research focus on the development of a novel In the 2009 ACS election for directors-at-large five magnetic nanoparticle based technique for the rapid candidates ran for two positions (Chem. Eng. News, detection of influenza viruses with high specificity Nov. 23, 2009, p 7). One of the elected candidates and sensitivity. The nanoparticle comprises of a received votes from ≤44.9% of the voters, councilors magnetic iron core and coated with carbohydrate who were allowed two non-prioritized votes each. A ligands that bind to the surface proteins of the virus. method is proposed to carry out elections in which The binding results in aggregation of nanoparticles two or more candidates are elected with each being and decrease in T2 (spin-spin relaxation time) can be elected by a majority of the voters. The method observed. (multiple instant run-offs) involves voters prioritizing their votes. The procedure in outline form is as 423. Design, Implementation, and Assessment follows. The first director-at-large is elected by a of an Undergraduate Protein Purification majority in exactly the same way a single candidate Protocol Using Riboflavin Binding Protein would be elected from five candidates. Then all the votes for the candidate just elected are removed from 1 1,2 Jamie Schwefel, Kyle O. Daly, Tracey Arnold the voting priority list of each voter. The second 1 1 Murray. Department of Chemistry and successful candidate is then determined in exactly the Biochemistry, Capital University, Columbus, OH, same manner as the first using the new prioritized list 2 United States; School of Natural Resources and of each voter. Thus both candidates are elected by a Environment, University of Michigan, Ann Arbor, majority. If more than two candidates are to be MI, United States. elected, the preceding procedure is repeated until the One of the cornerstones of any biochemistry required number of candidates has been elected, each laboratory is the purification of a protein of interest. by a majority of the voters. If one believes in election A protocol to purify riboflavin binding protein (RBP) by majorities, ACS elections procedures should be was modified from published and unpublished changed. sources for use in the undergraduate Biochemistry Laboratory course at Capital University (Chemistry 425. Small Business Issues in the Era of the 452). This protocol was successfully implemented in Great Recession the spring of 2009. A second protocol was added in David M. Manuta. Professional Consulting, Manuta the spring of 2010 to enhance student understanding Chemical Consulting, Inc., Waverly, OH, United of the properties of RBP. The added protocol studied States. the thermal unfolding of this protein, as monitored by riboflavin fluorescence. As an alternative to the more The Great Recession has had significant impact on traditional pre-lab lecture, a poster session was held many of our professional colleagues. As a chemist where each student presented one of the techniques who transitioned into an entrepreneur/small used in the purification and analysis of RBP, businessman more than one decade ago, I now often including ion exchange and size exclusion counsel colleagues on following this path.

films. Multilayer films with alternating layers of Many of these peers did not expect to be out of polyester (PET) and a polyvinylidene fluoride compensated work for an extended period of time. copolymer were produced to exploit the high We will discuss what the professional with a well- breakdown strength of PET and the high dielectric established skill set can do to survive these tough constant of PVDF. Biaxially oriented multilayered times. Thriving becomes the name of the game. films possessed high breakdown strength resulting in a 30% increase in energy density (16.2 J/cm3) over a 426. Using LinkedIn for Networking, Job PET control while maintaining the low dielectric loss Search, and Better Business typical of PET polymers. This novel approach is capable of producing high Frank Butwin. Consultant, Perrysburg, OH, United performance multilayer polymer films which possess States. enhanced properties compared to monolithic controls. For chemists, and most others, using the networking site www.LinkedIn.com can provide a wealth of 428. Low Loss and High Energy Density in benefit for finding and contacting new and old Poly(vinylidene Fluoride)/Polysulfone friends and associates. But beyond this, LinkedIn (LI) Multilayer Dielectric Films can, and is, being used successfully and professionally to search for needed employment, to Jung-Kai Tseng, Matt Mackey, Joel Carr, Anne find a more satisfactory job than one is currently in, Hiltner, Eric Baer, Lei Zhu. Department of to find good candidates to fill vacant positions, to do Macromolecular Science and Engineering, the Center your job better, and to increase the success of the for Layered Polymeric Systems, Case Western business that one is in, whether as the owner or as an Reserve University, Cleveland, Ohio, United States. employee. The main purpose of this study is to explore the Key ways to use LinkedIn for professional unique dielectric behaviors of multilayer (32- and contacting, career enhancement, and an improved 256-layer) poly(vinylidene fluoride) business will be discussed. There are many features (PVDF)/polysulfone (PSF) capacitor films. These on this social media website that seem hidden or that samples were characterized by electric displacement can be intimidating. These hidden treasures will be –electric filed hysteresis loop (D-E) measurements, revealed. Fears will be removed. There will be a brief FTIR, and AFM. According to D-E loops of discussion of other social media tools and platforms PVDF/PSF multilayer films, the suppression of that can be used, such as Twitter and Facebook. energy loss is associated with the increment of the PSF content. On the contrary, dielectric constants and 427. Dielectric Properties of Biaxially energy storage were promoted by the PVDF content. Oriented Micro and Nanolayered Films Additionally, these PVDF/PSF films showed the different frequency dependence in the D-E loop Joel Carr, Matthew Mackey, Anne Hiltner, Eric measurement. As the PVDF content is lower than 50 Baer. Macromolecular Science and Engineering, vol.%, hysteresis can’t be altered by variation the Case Western Reserve University, Cleveland, Ohio, frequency. However, as increasing the PVDF content United States. above 50 vol.%, the lower frequency leads to high Polymer films are commonly used for capacitor maximum polarization but more hysteresis. applications such as energy storage and pulsed Furthermore, through AC poling process, phase power. Polymers possess excellent processibility and transition was induced due to the external electric cost compared to ceramic materials, however field above 300 MV/m for the PVDF content more polymers typically have low energy densities. Efforts than 90 vol.%, contributing to the dramatically to improve the energy density of polymer films focus increasing energy storage density at high PVDF on increasing the breakdown strength and/or the content samples. From the results, we postulated that dielectric constant. An improvement of the ion relaxation during electric poling was minimized breakdown strength of polymer films was achieved due to confined space. Consequently, low loss and through multilayer coextrusion. The state-of-the-art relatively high energy density dielectric films were polymer films used for capacitors (polypropylene and successfully achieved. polyester) are biaxially oriented to improve toughness and film performance. We took the 429. Dielectric Properties of Micro and opportunity to explore the effects of multilayer Nanolayered PC/PVDF Films coextrusion combined with biaxial orientation on the Matt Mackey,1 Anne Hiltner,1 Eric Baer,1 Lei Zhu,1 dielectric performance properties of multilayered Lionel Flandin,3 Mason Wolak,2 James Shirk.2

