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DUQUESNE UNIVERSITY American Chemical Society Student Members

TWENTY-NINTH ANNUAL SYMPOSIUM

Indiana University of Pennsylvania

Duquesne University

Chatham University Featured Speakers:

Prof. Pete Smith Geneva College Westminster College

University of Pittsburgh Dr. Arash Parsi at Johnstown Westinghouse Electric Company

Seton Hill University Prof. Bohdan Schatschneider Penn State, Fayette Slippery Rock University

University of Pittsburgh

Pennsylvania State University at Fayette

April 11, 2015

Chemistry and Biochemistry Bayer School of Natural and Environmental Sciences Duquesne University Pittsburgh, PA 15282

The 29th ACS Symposium is supported by

Pittsburgh Section of the American Chemical Society

Bayer Corporation

Students Members of the American Chemical Society at Duquesne University

Department of Chemistry and Biochemistry, Duquesne University

Gaussian Incorporated

The Center for Computational Sciences, Duquesne University

2015 ACS Student Member Symposium

Duquesne ACS Student Executive Board Members: Sarah Kochanek – President; Ben Jagger – Vice President; Allison Jansto – Treasurer; Kasey Devlin – Secretary; Sarah Richards – Public Relations; Allison Williams, Marissa McGovern, Avani Dalal, Megan Hockman, Erin Gorse, Christian Gaetano, James Nielsen, and Stephen Ratvasky – Members

April 11th, 2015

Dear Faculty Advisors and Students,

This is the twenty-ninth Pittsburgh Section Student Member Meeting. Undergraduate research is a rewarding experience, which impacts your future career in chemistry and the chemical sciences. The Pittsburgh Section and all of its members are proud of the effort that you and your mentors have put forth to make our region exceptionally strong. In the past, over two hundred professionals have contributed to this special effort. Again, as with last year, we have over 50 participants! Many of the previous contributors have distinguished themselves in the medical, chemical, dental, educational, and other professions, and many have become leaders in the American Chemical Society. To all of these individuals, and to you, the Section is indebted. We hope that this meeting will be a successful and rewarding experience.

Sincerely, Sincerely, Sincerely,

Jeffrey D. Evanseck Paul G. Johnson Ellen S. Gawalt ACS Student Affiliate Advisor ACS Student Affiliate Advisor ACS Student Affiliate Advisor Professor Assistant Professor Associate professor Chemistry and Biochemistry Chemistry and Biochemistry Chemistry and Biochemistry Lauritis Chair of Teaching and Technology Duquesne University Duquesne University Duquesne University 600 Forbes Avenue 600 Forbes Avenue 600 Forbes Avenue Pittsburgh, PA 15282 Pittsburgh, PA 15282 Pittsburgh, PA 15282 E-mail: [email protected] E-mail: [email protected] E-mail: [email protected]

1. PARK in the FORBES garage. Take the 1. elevators to the 8th floor. BRING YOUR 2. TICKET ! 3.

2. From the 3. Mellon 8th floor, Hall is walk past across the student Academic union. Walk.

2015 ACS Student Member Symposium

April 11th, 2015

Meeting Location: Registration, talks, lunch and poster session: Mellon Hall and the Laura Lecture Room

Registration and Poster Setup 8:30 – 9:50 am Coffee, tea, bagels and donuts Morning Session (25 minute talks, 10 minutes of questions – with student prizes) 10:00 – 10:05 Prof. Ralph A. Wheeler, Duquesne University “Welcome and Introduction”

10:05 – 10:40 Prof. Pete Smith, Westminster College [email protected] "Recovering rare earths from scrap technological products "

10:40 – 11:15 Dr. Arash Parsi, Westinghouse Electric Company [email protected] “Using nanostructural characterization techniques to answer challenges in nuclear power generation "

11:15 – 11:50 Prof. Bohdan Schatschneider, Penn State, Fayette [email protected] "Dynamics of solid state materials "

Lunch (Laura Hall) 12:00 – 12:30 pm (Lunch provided – including vegetarian selection)

Student Poster Session (Mellon Hall) 12:30 – 1:45 pm Award Ceremony (Laura Hall) 1:45 – 2:30 pm Symposium concludes 2:30 pm

For more information and electronic registration, please visit our site

http://www.duq.edu/academics/schools/natural-and-environmental-sciences/academic-programs/chemistry-and-biochemistry/acs-student-member- symposium

Everyone (faculty, students and visitors) must register (free of charge), and students presenting posters must additionally submit their abstracts at the same site given above. Questions? Contact the Duquesne Student Members [email protected]

2014 Invited Speakers Prof. Yoosuf Picard, Carnegie Mellon University [email protected] "Energetic Beams for Materials Research at the Nanoscale" Prof. Paul J. Birckbichler, Slippery Rock University [email protected] “A Journey Through Science" Prof. Jeffrey J. Rohde, Franciscan University of Steubenville [email protected] "Preparation of Acyl Hydrazone Analogs for Anti-Parasitic Activity in Trypanosoma cruzi with a Focus on Collaborative, Humanitarian, and Educational Benefits"

2014 Award Winners Jessica Mols Slippery Rock University Ian MacKenzie Geneva College Matthew Stewart Franciscan University of Steubenville Joshua Doverspike and Evan Sawyer University of Pittsburgh at Johnstown Jennifer Moore and Christopher Copeland Youngstown State University

2013 Invited Speakers Lisa Bell-Loncella, University of Pittsburgh at Johnstown [email protected] “Models to Study Electron Transfer: Nanoscale Wires & Switches” Robbie J. Iuliucci, Washington & Jefferson College [email protected] “Chemical Shift Anisotropy Measurements and Applications Towards Crystal Structure Refinement” Irina Schwendeman & Courtney Balliet, PPG Coatings Innovation Center [email protected] “Next Generation Cool Roof Coatings”

2013 Award Winners Avani Dalal Duquesne University Rebecca L. Beadling Indiana University of Pennsylvania Megan Barringer Slippery Rock University Ethan Stern University of Pittsburgh, Johnstown Brian Lewis University of Pittsburgh, Johnstown

2012 Invited Speakers

Prof. Joel Bandstra, St. Francis University [email protected] “The Lab/Field Discrepancy in Mineral Weathering: Is Surface Evolution to Blame?”