1Department of Macromolecular Science and generated during BER, and halt the repair. In fact, Engineering, Center for Layered Polymeric Systems previous experiments had proven that the treatment (CLiPS), Case Western Reserve University, of TMZ with MX is more effective than using TMZ Cleveland, OH, United States; 2US Naval Research alone in either killing cancer cells or inhibiting tumor Laboratory, Washington, DC, United States; growth. To evaluate the efficacy of MX, it is 3LMOPS UMR 5041, CNRS Université de Savoie, necessary to quantify the MX conjugated DNA-AP 73376 LE Bourget Du Lac Cedex, France. sites from DNA of patients who are treated with TMZ and MX since MX-AP adduct is a molecular There is a need in electronic systems and pulsed endpoint of MX action mechanism. power applications for capacitors with high energy

density. Current state-of-the-art polymeric capacitors Our preliminary work showed that with a multi- (BOPP, PET) only have a maximum energy density enzyme system, we could simplify the quantification of 5-6 J/cm3. From a material standpoint, the energy by releasing the MX-AP adducts from DNA strand as density improves with increasing dielectric constant MX-deoxyribose (MX-dR) complex. Then the and/or breakdown strength, and the loss is diminished released MX-dR could be extracted, and analyzed by reducing dissipation factor and high field with LC-MS/MS. The linear calibration curve was polarization hysteresis. Our approach to improve established by spiking blank calf thymus DNA with polymer film capacitors is to combine, through DNA oligomers carrying known amount of MX-AP microlayer coextrusion, two polymers with 6 adducts, which was 1-500 adducts/10 bases. The complimentary properties: one with a high dielectric future work will focus on the method optimization constant (polyvinylidene fluoride type polymers - and validation. The fully developed method will be PVDF) and one with a high breakdown strength used in dosimetric studies of the drugs. (polycarbonate). Multilayered films with many alternating layers of polymers exhibited improved breakdown characteristics due to the development of 431. Metal Loading Capability, DNA a “treeing” type failure mechanism. In addition, a Photocleavage, and Photo-Cytotoxicity of Soil reduction of polarization hysteresis was observed due Humic Acids to layer confinement effects on the solid state Varun Chander Reddy Lenkala, Patty K.-L. Fu. structure of PVDF. These synergistic effects of Department of Chemistry, Governors State microlayering have produced films with energy University, University Park, IL, United States. densities of 15 J/cm3 while maintaining very low losses. Using the understanding gained from these Humic acids (HAs) are widely dispersed, naturally systems, selection and optimization of future layered occurring biopolymers most commonly found in soil, structures can be carried out to obtain even higher drinking water, and plants. It is known that HAs have energy densities and lower dielectric losses. a very strong affinity towards multivalent metal cations. In this study, humic acids were randomly 430. Determination of Methoxyamine selected and extracted from three different cities in Conjugated DNA-AP Sites by Liquid the Illinois Valley area of the USA. The amount of Chromatography and Tandem Mass metal absorbed by humic acid extract was quantitated using inductively coupled plasma atomic emission Spectrometry spectrometry (ICP-AES). Our results showed that the Lan Li, Yan Xu. Department of Chemistry, soil in the Illinois Valley area is abundent in humic Cleveland State University, Cleveland, OH, United acids and it has a high metal chelating capability States. especially toward iron, lead, and copper ions. Furthermore, upon irradiation with visible light, we Temozolomide (TMZ) is an FDA approved anti- have established that both the humic acids along and cancer drug mainly utilized in the treatment of the metal-loaded humic acids are able to photocleave glioma. TMZ damages DNA by adding methyl group plasmid DNA. This study examined the to nucleobases, which interrupts DNA replication. In environmental and physiological impact when spite of its high cytotoxicity to the cancer cells, TMZ humans and animals accidentally acquire these drug effect is often attenuated by tumor resistance harmful metals through humic acids. Our findings mechanisms such as DNA base excision repair bring to mind the potential danger of metal-loaded (BER). To reverse tumor drug resistance, humic acid presence on the sun-exposed skin. methoxyamine (MX), a novel therapeutic agent is currently in Phase I clinical trial, can be co- administrated with TMZ since MX can form stable adducts with the apurinic/apyrimidinic (AP) sites

432. Preparation, Charecterization, and tested in vitro for cytotoxicity on human cells. Finally Cytotoxicity Testing of Inverse Micelle these encapsulated nano particles will be tested for Encapsulated Rifampicin Nanoparticles their efficacy on Staphylococcus aureus (Gram (+) bacteria) responsible for diseases such as Pneumonia, Bhargav Guntupalli, Patty K.-L. Fu. Department of Meningitis, Osteomyelitis, Endocarditis and Urinary Chemistry, Governors State University, University tract infections. Park, IL, United States. Rifampicin is a semi-synthetic derivative of 433. Monitoring Protein Regulation between Rifamycin antibiotics produced by a strain of Normal Human Skin Cells and Malignant Streptomyces mediterranei. Rifampicin usually is Melanoma Cells – A Proteomic Approach administered as ophthalmic, parenteral or oral dosage Sreekanth Penumetsa, Patty K.-L. Fu. Chemistry, form. It is mainly absorbed by the gastrointestinal Governors State University, University Park, Il, tract and distributed throughout the body. Only a United States. small therapeutic concentration of about 5 to 10% will reach to central nervous system. Many studies The field of proteomics has rapidly evolved in the were carried out on the penetration capacity of past few years, with a series of innovations in Rifampicin through the blood brain barrier and found technology development. Unlike the traditional study it to be very poor. Increase in the initial dosage of proteins one by one, proteomics studies proteins in amount to obtain higher bioavailability may result in an automated manner. Proteomics monitors the sever adverse effects like diarrhea, expression of a large number of proteins in a cell or pseudomembranous colitis, nausea, vomiting, tissue and observes quantitatively how the pattern of abdominal pains etc. Using novel drug delivery expression changes under different circumstances, systems like micelles or liposomes can effectively such as in the presence of a drug or in diseased tissue. transport the antibiotic to the desired site of action In this study, a simple, reproducible and rapid with the required therapeutic concentration and keep proteomics method is developed to monitor the the interaction with the degrading enzymes to a regulations of protein in a normal and cancer cell by minimum. Rifampicin is found to be a hydrophilic ESI-MS/MS. The primary goal will be to quantitate drug which requires the design of a delivery system the concentrations of various proteins in cancerous with a hydrophilic core which best fits the model of and healthy cells simultaneously in a fast, efficient an inverse micelle. This encapsulation in the form of and reproducible manner. an inverse micelle also serves the purpose of improved antimicrobial efficacy and decreased side Proteins are extracted from 250 million cultured cells effects. Delivering the antibiotic in the by using the total protein extraction kit. Extracted nanoparticulate structures such as inverse micelles proteins are denatured and biotynlated. The can affect the biological behaviors at the cellular, streptavidin proteins binds with high affinity to subcellular and protein levels due to their small size biotin, it is the highest affinity between a ligand and a -15 and target specificity. protein (Kd = 10 ). Biotynlation is followed by the trypsin digestion that cleaves the proteins or peptides O-(Decylphosphoryl)choline and O- on the lysine residues or carboxyl side of arginine. (Tetradecylphosphoryl)choline will be the surfactants Digested proteins are loaded in 96-well strepatavidin used in the design of the inverse micelle. The Choline coated plates to recover the biotynlated compounds group contains a quarternary amine with a phosphate for the subsequent analysis using ESI. Our MS/MS charge, and the phosphate is ionic and polar which spectrum suggested there are some alterations in makes it soluble in water. The Tetradecyl long protein regulation between cancer and normal cells. hydrocarbon chain is nonpolar and insoluble in water. This experiment may aid as useful tool for various These surfactants falls into the class of Zwitterionic biophysical or biochemical studies of a cancer cell. surfactants this has the critical micellar concentration (CMC) approximately about 10-3M. These inverse 434. Photophysical Properties of Rifampicin micelles are transparent, isotropic and Nanoparticles and Its Application in Cancer thermodynamically stable which makes it is easier to Therapy solublize Rifampicin with a little increase in the temperature. Maintaining the in vitro stability of the Jyothirmaye Bandaru, Patty K.-L. Fu. Department prepared inverse micelle is a big challenge as most of of Chemistry, Governors State University, University them have very short lifetimes in the range of Park, IL, United States. nanoseconds. After the preparation of the stable inverse micelle, encapsulated Rifampicin will then be

Rifampicin is a very popular drug used in the first its maximum potency in the beginning of the light line treatment of various forms of tuberculosis and as exposure followed by gradual reduction in strength an additive in the treatment of leprosy. Rifampicin within 24 to 72 hours. The symptoms of phototoxic acts by inhibiting DNA-dependent RNA polymerase contact dermatitis are very similar to sunburn which activity in susceptible cells. At therapeutic are characterized by erythema, oedema, blisters, and concentration, it has demonstrated bactericidal hyperpigmentation. Continuously repeated activity against both intracellular and extracellular phototoxic damage may result in milia formation, Mycobacterium tuberculosis organisms. As the actinic keratoses and skin cancer. In this study, the treatment of these diseases involves long duration of photophysical, photochemical, and photobiological chemo therapy which lasts from 1-3 years it is quite properties of both K vitamins are characterized and susceptible that the bacteria become resistant to this determined. Each molecule will then be assessed and drug. In order to reduce the development of drug- put into categories of non-reactive, phototoxic, or resistant bacteria and maintain the uniform levels of photoallergic agent according to its photoirritation drug in the body and also to reduce the number of factor (PIF). doses of drug taken, many successful attempts were made to encapsulate Rifampicin into nanoparticles. 436. Electroactive Polymers for Electrical Energy Storage Rifampicin was encapsulated into nanoparticles using PLGA-PEG combination as polymer. We further Qing Wang. Materials Science and Engineering, The explored the photophysical properties of Rifampicin Pennsylvania State University, University Park, PA, by performing DNA photo cleavage. At a selected United States. concentration of the drug, Rifampicin shows Electrical energy storage plays a key role in mobile absorption maxima in the UV range and also shows electronic devices, stationary power systems, and fluorescence when excited at wavelength of 385nm. hybrid electric vehicles. This talk will describe our When a comparative fluorescence and UV studies recent efforts to develop new polymer based were done between Rifampicin drug solution and an dielectric materials for high energy density equivalent concentration of Rifampicin nanoparticles capacitors. Specifically, we have developed a suspended in PBS, the fluorescence intensity was modular approach toward poly(vinylidene fluoride) found to be decreased in case of nanoparticles which (PVDF)-based ferroelectric polymers exhibiting high imply that the drug was successfully encapsulated. In dielectric constants (K =50 at 1 kHz). This approach order to study the effect of Rifampicin nanoparticles, allows the chemical compositions of the resulting we also performed cell studies using human skin cells polymers to be precisely controlled, leading to a and have future ideas of testing the nanoparticles on library of ferroelectric polymers with tunable cancer cells. Nanoparticles also show better dielectric properties. The influence of molecular solubility, pharmacokinetics and bioavailability weight and chemical composition on the electrical compared to the drug. breakdown strength of the ferroelectric polymers has been investigated. An unprecedented energy density 435. Photocytotoxicity of Methylated (> 17 J/cm3) with fast discharge speed has been Naphthoquinone on Human Skin demonstrated in the defect-modified PVDF based copolymers. The synthesis and characterization of Rahul A. Khanke, Patty K.-L. Fu. Department of poly(phthalazinone ether ketone) (PPEK) for high- Chemistry, Governors State University, University temperature electric energy storage applications will Park, IL, United States. be presented. It was found that PPEK displayed Since late 1980’s, consumers have demanded more excellent stability of the dielectric properties over a effective personal care products. In today’s market- broad frequency and temperature range. Little change driven economy, there is probably no greater interest in the breakdown field and discharge time has been than the incorporation of vitamins and antioxidants in observed in PPEK with the increase of temperature the merchandise. Owing to the fact that some of these up to 190 oC. A linear correlation between the AC additives are possible photoactive compounds and conductance and the angular frequency implied that might induce serious adverse effects on human skin, the hopping as a dominant conduction process the objective of this study is to evaluate the contributed to the dielectric loss. Superior energy phototoxic and photoallergic potentials of popular densities, remarkable breakdown strengths, and fast vitamin additives such as phytomenadione (vitamin discharge speeds have been demonstrated in PPEK at K1) and menaquinone (vitamin K2). Distressed high temperatures. photoreactions often bring about photocontact dermatitis of the skin. Phototoxic reactions achieves