Prof. Jaeju Ko, Indiana University of Pennsylvania [email protected] “Prediction of Protein Function from Structure”

Dr. Peter Uthe, Bayer MaterialScience LLC [email protected] “Managing Innovation and Cost Leadership: Polyurethane Process Research” 2012 Award Winners Justin Wendzicki Duquesne University Rebecca Thoma Chatham University Melissa A. Maczis Slippery Rock University Thomas N. Rohrabaugh, Jr. University of Pittsburgh, Johnstown

2011 Invited Speakers Prof. Helen M. Boylan, Westminster College [email protected] “Efficacy of Passive Treatment for Abandoned Mine Drainage: Results from a Service Learning Study”

Prof. James Coffield, Wheeling Jesuit University [email protected] “Dithiocarbamate Chemistry at Wheeling Jesuit University: A Successful, Long-Term Research Program at a Primarily Undergraduate Institution”

Prof. Timothy L. Evans, University of Pittsburgh at Johnstown [email protected] “G quadruplex Forming mRNA and the Brain”

Prof. P. J. Persichini III, Allegheny College [email protected] “Boron Mediated Tandem and Transfer Strategies in Synthesis & Beyond”

2011 Award Winners Jordan Creany University of Pittsburgh, Johnstown Breeanna Mintmier Indiana University of Pennsylvania Logan Miller Slippery Rock University Cheri Dover Slippery Rock University

2010 Invited Speakers Prof. Peter Norris, Youngstown State University [email protected] “Sulfonyl azides as diazo and azido transfer reagents”

Prof. Ebony Roper, Lincoln University [email protected] “Aerosol chemistry”

Prof. Min Soo Lim, Slippery Rock University [email protected] “Realization of the quantum world. Scanning probe microscopy - Its principle and applications” Prof. Jason Vohs, St. Vincent College [email protected] “Mentoring through undergraduate research: What I’ve learned after five years”

2010 Award Winners Anthony Horner St. Francis University Michael Washington Seton Hill University

2009 Invited Speakers

Prof. Joseph MacNeil, Chatham University [email protected] “A Field of Dreams: Exploring the Role for Sunflowers in the Phytoremediation of Heavy Metals”

Prof. Nina Stourman, Youngstown State University [email protected] “Functional genomics of E. coli: Glutathione metabolism”

Prof. Michael Leonard, Washington and Jefferson College [email protected] “Synthetic organic research with undergraduate and high school students at W&J College”

Dr. Karl W. Haider, Bayer Material Science, LLC Innovation Manager, New Technologies Group [email protected] "Industrially Relevant Bio-sourced Polymers and Feedstocks"

2009 Award Winners Jacob Rosenbaum University of Pittsburgh at Johnstown Erin M. Lawrence Slippery Rock University

Heather J. Harteis Saint Francis University Kristin Johnson & Brooke Katzman Youngstown State University Beth Leverett Indiana University of Pennsylvania

2008 Invited Speakers Prof. Rose Clark, St. Francis University [email protected] “Probing the Effects of Self-assembled Monolayer Composition on Cytochrome c Electrochemical Response” Prof. Charles Lake, Indiana University of Pennsylvania [email protected] “Winning in the Adamantine-Like Quaternary Calcogenide Li2ZnSnS4; A Crystallographic Detective Story” Prof. Benny G. Johnson, Quantum Simulations, Inc. [email protected] “Artificial Intelligence Tutoring Software for General Chemistry”

2008 Award Winners Kayce Tomcho Slippery Rock University Kimberly A. Schrock St. Francis University Caitlin Williamson Indiana University of Pennsylvania Carlene Pasipanki Seton Hill University

10 Symposium Attendees

Name Institution Email Poster #

Ahmed, Ayan Duquesne University [email protected] 22

Alshoaibi, Haneen Chatham University [email protected] 8

Baer, Ryan Pennsylvania State University - Fayette [email protected] 29

Bandi, Kathryn Duquesne University

Bautista, Danielle Duquesne University [email protected] 10

Bell-Loncella, Lisa University of Pittsburgh - Johnstown [email protected]

Birkbichler, Paul Slippery Rock University [email protected]

Bruneel, Cheryl Guest

Bruneel, Nicole Duquesne University [email protected] 6

Caro, Veronica Indiana University of Pennsylvania [email protected] 12

Cribbs, Marvene Duquesne University [email protected]

Czegan, Demetra Seton Hill University [email protected]

Devlin, Kasey Duquesne University [email protected] 18

Doverspike, Joshua University of Pittsburgh - Johnstown [email protected] 2

Evans, Tim University of Pittsburgh - Johnstown [email protected]

Evanseck, Jeffrey Duquesne University [email protected]

Gaetano, Christian Duquesne University [email protected] 4

Garcia, Taylor Pennsylvania State University - Fayette [email protected] 30

Gobrish, Briana Seton Hill University [email protected] 14

11 Gorse, Erin Duquesne University [email protected] 1

Graham, Aschleigh Indiana University of Pennsylvania [email protected] 13

Grimminger, Marsha University of Pittsburgh - Johnstown [email protected] 7

Highland, Jaclyn Slippery Rock University [email protected] 28

Hockman, Megan Duquesne University [email protected] 26

Hoover, Diana Seton Hill University [email protected]