437. Nano-Scale Layered Approaches to Future applications, such as all-electrical aircraft, Improving Breakdown Strength in Polymer- require new energy storage technologies with Clay Nanocomposites combinations of high energy density (> 20 J/cc), efficiency (dielectric loss < 10-4) and discharge rate 1,2 1 3 Scott P. Fillery, Hilmar Koerner, Eric Dunkerley, (< 1 µs). These must incorporate innovative materials 3 1 Daniel F. Schmidt, Michael F. Durstock, Richard A. that combine increased dielectric strength (> 1000 1 1 Vaia. Materials and Manufacturing Directorate, Air V/µm) and dielectric constant (> 3) with gradual Force Research Laboratory, WPAFB, OH, United failure modes and higher temperature durability. 2 States; National Research Council, Washington, DC, Polymeric nanocomposites offer potential material 3 United States; Department of Plastics Engineering, option by combining high dielectric constant of University of Massachusetts Lowell, Lowell, MA, inorganic fillers with high dielectric strength of United States. polymers. Traditional nanocomposites produced by Polymer films are widely used as the active dielectric blending of components, however, do not provide in current capacitor designs due to their low dielectric sufficient control over morphology, and therefore at loss and high reliability. However, higher energy high inorganic loadings exhibit a drastic reduction in density capacitors are likely to necessitate dielectric dielectric strength. Assemblies of core-shell materials with improved permittivity or dielectric nanoparticles, as a single-component system, offer a strength. The current nanocomposite approaches to possibility for optimization of structure and this challenge have been dominated by random properties through the modification of the interface. morphologies that exhibit drastic reductions in Herein, we report the synthesis and dielectric breakdown strength at higher filler loadings. One properties of the assembly of hybrid nanoparticles promising approach is the creation of a polymer consisted of ceramic core surrounded by covalently nanocomposite with an extreme density of internal attached polystyrene corona via phosphonate interfaces (500-1000 m2/g) which could effectively coupling and “click” chemistry. Titanium dioxide and trap locally injected carriers, inhibiting the barium titanate nanoparticles were used for the core. breakdown event. In this contribution, we report on The chosen synthetic approach afforded materials the fabrication and characterization of two polymer with highly uniform distribution of particles at very layered silicate (PLS) nanocomposite systems, a high loadings (30-60 wt %). Direct solution casting poly(vinyl butyral) – organically modified of these hybrid particles without addition of free montmorillonite clay system and a polyisobutylene – polymer yielded the solid films of high inorganic organically modified montmorillonite clay system. content and sufficient robustness. Results on Film fabrication using either solvent or spray casting, dielectric properties of these materials will be as well as clay contents varying from 5 to 90 vol%, presented. allowed for a high degree of platelet orientation with respect to the electrode orientation. The effects of 439. Electric Energy Storage in Ferroelectric polymer intercalation, clay content and platelet Polymers alignment were characterized and related to the Fangxiao Guan,1 Jing Wang,1 Jilin Pan,2 Qing breakdown strength. Clay contents up to 70vol% Wang,2 Lei Zhu.1,3 1Polymer Program, Institute of were found to exhibit improved breakdown strengths, Materials Science and Department of Chemical, up to thirty three percent for the intercalated single Materials and Biomolecular Engineering, University phase composite system. of Connecticut, Storrs, CT, United States; 2Department of Materials Science and Engineering, 438. Nanoparticles Assemblies for Energy Pennsylvania State University, University Park, PA, Storage United States; 3Department of Macromolecular Maxim N. Tchoul,1 Scott P. Fillery,1 Hilmar Science and Engineering, Case Western Reserve Koerner,2 Lawrence F. Drummy,2 Peter A. Mirau,1 University, Cleveland, OH, United States. 1 3 Michael F. Durstock, Christopher W. Beier, Electric energy storage is extremely important in the 3 1 1 Richard L. Brutchey, Richard A. Vaia. Materials future life of human being. Different forms of electric and Manufacturing Directorate, Air Force Research energy storage generally include batteries and 2 Laboratory, WPAFB, OH, United States; UES Inc., capacitors, each of which have rich condensed matter 3 Dayton, OH, United States; Department of physics ranging from inorganics to organics. On the Chemistry, University of Southern California, Los basis of our recent work on polymer film capacitors, Angeles, CA, United States. fundamental material physics of orientational dipole polarization in ferroelectric polymers and its application in electric energy storage will be

introduced. It is observed that a number of correlations between the thermo-mechanical controlling factors such as crystal orientation (or properties of the polymer films and their high anisotropy), polymorphism (ferroelectric vs. temperature dielectric properties are examined and paraelectric phases), crystallite (grain) size, and the implications for potential long-term electro- crystallinity all play an important role in the overall mechanical stability in wide-temperature power electric energy storage. Understanding of the electronics applications are discussed. polarization physics will help us design and develop better polymeric materials for better electric energy 441. Biopolymer Materials for Electronics, storage. Dielectric and Photonics Applications Fahima Ouchen,1 Donna M. Joyce,2 James E. 440. Thermally Robust Polymer Film 1 1 Dielectrics for Aerospace Power Conditioning Grote. AFRL/RXPS, Air Force Research Laboratory, Wright-Patterson Air Force Base, OH, Capacitors United States; 2AFRL/RYTA, Air Force Research Narayanan Venkat,1 Thuy D. Dang,2 Zongwu Bai,1 Laboratory, Wright-Patterson Air force Base, OH, Jeffery T. Stricker,3 Jennifer N. DeCerbo.3 1Multi- United States. scale Composites and Polymers Division, University DNA-based biopolymer materials offer a versatile of Dayton Research Institute, 300 College Park 2 platform for a wide variety of applications. These Drive, Dayton OH, United States; Nanostructured include, but are not limited to, organic field effect and Biological Materials Branch, Air Force Research transistors (OFETs), organic light-emitting diodes Laboratory, Wright-Patterson AFB, OH, United 3 (OLEDs), and non-linear optical (NLO) polymer States; Electrical technology and Power systems electro-optic (EO) modulators. Devices fabricated Branch, Air Force Research Laboratory, Wright- from these biopolymers have demonstrated Patterson AFB, OH, United States. performance which has often exceeded that of the Thermally stable, mechanically robust, compact state-of-the-art devices made with currently available capacitors are the technology driver for high organic-based materials. A relatively new area of performance power systems. The increasing promise is that of capacitors fabricated from bio- proximity of power electronics to heat sources dielectrics. Specifically, preliminary investigation of demands that the thermal load for electronic system the dielectric and electrical properties of sol- cooling be reduced or even eliminated in the new gel/DNA-CTMA (CTMA = generation aircraft power systems. While aerospace hexadecyltrimethylammonium chloride) complex power system conditioning capacitors typically use hybrids for energy storage applications has revealed polycarbonate (PC) films in wound capacitors for the immense potential of these bio-dielectrics for the operation in the -55ºC to 125ºC range, there is a fabrication of high energy density capacitor devices. current need for high temperature polymer film Film breakdown strength > 800 V/µm and a dielectrics with dielectric stability up to 300ºC or relatively high dielectric constant of 7.5 at <10 kHz higher. As part of our research toward meeting the frequency were measured for spin-coated thin film objective of dielectric stability and reliability in devices of these blends. This talk will present an capacitor devices at temperatures as high as 350ºC, overview of the biotronics/bio-dielectrics we designed and evaluated high strength polymer applications utilizing DNA-based biopolymers. films with high glass transition temperatures (375- 450ºC) as well as high thermal stabilities (470- 442. Chemical Sensing and Imaging in 520ºC). Variable temperature dielectric properties of Combustion Environments Using Terahertz metalized thin films in the RT-350ºC range are Spectroscopy and Imaging reported for high temperature polymer systems such 1,2 4 4 as fluorinated polybenzoxazoles (6F-PBO) and a Jason Deibel, Lin Ma, Sebastian B. Zhang, Weiwei Cai,4 James R. Gord,5 Sukesh Roy,6 Nicholas fluorenyl polyester incorporating a diamond-like 3 3 1 hydrocarbon unit, known as FDAPE. A comparative Schroeder, Satya Ganti, Stanley Smith, Douglas T. Petki.1,2 1Department of Physics, Wright State dielectric evaluation of the state-of-the-art fluorenyl 2 polyester film FPE, with a glass transition University, Dayton, OH, United States; Department of Electrical Engineering, Wright State University, temperature of 330ºC, has also been performed. The 3 focus of the study is on wide temperature Dayton, OH, United States; Department of Mechanical and Materials Engineering, Wright State measurements of film capacitance, dissipation factor, 4 and insulation resistance and on the effects of thermal University, Dayton, OH, United States; Department cycling on polymer dielectric stability. Possible of Mechanical Engineering, Clemson University, Clemson, SC, United States; 5Propulsion Directorate,

Air Force Research Laboratory, Wright Patterson trend of innovation to push back the THz tissue AFB, OH, United States; 6Spectral Energies LLC, imaging frontier. Dayton, OH, United States. Terahertz spectroscopy and imaging is an 444. Far-Infrared Remote Chemical Sensing advantageous technique for combustion diagnostics and Threat Detection due to its non-ionizing nature, broad transparency in Michael A. Gord,1 Anita R. Taulbee-Combs,2 David many mediums, and chemical sensitivity. We will C. Hufnagle,3 Gilbert E. Pacey,3 Carla R. Benton,4 review the use of terahertz technology in chemical Douglas A. Petkie,4 Satya Ganti,4 Jason A. Deibel,4 sensing and specifically combustion measurements Michael C. Moulton,5 James R. Gord.5 1Dayton and focus on our work imaging chemical species Christian High School, Miamisburg, OH, United using a novel tomographic imaging and States; 2University of Dayton Research Insitute, reconstruction technique in conjunction with Dayton, OH, United States; 3Department of terahertz absorption spectroscopy. This will include Chemistry and Biochemistry, Miami University, our work in which a jet flow of steam is imaged and Oxford, OH, United States; 4Departments of Physics the mole fraction of water as a function of spatial and Mechanical and Materials Engineering, Wright dependence is determined. The talk will conclude State University, Dayton, OH, United States; 5Air with a discussion of how this technique will be Force Research Laboratory, Wright-Patterson AFB, expanded in the near future to further include OH, United States. increased spatial resolution, temperature measurements, and species identification. Many current and future applications require new techniques for detecting and identifying hazardous 443. Terahertz Imaging of Biological Tissues: chemicals and other potential threats. Such Reacting, Adapting and Innovating for applications include the Global War on Terror, homeland and portal security, medicine, industrial Medical Applications process monitoring, and atmospheric and Anita R. Taulbee-Combs,1 Gilbert E. Pacey.2 environmental studies, including exploration of 1Department of IDCAST, UDRI, Dayton, Ohio, greenhouse gases and global warming. CBRNE United States; 2Department of Chemistry, Miami (chemical, biological, radiological, nuclear, and University, Oxford, Ohio, United States. explosive) threats are of particular interest. Millimeter-wave and terahertz (THz) radiation is Terahertz (THz) imaging has emerged as a valuable ideally suited for many such applications. Eye-safe technique for nondestructive evaluation of tissues. radiation in this spectral region has been used with This presentation discusses past to future innovations techniques that include absorption spectroscopy, in the field of THz medical imaging including: interferometry, and frequency-modulated continuous- discoveries made using time-domain THz imaging, wave (FM CW) radar to identify various classes of recent advances in continuous-wave (CW) systems, gaseous and solid chemicals and to detect concealed and the development of focal-plane array (FPA) threats. Standoff measurements at safe distances have detectors. Time-domain THz pulse imaging been demonstrated using radiation beams and facilitated ground-breaking studies on small areas of remotely operated vehicles (ROVs) as well. skin and excised tissue. The knowledge base generated by these studies revealed that THz β technology has the potential to detect and contrast 445. Effect of Meso-Substitution and -Bromo injured or diseased tissue from healthy tissue. Substitution on the Photophysical Properties Unfortunately, lengthy acquisition times of raster- of Porphyrins scan imaging methods, and the need to eliminate Joy E. Haley,1,2 Weijie Su,1,3 Jonathan E. Slagle,1,4 water vapor, made implementation of broadband Jennifer L. Monahan,1,5 Daniel G. McLean,1,4 methods in the medical field impractical. Reacting to Thomas M. Cooper.1 1Materials and Manufacturing the needs of its audience, the THz community is Directorate, Air Force Research Laboratory, adapting tissue imaging studies to employ CW THz WPAFB, OH, United States; 2UES, Inc., Dayton, technology. The stand-off capabilities and short OH, United States; 3General Dynamics Information acquisition times provided by CW THz systems Technology, Dayton, OH, United States; 4Science facilitate in vivo tissue imaging over larger areas in a Applications International Technology, Dayton, OH, fraction of the time, encouraging higher data volume United States; 5Southwestern Ohio Council for and inclusion of new studies that were not previously Higher Education, Dayton, OH, United States. feasible. As we look toward the future, technological developments such as FPA detectors continue the