Jagger, Benjamin Duquesne University [email protected] 24

Jansto, Allison Duquesne University [email protected] 16

Jesikiewicz, Elise Duquesne University [email protected] 9

Johnson, Paul Duquesne University [email protected]

Jones, Celeste Seton Hill University [email protected]

Ko, Jaeju Indiana University of Pennsylvania [email protected]

Kochanek, Sarah Duquesne University [email protected] 23

Lang, Cara University of Pittsburgh - Johnstown [email protected] 3

Malosh, Thomas University of Pittsburgh - Johnstown [email protected]

McCray, Brosnan University of Pittsburgh - Johnstown [email protected]

McMahon, Kerry Geneva College [email protected]

McCarthy, Angela Seton Hill University [email protected] 20

Mols, Jessica Slippery Rock University [email protected] 27

Mummert, Jordan University of Pittsburgh [email protected]

Nathaniel, Mark University of Pittsburgh - Johnstown [email protected]

12 Richards, Sarah Duquesne University [email protected] 15

Roland, Ashley Slippery Rock University [email protected]

Schaffer, Jacob University of Pittsburgh - Johnstown [email protected] 11

Schomer, Chelsie Seton Hill University [email protected] 17

See, Noreen Guest

See, Ronald Indiana University of Pennsylvania [email protected]

Senock, Zackery University of Pittsburgh - Johnstown [email protected]

Sweger, Sarah Duquesne University [email protected] 21

Vivis, Samantha University of Pittsburgh - Johnstown [email protected]

Weiland, Ashley Duquesne University [email protected] 5

Wheeler, Ralph Duquesne University [email protected]

Williams, Allison Duquesne University [email protected] 25

Wise, Christopher Indiana University of Pennsylvania [email protected] 19

13 2015 ACS Mini-Symposium Abstract Index 1 2 Atom transfer radical addition (ATRA) catalyzed by Dinuclear ruthenium(I) complexes with N-heterocyclic copper complexes with N,N,N′,N′-tetrakis(2- carbene ligands pyridylmethyl)ethylenediamine (TPEN) ligand Doverspike, Joshua C.; Malosh, Thomas J. Gorse, Erin E; Kaur, Aman; Ribelli, Thomas G.; Jerman, Department of Chemistry Callista C; Pintauer, Tomislav University of Pittsburgh at Johnstown Department of Chemistry and Biochemistry, Duquesne Department of Chemistry, Carnegie Mellon University Dimeric bis(phosphine) ruthenium(I) carbonyl carboxylates are known to catalyze a variety of molecular Atom Transfer Radical Addition reactions have been transformations including: alkene isomerization, traditionally performed using TPMA (tris(2- hydroformylation of alkenes, and hydrogenation of ketones. pyridylmethyl)amine) in methanol as a solvent . Structurally To evaluate their potential for improved activity, a number of similar multidentate ligands TPEN (N,N,N',N'-tetrakis(2- dinuclear ruthenium(I) complexes substituted with an N- pyridylmethyl)ethane-1,2-diamine) and TPEN* (methyl heterocyclic carbene and/or various phosphine ligands have groups in 3,5 and methoxy on 4 positions of the pyridine been prepared and characterized. Treatment of rings) were predicted to catalyze the ATRA more efficiently [Ru(CO)2CH3COO]n with 2-electron donating ligands (L) than previous catalysts. The low halidophilicity of both TPEN yields the derivatives Ru2(µ-CH3COO)2(CO)4L2, where L = and TPEN* in methanol contributed to the previously poor IMes [1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene], P(o- performance of the two ligands, but the values increased tolyl)3, or P(C6F5)3. Treatment of Ru2(µ-CH3COO)2(CO)4L2, when the complexes were examined in the polar aprotic where L = PCy3, or PPh3, with IMes (L′) yields the mixed N- solvent acetone. The Kx of TPEN * increased from 12 ± 2 in heterocyclic carbene/phosphine derivatives Ru2(µ- methanol to 16000 ± 4000 in acetone, with TPEN acting CH3COO)2(CO)4L′L. All complexes have been isolated in similarly. ATRA was then performed with the TPEN and pure form as yellow solids. Reactions of these complexes TPEN* complexes in varying ratios of acetone and methanol with H2, RCHCH2, and RC(O)R will be described, with a variety of alkenes, including methyl acrylate, methyl discussed, and evaluated. methacrylate, 1-octene, styrene, and 1-hexene, with catalyst loadings between 0.002 and 0.0001 compared to alkene.

3 4 Determination and Characterization of G-quadruplex Reduction of Infectious Biofilms on the Native Oxide Structures in Various Messenger Ribonucleic Acids Surface of Titanium Lang, Cara N.1; Evans, Timothy L.1; Mihailescu, M. Rita2 Bruneel, Nicole; Reger, Nina A.; Gawalt, Ellen S. University of Pittsburgh at Johnstown, Department of Duquesne University, Department of Chemistry and Chemistry, Johnstown, PA1 Biochemistry Duquesne University, Department of Chemistry and Biochemistry, Pittsburgh, PA2 Titanium is a key biomedical material used for surgical implants, due to its biocompatibility, high strength, low Guanine-rich sequences of RNA have the ability to fold into a density, corrosion resistance, and non-toxicity to the host. G-quadruplex structure. It has been demonstrated that the However, titanium implants can be infected by presence of a G-quadruplex in the 5’ untranslated region Staphylococcus aureus and Pseudomonas aeruginosa (UTR) of the mRNA has the ability to regulate its translation. biofilms. Biofilms formed by microbial colonies can be Correlations between the structural properties of the G- resistant to antimicrobial treatments. Nitric oxide can be a quadruplex and translation regulation activity still remain biofilm dispersant by inducing nitrosative and oxidative unclear. Therefore, the G-quadruplex structures of each stress on the bacteria, transitioning sessile biofilm cells to mRNA must be characterized. Various techniques such as free swimming planktonic cells, which are more susceptible circular dichroism (CD) spectroscopy, UV spectroscopy to antimicrobial treatments. It is hypothesized that the thermal denaturation, nuclear magnetic resonance (NMR) oxidized surface of titanium can be modified with a self- spectroscopy, and native polyacrylamide gel electrophoresis assembled monolayer containing a functional group that (PAGE) can be used to characterize the structural properties releases nitric oxide under physiological conditions. Diffuse of each G-quadruplex. The purpose of this study was to use Reflectance Infrared Fourier Transform spectroscopy and these biophysical methods to determine whether a G- contact angle measurements were used to analyze the quadruplex structure forms in several neuronal mRNAs, such change in the organization of the monolayer on the surface. as SMNDC1, CHRNA4, LRP1, and Drebrin mRNAs. These substrates were then be modified for nitric oxide release using nitrosoamines.