Due to the ease of modification of porphyrins a large conductivity of the thin film samples studied here are amount of effort has gone into developing new all well below that of single crystal RuO2 with chromophores that display certain characteristics for tetragonal rutile structure (50 W m-1 K-1 [1]). The certain applications as evidenced by the vast amount samples also have an inverse relationship of thermal of literature. The optical properties of the porphyrins conductivity with Seebeck coefficient [2], which is along with the vast synthetic methodologies available desirable for improving the figure of merit for make porphyrins a target choice for use as nonlinear thermoelectric performance. optical materials. We have recently synthesized and studied the structure property relationship of a series References of meso-carbazole and meso-triphenylamine octabromoporphyrins including absorbance, [1] Ferizovic D, Hussey LK, Huang Y-S, Munoz M. emission, femtosecond transient absorption, and Determination of the room temperature thermal nanosecond laser flash photolysis techniques. conductivity of RuO2 by the photothermal deflection Various changes have been made to the porphyrins technique. Appl Phys Lett 2009;94:131913. such as the central metal, changes at the meso position, and addition of bromine to the b-position. [2] Music D, Basse F H-U, Habdorf R, Schneider JM. One effect of interest is the addition of Synthesis and thermoelectric properties of RuO2 triphenylamine and carbazole relative to phenyl in the nanorods. J Appl Phys, submiited for review. meso position to the triplet excited state properties. In general we observe a large triplet excited state 447. Optical Visualization of Energy Release absorption in the near infrared region and a dramatic Following Ignition of Energetic shortening of the triplet excited state lifetime upon Nanomaterials the addition of the bromine. This is expected due to 1 2 the heavy atom effect of the bromine but is also Hans U. Stauffer, William K. Lewis, Christopher 1 3 1 consistent with more distortion of the porphyrin E. Bunker, Sukesh Roy, James R. Gord. 1 structure. The overall findings will be discussed in Propulsion Directorate, Air Force Research more detail. Laboratory, Wright-Patterson Air Force Base, OH, United States; 2Sensors Technology Office, University of Dayton Research Institute, Dayton, OH, 446. Thermal Conductivity Measurements of 3 RuO Nanorods United States; Spectral Energies, LLC, Dayton, OH, x United States. Jamie J. Gengler,1,2 Andrey A. Voevodin,1 Denis Music,3 Felix H.-U. Basse,3 Ralf Hassdorf,4 Jochen Materials containing nanometer-scale particles of M. Schneider.3 1Materials and Manufacturing aluminum have recently shown considerable promise Directorate, Thermal Sciences and Materials Branch, in allowing improved control of energy density and Air Force Research Laboratory, Wright-Patterson Air energy release rates associated with the next Force Base, OH, United States; 2Spectral Energies generation of explosives and propellants. Several LLC, Dayton, OH, United States; 3Materials variables are known to contribute to the energetic Chemistry, RWTH Aachen University, Aachen, properties of these materials, including nanoparticle Germany; 4Institute of Materials Research, DLR size and size distribution, proximity to and chemical German Aerospace Centre, Cologne, Germany. composition of surrounding oxidant, nanoparticle density within composites containing oxidizing Thermal conductivity trends in RuOx thin films of species, and nature of the nanoparticle passivating varying stoichiometry were characterized with a layer. However, the direct measurement of the time- time-domain thermoreflectance (TDTR) technique. dependent energy release rates during ignition of At an O/Ru ratio of x = 1.69, a faceted film surface is these materials has until recently proven challenging. observed with a measured thermal conductivity value Results will be presented in which time-dependent -1 -1 of 28.8 ± 0.8 W m K . With an O/Ru ratio of x = energy release is observed and characterized for 2.24, nanorod formation occurs. These films were several energetic materials containing nano- grown by a reactive magnetron sputtering technique aluminum using time-resolved optical probe 0 with nonrotating substrates oriented 20 normal to the techniques. Ru target. Such material synthesis conditions resulted in a gradient sample structure at the onset of nanorod 448. Autonomic Healing in Polymers and formation. As a result, the RuO2.24 samples exhibited Composites gradually changing surface roughness (rms of 12 nm 1,2 4 – 200 nm) and thermal conductivity values (22 W m-1 Scott R. White, Nancy R. Sottos, Jeffrey S. 3 4 3 K-1 – 5 W m-1 K-1), respectively. The thermal Moore, Amit J. Patel, Mary M. Caruso, Andrew R.

Hamilton,5 Benjamin J. Blaiszik.2 1Department of between different states, which can be triggered with Aerospace Engineering, University of Illinois at heat, results in a reversible change from a structural Urbana-Champaign, Urbana, IL, United States; composite material to a soft composite material 2Beckman Institute for Advanced Science and capable of high strains. In addition, increased Technology, University of Illinois at Urbana- survivability can be achieved through the design and Champaign, Urbana, IL, United States; 3Department integration of intelligent and adaptive systems with of Chemistry, University of Illinois at Urbana- modified SMP matrices that are capable of healing Champaign, Urbana, IL, United States; 4Department into structural composites. The material technology, of Materials Science and Engineering, University of when coupled with an appropriate control system has Illinois at Urbana-Champaign, Urbana, IL, United the ability to enable a new philosophy in vehicle States; 5Department of Mechanical Science and design capable of generating dramatic increases in Engineering, U, Urbana, IL, United States. vehicle survivability and vehicle performance through the establishment of real-time data on Autonomic materials systems are inspired by structural health and vehicle adaptability. biological systems in which an external trigger produces an autonomic functional response. As an example, structural polymers and polymer matrix 450. Novel Approach to Synthesizing composites have recently been developed that Polyaspartimide-Polyurea Based Shape possess the ability to self-heal. Self-healing is Memory Polymers accomplished via the release of healing agents Joseph A. Shumaker,1,3 Amber J. W. McClung,2,3 embedded within a polymer matrix. Damage triggers Shawna A. Matthys,3 Jeffery W. Baur.3 1University the healing response and it proceeds at room of Dayton Research Institute, Dayton, Ohio, United temperature without human intervention. The States; 2National Research Council Research autonomic nature of the healing functionality makes Associate, WPAFB, Ohio, United States; 3Air Force these materials particularly appealing for industrial Research Laboratory, WPAFB, Ohio, United States. applications. Shape memory polymers (SMPs) have attracted great In this talk the initial development of self-healing interest in recent years for application in adaptive polymers and their demonstration for a variety of (multi-mission) structures. However, Air Force damage states will be reviewed. Beyond these early relevant environments require materials with microencapsulated self-healing concepts, more recent enhanced durability and transition temperatures well research on microvascular materials systems and in excess of those produced for biomedical mechanochemically active polymers will also be applications. Commercially available SMPs with presented. Such materials may one day provide the durability, transition temperatures, and processability capability for self-sensing, thermal stasis, regrowth closer to that of a structural resin have limited and other biologically-inspired functions. tailorability due to their proprietary nature. A robust and scalable structural resin system that can be 449. Shape Memory Polymer Innovations in synthetically tailored to withstand typical Aerospace aerodynamic loadings, environmental exposures and operating temperatures while also being tailorable to Tat Tong, Thomas J. Barnell, Thomas W. Margraf, lower transition temperatures is desired to meet Michael R. Maddux, Jason M. Hermiller, David E. emerging adaptive applications. In the present study, Havens, Chris D. Hemmelgarn. Cornerstone a series of novel linear polyaspartimide-polyurea Research Group, Inc., Dayton, OH, United States. based polymers are synthesized. To increase material Shape memory polymers (SMP) offer unique toughness/strength to these systems, as well as, shape performance capabilities not found in traditional memory capabilities, a diisocyanate resin is being polymers. This class of material often functions as incorporated to create a thermosetting material with both an elastomer and a rigid plastic in the same varying crosslink densities. The chemical structures application. SMP’s ability to change stiffness and thermal properties were determined with infrared modulus and shape configuration upon stimulus spectroscopy, thermogravimetric analysis, differential makes it ideal for applications requiring lightweight, scanning calorimetry, and dynamic mechanical dynamic, and adaptable materials. Applications of analysis. These thermosets offer a controllable new SMP composite materials in aerosystems approach for the study of the mechanisms and the focused on damage response and adaptability have optimization of shape memory performance in been developed, embodied by reflexive composites ongoing research. and morphing structures. The transformation of SMP

451. Electropun Smart Polymeric Composites student critical thinking skills. These lessons will be discussed here. Patrick T. Mather,1 Xiaofan Luo,1 Erika D. Rodriguez.2 1Biomedical and Chemical Engineering, & Syracuse University, Syracuse, NY, United States; 453. Teaching Chemistry Content 2Mechanical and Aerospace Engineering, Syracuse Pedagogy – A Project-Based Learning University, Syracuse, NY, United States. Approach at the Graduate Level It is well established that the properties of polymeric Katherine W. Stickney, Jennifer Drake. Department materials can be tailored at multiple scales, from of Chemistry, University of Indianapolis, macromolecular composition and architecture to Indianapolis, IN, United States. macroscopic reinforcement with fillers or fibers. The Woodrow Wilson Indiana Teaching Fellows Reinforcement of polymeric materials at the Program was launched in 2009 with a specific goal of nanometer scale offers advantages of homogeneity preparing career changers (bachelor degree holders in and synergistic effects intrinsic to the 1-100 nm scale STEM areas) to teaching careers in high needs and interphase formation. Nevertheless, preparation schools. The University of Indianapolis was one of of nanocomposites is challenging. In the past, routes four Indiana universities selected to pilot this new to polymeric nanocomposites have largely fallen into program. Charged with writing an innovative one of two categories: (i) top-down processing of curriculum for this Master of Arts in Teaching nanocomposites by dispersion of nanofillers in degree, UIndy faculty and school district partners monomer or polymer melts and solutions, or (ii) wrote a novel, project-based learning curriculum for bottom-up synthesis of nanocomposites by the first year course work. A brief overview of the polymerization of nanostructured monomers. In both Woodrow Wilson Indiana Teaching Fellows Program cases, it has been challenging for researchers to will be given here. A specific look at teaching achieve the interpenetration of matrix and relevant chemistry content, via a PBL approach to reinforcement often desired for full exploitation of master degree candidates, as well as reflections after the two phases. In this presentation, a third the first year of the program, will be also presented alternative to the preparation of nanocomposites is here. presented in the context of several distinct project implementations: electrospun nanocomposites. Here, 454. Will It Blend: Large Lecture Course, we first electrospin an interconnected (welded) polymeric nanofiber web using established methods. Clickers, and Team-Based Learning? Then, this web is imbibed with a matrix precursor Mark D. McClain,1 Susan C. Warner,2 Donald S. liquid and crosslinked or otherwise solidified. Humphreys.2 1Department of Science and The result is an interpenetrating nanocomposite with Mathematics, Cedarville University, Cedarville, tailored properties. The presentation will reveal four Ohio, United States; 2Center for Teaching and utilizations of such materials, including: (i) Fuel cell Learning, Cedarville University, Cedarville, Ohio, membranes, (ii) Shape Memory Elastomeric United States. Composites, (iii) Triple Shape Memory Polymers, and (iv) Electrically Triggered Shape Memory Audience response devices and team-based learning Polymers. techniques were incorporated in 100+ student General Chemistry lecture courses to increase engagement, insure readiness for class, and leverage 452. Critical Thinking in Early Childhood student abilities for mutual advantage. Clickers were Education used to assess learning throughout class sessions. Daniel D. Bombick. Chemistry, Wright State Individual and team readiness assurance testing University, Dayton, Ohio, United States. showed substantial improvement through cooperative learning. Surveys showed significant improvement in I have been involved in teaching science courses for student’s attitudes toward group activities. early childhood education majors for a short time. My initial thought on the level of critical thinking 455. From High School to Ph.D: Reacting to skills possessed by the students upon entering the science course was much higher than reality. the Question, “What Can You Do with a Evidence for this comes primarily from pre-exams Degree in Chemistry?” given at the beginning of the course. Lessons were Jennifer N. Williams, Sidney Jones, Simuli developed with the intention of raising the level of Wabuyele. Department of Chemistry, Cleveland State University, Cleveland, OH, United States.

What explanation do you give to high school students 457. Color, Light, Vision and Perception in when asked the infamous question, “What can you do Chemistry with a degree in chemistry?” More often than not inner-city high school students lack exposure to the Bassam Z. Shakhashiri, Rodney Schreiner, Jerry intimate details of the steps required to successfully Bell. Department of Chemistry, University of matriculate through the path to STEM careers. Wisconsin-Madison, Madison, WI, United States. Resultantly, students frequently make critical career Chemical concepts and principles are at the heart of decisions without consideration of the fundamental the ways we perceive the world around us, but our information involved and do not develop the students often do not appreciate these connections. appreciation for chemistry until later years, if ever. Staff at the Wisconsin Initiative for Science Literacy The journey to both academic and career success here (www.scifun.org) completed a project to help to is often vague and misunderstood. So in efforts to connect chemistry with what we receive via our sense increase STEM awareness, particularly the of sight. The project brings color and light to the opportunities for students in the vast field of forefront, provides detailed instructions both for chemistry, Cleveland State University chemistry displaying colorful phenomena and illustrating graduate students have began to tackle this issue. scientific principles, and describes what happens Members of the CSU Graduate Student when visual information enters the human eye and is Interdisciplinary Research Club (G-Sirc) have perceived by the brain. With over 50 demonstrations, embraced the opportunity to bridge the knowledge this project sets new goals and expectations for gap that inner-city high school students face when arousing and sustaining interest in chemical investigating higher education and careers in transformations. Also included is a rich introductory chemistry. With a “layman’s terms” approach, section that explains the science of color and light graduate students recently visited John Hay High and outlines the chemical processes of vision and the School’s “Early College Program” to debunk many effects of visual stimuli that lead to perception. At myths associated with degrees in chemistry, while this session we shall display several new unveiling their research studies undertaken in the demonstrations. fields of drug development, cancer research and alternative fuel sources. 458. Modeling of Random Unidirectionally Fiber-Reinforced Composites 456. Communicating Chemistry in the Classroom and to the General Public Stephen Davis. Department of Aerospace Engineering, Texas A&M University, College Bassam Z. Shakhashiri. Department of Chemistry, Station, TX, United States. University of Wisconsin-Madison, Madison, WI, United States. This research project examines the applicability of a particular software interface used to create a random Chemists have a responsibility to communicate array of unidirectional fibers within a matrix. When science to fellow scientists and to the general public. used in conjunction with the Air Force Research Beyond advancing science and technology we must Laboratory’s in-house finite element software known help all citizens develop an appreciation of science, as B-Spline Analysis Method (BSAM), this creates the benefits of technology, and the potential risks an accurate carbon fiber composite representation associated with advances in both. Citizens must gain within individual plies. Specifically, this is done by “science literacy.” I make a distinction between developing a pre-processor in Microsoft Visual Basic scientific literacy, expertise in a particular field, and that allows the user to specify several options science literacy, a broad appreciation and including volume fraction of fibers relative to the understanding of science and its practitioners, and of matrix and number of inclusions. After generating what science is capable of achieving and what it suitable composites, the homogenous properties are cannot accomplish. Science literacy enlightens and found by analyzing the file in BSAM. The results are enables people to make informed choices, to be compared with good agreement to those of skeptical, and to reject shams, quackery, unproven rectangular and hexagonal fiber packing distribution. conjecture, and to avoid being bamboozled into making foolish decisions where matters of science 459. Molecular Simulations of Peptide and technology are concerned. Science literacy is for everyone: chemists, artists, humanists, all Binding to Silica professionals, the general public, youth and adults Yen Ngo,1 S. Bacon.2 1College of Arts & Science, alike. Achieving science literacy is necessary for the Wright State University, Dayton, OH, United States; democratic process to work.