14 2015 ACS Mini-Symposium Abstract Index 5 6 Biochemical Analysis of G-quadruplex Secondary Optical and Thermal Properties of Lithium-Containing Structures in CDK5R2 mRNA and Their Role in Fragile X Thiostannate with Potential Nonlinear Optical Syndrome Applications Gaetano, Christian; Mihailescu, Mihaela Rita Weiland, Ashley; Brant, Jacilynn A.; Zhang Jian-Han; Department of Chemistry and Biochemistry Aitken, Jennifer A. Duquesne University Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh PA 15282 In silico energy modeling has shown that guanine-rich regions of nucleic acids are capable of forming secondary Diamond-like semiconductors (DLSs) have applications in structures called G-quadruplexes. These structures are many areas such as photovoltaics and nonlinear optics. All subject to unique protein binding and partake in gene diamond-like semiconductors possess a regulation by mediating translation of messenger RNA noncentrosymmetric structure and are potential candidates (mRNA). Such regulation implicates G-quadruplex-containing for second harmonic generation. Properties of these mRNAs as probable components in the pathogenesis of materials such as second-order nonlinearity in the IR can genetic disorders. We have selected a guanine-rich portion be tuned by employing a wide range of predictable of the mouse cyclin-dependent kinase 5 regulatory subunit 2 compositions. The majority of benchmark IR nonlinear (CDK5R2) mRNA 3’ untranslated region for the study of optical (NLO) materials are DLSs. Compounds of the these regulatory G-quadruplexes. Circular dichroism formula Li2MSnS4 (where M = a divalent tetrahedrally spectroscopy, 1H-nuclear magnetic resonance spectroscopy, coordinated metal) were prepared by high-temperature UV spectroscopy, thermal denaturation experiments, and solid-state synthesis under vacuum. One of these polyacrylamide gel electrophoresis (PAGE) were utilized to compounds, Li2CdSnS4, was prepared as a phase-pure confirm the presence of and characterize G-quadruplex material as determined by synchrotron X-ray powder structures in the selected sequence. Additionally, PAGE diffraction and Rietveld refinement. Diffuse reflectance binding assays and fluorescence spectroscopy were used to spectroscopy shows that the compound exhibits a direct illustrate the binding of fragile X mental retardation protein, optical bandgap of 2.718(1) eV and an Urbach energy of which plays a major role in the development of the genetic 0.1994(6) eV. The compound is relatively transparent (75- disorder fragile X syndrome, to CDK5R2 mRNA. 80%) from approximately 0.6 to 25 µm. Differential thermal analysis shows that the compound melts at about 917 °C. The material is a promising candidate for nonlinear optical applications due to the wide bandgap, broad range of optical transparency, relatively high thermal stability, and stability under ambient conditions.

7 8 Cost Effective Dye Sensitized Solar Cells for Renewable Asymmetric Synthesis of Bicyclic Aza-heterocycles Energy Utilizing Chiral Memory Cycloaddition Vivis, Samantha; Senock, Zackery; McCray, Brosnan; Haneen Alshoaibi and Robert B. Lettan II* Hansen, Leah; Mummert, Jordan; and Grimminger, Marsha Chemistry Department Department of Chemistry Chatham University University of Pittsburgh at Johnstown Researchers in synthetic organic chemistry continue to Alternative energy is a growing concern since easily strive in creating robust and reliable synthetic methods accessible, non-renewable resources are diminishing while using simple starting materials to generate complex chiral prices are skyrocketing. Photovoltaic cells convert light into molecules. Memory of chirality is a relatively underexplored electrical energy, which can be stored or used to power strategic technique for the asymmetric synthesis or organic electrical devices. Traditional solar cells have shown high molecules. This research proposal aims to synthesize reliability, but installation costs are prohibitive. Dye bicyclic aza-heterocycles from simple organic molecules as sensitized solar cells (DSSC) are a promising alternative at a starting materials. An intramolecular [4+2] chiral memory fraction of the cost. DSSCs operate by using dyes deposited cyclization process will synthesize the proposed bicyclic on a titanium dioxide film to absorb and transfer electrons. aza-heterocycles. Bicyclic aza-heterocycles are invaluable We are using anthocyanin dyes found naturally in red- molecules with extensive use and application in pigmented fruits as inexpensive materials for fabrication and pharmaceuticals. The primary objective of this synthesis is testing of DSSCs. Cells made from convert up to 0.3% of the to find a convenient method that utilizes simple starting indoor light to power at a cost of about $6 per cell. We plan materials. This paper explores the proposed method for the to improve device stability, data collection, and optimize cell synthesis of aza-heterocycles. construction. We will also explore synthesis and purification of organic pigments from recycled or biomass sources such as cornhusks.