2Prairie View A & M University, Prairie View, TX, flow rate, deposition temperature, and deposition United States. power were varied. Spectroscopic Ellipsometry measurements, utilizing wavelengths in the range of The project was primarily focused on the interaction 250nm-1200nm, were taken in order to evaluate the energies of peptides with silica surfaces. The optical constants. Atomic Force Microscopy was objective was to imitate the biosilification process by performed to understand the effect of growth using model peptide fragments such as P1, P4, H4, conditions on the surface-structure, specific to the R5, and LSRH. Most of the data obtained in the size and distribution of the particles on the surface. project were taken from the Molecular Dynamic Furthermore, the thin films were subjected to an X- simulations of the H4 peptide. The results obtained, Ray Photoelectric Spectroscopic study so as to proved the binding energies, of the peptide to the determine the effects of the varying deposition silica surface, were greater in high concentration parameters on the surface elemental composition. solutions. 462. Oxidation of BMI 5250 460. Biological Effects of Carbon Foam on the Neuroblastoma Cell Line Stephanie Reed. Dayton Early College Academy High School, Dayton, OH, United States. Hadil Issa. Department of Mechanical & Aerospace Engineering, University of Dayton, Dayton, OH, Bismaleimide (BMI) 5250 are uni-directional United States. composites, which are used for high temperature applications, such as engine parts in aircraft. Porous structures have been used in wide array of Durability of the composites was conducted by applications: tissue engineering, biology and thermal studying the oxidation process of the composites with management. Due to its unique structure and respect to time. To conduct the test durability the exceptional properties, carbon foam has made BMI 5250 were aged in an oven for varying hours. significant advancements in the fields of science and They were then prepped for optical microscopy using technology. Microcellular carbon foam, like that of the Nikon Optical Microscope, to observe oxidation other porous structures, is being explored in the fields and degradation, which are both harmful to the of medicine, mechanics and engineering. Due to specimens. As a control, aluminum and silver coating recent findings of enhancing osteoblast cell growth were added to observe whether or not adding a metal and proliferation, carbon foam is being tested to for coating would aid in the decrease of the oxidation the biological and morphological effects on different and degradation on the specimen. There were 14 cell lines. In this project, the effect of carbon foam on specimens split into two groups: 7 specimens with the growth of neuroblastoma cell line is being tested silver coating, and 7 specimen with aluminum through mitochondrial function assays and various coating. The first group of specimens aged for 4 hrs, imaging techniques. The results have shown an the second group aged for 24hrs, the third group aged increase in cell function, and proliferation. Carbon for 100hrs, the fourth group aged for 200hrs, the fifth foam could be further functionalized for future group aged for 400hrs, the sixth group aged for applications to enhance the cognitive abilities of the 731hrs, and the last group aged for 1000hrs. war-fighter. 463. Phototresponsive Azobenzene Liquid 461. On the Effect of Deposition Conditions Crystal Polymer Networks on the Optical and Surface Characteristics of Zirconium-Based Oxide, Oxynitride, and Yanira Torres. Department of Mechanical Nitride Thin Films Engineering, Florida State University, Tallahassee, Florida, United States. Issac Fernandez. Department of Mechanical Engineering, University of Texas at El Paso, El Paso, Azobenzene liquid crystal polymers and polymer networks are adaptive materials capable of TX, United States. converting light into mechanical work. Often, the Zirconium oxide, zirconium nitride, and zirconium photomechanical output of the azobenzene liquid oxy-nitride offer interesting optical and electrical crystal network (azo-LCN) is observed as a bending properties, which depend on the nitrogen cantilever. The response of these materials can be stoichiometry. Thin films of the aforementioned either static (e.g. a simple bending cantilever) or compounds were deposited on glass, quartz, and dynamic (e.g. oscillating cantilever of 20-270 Hz). silicon (100) substrates by RF Magnetron Sputtering. The resulting photomechanical output is dependent In each category, the argon, oxygen, and nitrogen upon the domain orientation of the polymer network

and the wavelength and polarization of the actinic I will talk about our celebration of Mole Day and our light. Polydomain azobenzene liquid crystal polymer Chemistry Club. I will also share experiments we networks, which have the capability of bending both have developed for teaching moles. We participate in backwards and forwards with the change of National Chemistry Week contests sponsored by the polarization angle, is of particular interest this ACS Cleveland section. summer. Exploration of the mechanical behavior at different temperatures and examination of structure- 468. A STEM Overview property relationships in the polymerization process, including curing temperatures, liquid crystal cell Pat Fife. Kettering Fairmont High School, United alignment rubbing methods, and monomers used will States. be explored. Using dynamic mechanical analysis I will address: what is STEM? What does it mean for (DMA) the mechanical properties and the students and teachers? What is happening in STEM photogenerated stress in the polymer will be in the Miami Valley? examined. Specifically, two azo-LCN will be compared – equivalent in all respects except for one 469. Surviving the First Five Years of contains pendant azobenzene mesogens (1azo, azo- Chemistry Teaching monoacrylate) and the other is based on crosslinked azobenzene mesogens (2azo, azo-diacrylate). Christina Tetzlaff. Indian Springs School, United States. 464. Simple Stimulating Classroom I will provide tips and thoughts on how to survive the Demonstrations beginning of a teaching career both inside and John J. Fortman. Department of Chemistry, Wright outside the classroom. Building a respectful State University, Dayton, OH, United States. classroom environment is crucial in both the learning and motivating process of teaching students. Demonstrations using common materials will be done. They will illustrate principles such as gas laws, 470. Students Teaching Younger Students: atmospheric pressure, and combustion, and their The Chem Buddies Program application such as flight, soda pop, and engines. Bonnie Buddendeck. Centerville High School, 465. A Vibrant Classroom – 37 Years’ United States. Worth! For 18 years, my AP Chemistry students have done Linda Ford. The Seven Hills School, Cincinnati, community service by judging science fairs, helping OH, United States. out with COSI visits and going into elementary school classrooms to present demonstrations and I will share some of the ways – both intentional and assist with experiments. This program benefits the unintentional – that have helped me to maintain a high school students who get to teach chemistry vibrant classroom over a thirty-seven year career. concepts, elementary students who see the excitement of science, and elementary teachers, who often do not 466. Lighting the Fire for Science! know how to explain the science. Andrew Felczan. Wyoming High School, United States. Success stories (and a few cautionary tales!) from teaching at the college, high school, middle and elementary levels will be discussed. Topics include shifting from knowledge=-based lessons to process- based lessons, putting students in teams that work, and the importance of teaching students to risk. Also, I will share my favorite (and not so favorite) ideas for explosions!

467. Motivating Students in Chemistry Elizabeth Dabrowski. Magnificat High School, United States.