15 2015 ACS Mini-Symposium Abstract Index 9 10 Ab initio dynamics of pseudo-chair carboxyphosphate in Investigation of Macromolecular Crowding on aqueous solution using QM/QM and QM/MM models Ferredoxin and Ferredoxin-NADP+ Reductase Kinetics Jesikiewicz, Elise*; Boesch, Scott; Firestine, Steven M.; Bautista, Danielle; Owen, Svea; Seybert, David W. Evanseck, Jeffrey D. Department of Chemistry and Biochemistry Department of Chemistry and Biochemistry; Center for Duquesne University, Pittsburgh, PA Computational Sciences Duquesne University Macromolecular crowding is the phenomenon in which biomolecular properties are altered due to high Carboxyphosphate is an intermediate in the de novo purine concentrations of macromolecules in an environment. In biosynthesis pathway in microbes but not humans. Inhibiting order to test the effects of macromolecular crowding on this pathway can create novel antibiotics. The biological redox reactions, the proteins ferredoxin (Fdx), decarboxylation mechanism of carboxyphosphate is and ferredoxin-NADP+ reductase (FNR), were purified from unknown. Short half-life in aqueous solution makes Spinacia oleracea. Extraction was implemented through experimental synthesis and study impossible. It is tissue homogenization and sonication followed by a series hypothesized that the carboxyphosphate monoanion will of chromatographic steps. provide a viable decarboxylation pathway but not the dianion. Utilizing NADPH as a reductant, FNR is capable of reducing Four different simulations were carried out investigating the cytochrome c through Fdx, or reducing two ionization states of the pseudo-chair conformations. dichlorophenolindophenol (DCIP) directly. Fdx-dependent TeraChem was used with GPUs and the B3LYP/6-31G(d) cytochrome c reduction was measured using NADPH, functional. Spherical boundary conditions were used with a cytochrome c, Fdx and FNR; whereas Fdx-independent 300 K hold. The first simulation surrounded DCIP reduction activity was measured with NADPH, FNR, carboxyphosphate with 102 QM waters. The second treated and DCIP. To investigate the effects of macromolecular the waters with a molecular mechanics. The third included 11 crowding on electron transfer, the polymers Ficoll, Dextran, QM waters in the first hydration shell. Last, 2 QM waters and ovalbumin were utilized as model crowding species. were used with 58 MM waters. Only the QM/QM monoanion Each polymer tested has shown inhibitory kinetic effects model showed potential for decarboxylation through C-O and we are using steady-state kinetics to explore the bridge bond elongation. specific nature of this inhibition.

11 12 Determination of Optimal Large Scale in vitro Synthesis The importance of being d9: the coordination Conditions for Human Messenger Ribonucleic Acids geometries of 4- and 5-coordinate copper (II). Predicted to Fold into the G quadruplex Structure Caro, Veronica L.; Graham, Aschleigh E.; See, Ronald F. Shaffer, Jacob M.; Lang, Cara N.; Monnie, Christina M.; Department of Chemistry Nathaniel, Mark; Evans, Timothy L. Indiana University of Pennsylvania Department of Chemistry University of Pittsburgh at Johnstown Copper (II) is the only common metal center known in d9 electron configuration. While most metals form highly Certain guanine-rich segments of RNA have been shown to predictable four-coordinate geometries, four-coordinate fold into the G quadruplex structure. Several G quadruplex Cu2+ complexes are found not only in square planar structures located near the beginning of mRNA strands have geometry, but also in orientations intermediate between shown inhibition of translation, and 2334 sequences are square planar and tetrahedral. This behavior is all the more predicted to fold into the G quadruplex structure in this region intriguing because a variety of geometries are found for the 2- 2+ of various human mRNA strands. Each of these unique G same complexes, such as CuCl4 . Additionally, Cu forms, quadruplex structures would possess structural and by far, more five-coordinate complexes than any other thermodynamic stability properties. Despite evidence transition metal. Again, complexes are observed in the two supporting the mRNA G quadruplex structure as a translation established five-coordinate geometries (trigonal bipyramid regulator, correlations between structural properties, and square pyramid), and in many intermediate thermodynamic characteristics, and translation inhibition orientations. For both four- and five-coordinate complexes, activity remain unclear. Each mRNA target must be large- metal-ligand distances are shown to be a function of the scale synthesized and purified in order to perform analyses. coordination sphere, suggesting that both Ligand Field Determination of the large-scale synthesis parameters Stabilization Energy and ligand-ligand repulsion play a role occurs via small-scale syntheses. We investigated the in determining these distances. The results of optimal large-scale synthesis parameters for the computations, concerning the energy differences between synaptotagmin 5 (SYT5), breast cancer anti-estrogen the various geometries, will also be presented. resistance protein 3 (BCAR3), neuromodulin (GAP43), multidrug resistant protein 3 (MRP3), BTB/POZ domain- containing protein (KCTD8), and zinc transporter ZIP1 (SLC39A1) mRNAs.

16 2015 ACS Mini-Symposium Abstract Index 14 13 Internship with ACOME and Crime Lab Oxidation state and ligand binding mode at the active Gobrish, Briana site of myoglobin. Natural and Health Sciences Division Graham, Aschleigh E.; Caro, Veronica L.; Villemain, Jana L.; Seton Hill University See, Ronald F. Department of Chemistry Summary of experiences and opportunities at Allegheny Indiana University of Pennsylvania County Office of the Medical Examiner and crime lab in the Trace analysis section. Includes research on self-heating Myoglobin is an important and well-studied protein which is and spontaneous ignition of nine familiar household oils responsible for oxygen transport in muscles. The active site common in cooking and dryer fires, and the effect of heat of myoglobin contains an iron atom, which is bound to five on molecular structures of oils using gas chromatography nitrogen atoms from the protein, leaving one coordination site and mass spectroscopy. There was no direct effect on the available for binding to a ligand. The usual ligand is an molecules compared to the pure samples when test burning oxygen (O2) molecule, but several other small molecules, occurred from no burning through self-extinguishing, such as CO and NO, can also bind to the iron. This study mimicking cooking fires. addresses two specific questions: 1) is the oxidation state of . the iron atom in O2-bound myoglobin (oxymyoglobin) better described as 2+ or 3+; 2) what structural changes occur in the ligand upon binding to iron? Using rigorous definitions of oxidation state and bond order, results indicate that the iron center is better described as 2+, and that the bound O2 in oxymyoglobin undergoes bond weakening similar to other ligands when they bind to a metal center.

15 16 Nucleation mechanisms of γD-crystallin protein Utilization of Monohalogenated Alkyl Halides in aggregates found in cataracts Copper-Catalyzed Atom Transfer Radical Addition Sarah A. Richards and Ralph A. Wheeler (ATRA) at Elevated Temperature Department of Chemistry and Biochemistry Jansto, Allison and Pintauer, Tomislav Duquesne University Department of Chemistry and Biochemistry Duquesne University Many diseases are a result of protein aggregation, which occurs when the protein is damaged and subsequently Catalyst regeneration in atom transfer radical addition misfolds and aggregates. Cataracts are formed by damage (ATRA) in the presence of a reducing agent has to the proteins that compose the lens of the eye, specifically significantly reduced the amount of catalyst needed, thus γD-crystallin. Molecular dynamics simulations were creating a “greener” process. This method was first applied performed to determine if one of the hydrophobic cores, a in the addition of polyhalogenated alkyl halides to various contiguous section of five or more hydrophobic residues, alkenes, and was extended to the utilization of within γD-crystallin is critical for aggregation. Determining the monohalogenated substrates such as bromoacetonitrile propensity for aggregation of this hydrophobic core might be (BrACN), 2-bromopropionitrile (BrPN), and 2- used to design a drug that can prevent or treat cataracts. The ethylbromophenylacetate (EBrP). The single carbon- aggregation methods exhibited with these small peptides halogen bond formed from the monohalogenated alkyl were also examined and mechanism(s) for aggregation halides is more expedient for further organic between γD-crystallin peptides containing a hydrophobic transformations. After optimizing the reactions in NMR core will be described. tubes, it was found that significantly higher yields were . achieved when performed in pressure tubes with BrACN, BrPN, and EBrP, allowing reaction temperature to exceed the boiling point of the solvent; solvents with lower boiling points may be utilized. ATRA reactions in pressure tubes were generally much faster than those in NMR tubes. The reactions were performed using BrACN, BrPN, and EBrP as the monohalogenated alkyl halides with alkenes such as 1- octene, styrene, methyl acrylate, and methyl methacrylate.

17 2015 ACS Mini-Symposium Abstract Index 17 18 Comparison of Powders and Lifting Techniques of An Investigation of Novel Polymorphic Li2-II-IV-S4 Fingerprints on Smooth and Rough Surfaces Diamond-like Semiconductors utilizing Synchrotron X- Schomer, Chelsie ray Powder Diffraction Natural and Health Sciences Division, Seton Hill University, Devlin, Kasey P.; Daley, Kimberly R.; Moreau, Meghann A.; Greensburg, PA Brant, Jacilynn, A.; Aitken, Jennifer, A. Department of Chemistry and Biochemistry Fingerprinting is a fundamental tool of Forensic Science. This Duquesne University research compared latent print powders on rough versus smooth surfaces and took a look at a product from Spex Diamond-like semiconductors (DLSs) have structures Forensics called Tex-lift. White magnetic powder, green derived from the cubic or hexagonal form of diamond. The magnetic fluorescent powder, and black powder were I2-II-IV-VI4 DLS systems are of particular interest due to compared on eleven surfaces, some smooth and some their tunable nature and possible technological applications rough. Participants placed prints on all of the surfaces and in photovoltaics, spintronics, and non-linear optics. then the surfaces were dusted with each of the powders and Polymorphism may affect important physicochemical lifted with C-lifts. properties. Most Commonly, polymorphic DLS materials For the Tex-lift, a procedure was validated and then the it arise from differing cation ordering in a structure. In was used with white magnetic powder to determine if it would quaternary DLSs, polymorphism may be observed in give better results on textured surfaces versus the powder structures that maintain the same anion packing, but differ and brush technique with a C-lift. in the cation ordering arrangement within the tetrahedral The research concluded that white magnetic powder with a holes. In this work, high-temperature solid-state synthesis in C-lift is the best on rough surfaces and black powder with a a Li2-II-IV-VI4 system led to the discovery of two C-lift is best on smooth surfaces. The Tex-lift works on polymorphs, crystallizing in the Li2CoSiO4 (Pna21) and textures, but not better than the C-lift with a magnetic wurtz-kesterite (Pn) structures. The two polymorphs were powder. analyzed using optical diffuse reflectance UV/Vis/NIR spectroscopy, single crystal X-ray diffraction, and synchrotron X-ray powder diffraction together with Rietveld refinement. The National Science Foundation supports this work under Grant No. DMR-1201729.

19 20 Post-Translational Regulation of Membrane-bound The Investigation of Metals in Various Applesauce Proteins Samples Through Atomic Absorption Spectroscopy Wise, Christopher Angela M. McCarthy* and Demetra A.C. Czegan College of Natural Sciences and Mathematics, Biochemistry Seton Hill University Department of Chemistry, Greensburg, Program Pennsylvania 15601 Indiana University of Pennsylvania Due to the proliferation of heavy metals in the environment Information on the post translational regulation of the and growing awareness of their health impacts, it is of degradation and processing of membrane-bound proteins is interest to determine if food products contain metal lacking, however using fluorescent confocal microscopy to contaminants at levels sufficient for concern. Incidences of follow these processes in the eukaryotic model organism, arsenic, lead and nickel in apple juice samples have been Saccharomyces cerevisiae promises to uncover more recently reported in the literature; to determine if this information. Specifically, by using an IMIC fluorescence contamination extended into other apple products as well, confocal microscope, the in vivo trafficking of GFP-labeled various brands of applesauce were investigated for the maltose permease is observed as it is removed from the presence of metals using Atomic Absorption Spectroscopy membrane by endocytosis, in response to changes in (AAS). The applesauce samples were tested for both carbohydrate sources. By comparing in vivo trafficking metals of concern (lead and chromium) as well as metals patterns in the presence and absence of reagents, such as that pose no health risk at low concentrations (iron, calcium ethanol and the actin polymerization inhibitor, Cytochalasin and potassium) to verify the feasibility of the analytical D, the mechanisms may be further elucidated. To help methods. The applesauce samples were digested in interpret the visual results from microscopic imaging and concentrated nitric and hydrochloric acids and analyzed on screen possible effectors, biochemical assays are conducted a Perkin Elmer 3100 AAS. In the five types of applesauce to measure p-Nitrophenol-α-D-Glucoside (PNP-αG) studied, iron, calcium and potassium were detected; hydrolysis in Saccharomyces cerevisiae grown under however, chromium and lead were not present at detectable corresponding culture conditions. These assays report on levels. the level of maltose permease activity within the cell over a 90-minute period.

18 2015 ACS Mini-Symposium Abstract Index 21 22 Effects of Viscosity and Macromolecular Crowding on Group 13 chiral Lewis acid stereoselective control of the Diffusion-Controlled Rate Constant of Ferredoxin enal Diels-Alder reactions with Ferredoxin NADP+ Reductase Ahmed, Ayan; Kelly, Allison; Vernier, Brandon; Rohde, Sweger, Sarah; Madura, Jeffry Jeffrey J.; Evanseck, Jeffrey D. Department of Chemistry Center for Computational Sciences and Department of Duquesne University Chemistry and Biochemistry Duquesne University and Franciscan University of The rate at which many reactions occur is controlled by the Steubenville ability of one particle to diffuse to another. One such reaction is the protein-protein association between ferredoxin NADP+ Group 13 chiral Lewis acids MCl2OR (M = B, Al, Ga) reductase (FNR) and ferredoxin (Fd), a key mechanism in complexed with substituted enal dieneophiles have been the overall process of photosynthesis. Experiments used in asymmetric Diels-Alder reactions; however, the simulating the intracellular environment often neglect to factors that influence stereochemical control are not yet well include the high concentration of macromolecules within the understood. A “formyl hydrogen bond” between a boron cytosol of the cell. The presence of these macromolecules Lewis acid and the formyl hydrogen of an enal has been causes a crowding effect impacting the rate at which proposed to explain selectivity. New competing interactions reactions occur within the cell. Utilizing the methods of between the enal vinylic alpha- and beta-hydrogens and the Brownian dynamics, simulations were run to calculate the Group 13 chiral Lewis acids have been investigated. reaction rate of the ferredoxin NADP+reductase enzyme Second-order Moller-Plesset theory and M06-2X density binding with a corresponding ferredoxin molecule under functional with Dunning basis sets have been used to study standard conditions as well as conditions including these three bidentate complexes. It is found that the macromolecular crowding. The resulting data indicated that previously unconsidered, alpha-hydrogen effectively the diffusion-controlled rate of the reaction was reduced competes for complexation in the chiral Lewis acid when introduced to crowded conditions. The results indicate complexes. Evidence is found for competition between the a greater understanding of the interactions occurring using a formyl and alpha-hydrogen interactions in aluminum and realistic model of the intracellular environment. gallium chiral Lewis acid complexes, but not with boron. These two organizing elements explain experimental selectivity reported by Koga.

23 24 Intramolecular Charge-Assisted Hydrogen Bond Distinguishing the protonation states of the histidine Strength in Pseudo-Chair Carboxyphosphate ligands of the Rieske iron- sulfur cluster by 15N isotopic Sarah E. Kochanek, Traci M. Clymer, Steven M. Firestine, substitution and vibrational frequency shifts and Jeffrey D. Evanseck Jagger, Benjamin R., Koval, Ashlyn M.. and Wheeler, Ralph A. Dianionic and monoanionic carboxyphosphate is predicted to Department of Chemistry and Biochemistry exist in a novel conformation known as pseudo-chair, Duquesne University stabilized by an intramolecular charge-assisted hydrogen bond (CAHB). Separate additive and subtractive correction The Rieske [2Fe-2S] clusters of mitochondrial cytochrome schemes to the open-closed method are used to estimate the bc1 and its chloroplast equivalent, cytochrome b6f, are strength of the CAHB. Truhlar's Minnesota M06-2X essential for electron transfer, acting as the first electron functional with Dunning's aug-cc-pVTZ basis set is utilized for acceptor in a modified Q cycle. The protonation states of all computations. The CHARMM force field has been used to the cluster’s His ligands determine its ability to accept a approximate the Pauli repulsive terms in the closed and open proton and possibly an electron via a hydrogen bond to the forms of carboxyphosphate. From our additive correction electron carrier, ubiquinol. Experimental determination of scheme, differential Pauli repulsion contributions between the protonation states of the His ligands by NMR the pseudo-chair and open conformations of spectroscopy is difficult due to the close proximity of the two carboxyphosphate are found to be significant in determining paramagnetic iron atoms of the cluster. Therefore, this work the CAHB strength. Knowledge of an accurate CAHB reports density functional calculations and proposes that strength provides deeper insight into the pseudo-chair difference vibrational spectroscopy with 15N isotopic conformation of carboxyphosphate, offers a partial substitution may be used to assign the protonation states of explanation of its instability in the aq. phase, and leads to an the His ligands of the Rieske [2Fe-2S] complex. improved mechanistic understanding regarding how carboxyphosphate is stabilized and used in ATP-dependent carboxylases.

19 2015 ACS Mini-Symposium Abstract Index 25 27 The Messenger RNA p250GAP G-Quadruplex Secondary Adhesion Analysis of Human Erythroleukemia Cells to Structure Biophysical Classification and RGG box Human Lung Fibroblasts Domain/ISO1 Interaction Mols, Jessica L., Dr. Paul J. Birckbichler Williams, Allison; Stefanovic, Snezana; Mihailescu, M. Rita Chemistry Department Department of Chemistry and Biochemistry Slippery Rock University Duquesne Universitya Study of attachment between human erythroleukemia (HEL) The gene that encodes for p250GAP is found on cells and human lung fibroblasts (WI-38) mimics simulated chromosome 11 and encodes a protein belonging to the in vivo environment for the study of metastasis. Exposing RhoGAP family which affects the plasticity of neurons, adherent fibroblasts cells to cancer cells growing in specifically in the brain. It is hypothesized that mRNA suspension provides an excellent metastatic model for p250GAP interacts with the Fragile X Mental Retardation adhesion of transformed cells to normal tissues. Ninety Protein (FMRP), a protein linked to Fragile X Syndrome, the percent of HEL cells adhered to WI-38 cells, when the two most common form of inherited mental impairment. FMRP cell types were mixed. Seventy percent of HEL cells added uses its arginine-glycine-glycine (RGG) box to interact within to a fibronectin-coated plate adhered to the plate its mRNA targets, named a G-quadruplex. To confirm first suggesting that fibronectin, an extracellular matrix protein, the presence of a G-quadruplex in p250GAP mRNA, a series might play a role in adhesion of the two cell types. Current of biophysical techniques were employed including 1H NMR studies are investigating the nature of the binding. One spectroscopy, CD spectroscopy, UV spectroscopy, and candidate is the isopeptide, €-(γ-glutamyl)lysine, catalyzed native PAGE gels. Following these experiments, by tissue transglutaminase. WI-38 cells are rich in the fluorescence spectroscopy and native PAGE were used to enzyme and fibronectin is a substrate for the enzyme. quantify the interactions of p250GAP mRNA G-quadruplex Monoclonal antibodies to tissue transglutaminase, the with the RGG box domain and full length FMRP. isopeptide and a4β1 integrin will be studied to investigate the involvement of these antigens in attachment. This research was supported by funds provided by the Department of Chemistry and RFP Research Grants, Slippery Rock University.

26 28 Evaluation of Heteroarotinoids for Biological Response in Human Erythroluekemia Cells Highland, Jaclyn Chemistry Slippery Rock University

Retinoids, a class of molecules related to Vitamin A, have demonstrated various medicinal applications. All-trans retinoic acid has shown anticancer activity; however, its usefulness in chemotherapeutic applications is limited by its toxicity. Heteroarotinoids—synthetic retinoids with one or more heteroatom—are structural analogues of retinoic acid. Heteroarotinoids exhibit lowered toxicity while maintaining significant biological activity. In this study, human erythroleukemia cells (K562 and HEL) were evaluated for biological response following exposure to retinoic acid and heteroarotinoids. Camptothecin was included as a positive control for the induction of apoptosis. Cell cultures were evaluated for growth, viability, and prevalence of apoptosis using flow cytometry. Treatment with heteroarotinoids resulted in growth inhibition and induction of apoptosis, similar to the effects of retinoic acid, but with lowered toxicity.

20 2015 ACS Mini-Symposium Abstract Index 29 31 Electronic Genome Mapping of Halogenobenzenes BIOPHYSICAL ANALYSIS OF CDK5R2 DNA Baer, Ryan SECONDARY STRUCTURES Department of Chemistry Kathryn J. Bandi, Brett DeMarco, Mihaela-Rita Mihailescu Penn State Fayette Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA The rate at which many reactions occur is controlled by the ability of one particle to diffuse to another. One such reaction In addition to the classic DNA double helix structure, certain is the protein-protein association between ferredoxin NADP+ guanine rich DNA sequences can form secondary reductase (FNR) and ferredoxin (Fd), a key mechanism in structures known as G-quadruplexes, and their the overall process of photosynthesis. Experiments complementary cytosine rich strand can form i-motif simulating the intracellular environment often neglect to structures. G-quadruplexes can be formed by the stacking include the high concentration of macromolecules within the of multiple G-quartets which are formed by the Hoogsteen cytosol of the cell. The presence of these macromolecules base pairing of several guanine residues. The i-motif causes a crowding effect impacting the rate at which structures are formed by the stacking of cytosine- cytosine reactions occur within the cell. Utilizing the methods of base pairs and are stabilized at low pH values. The Brownian dynamics, simulations were run to calculate the CDK5R2 DNA contains multiple guanine and cytosine base reaction rate of the ferredoxin NADP+reductase enzyme pairs and has the capability to form both a G-quadruplex binding with a corresponding ferredoxin molecule under and an i-motif secondary structure. These secondary standard conditions as well as conditions including structures are important because being aware of the macromolecular crowding. The resulting data indicated that structure of the DNA allows a person to understand the the diffusion-controlled rate of the reaction was reduced function of the protein within the cell. To characterize the when introduced to crowded conditions. The results indicate different secondary structures of these DNA strands, many a greater understanding of the interactions occurring using a biophysical techniques were utilized including circular realistic model of the intracellular environment. dichroism spectroscopy, 1H nuclear magnetic resonance spectroscopy, UV spectroscopy, and native polyacrylamide gel electrophoresis (PAGE).

21 Notes

20 Notes