Graduate Brochure 2014 Draft.Pub

THETHE UNIVERSITYUNIVERSITY OFOF MISSOURIMISSOURI——ST.ST. LOUISLOUIS 315 Benton Hall (MC 27) One University Blvd. St. Louis, MO 63121-4400 http://www.umsl.edu/chemistry/

DepartmentDepartment ofof ChemistryChemistry && BiochemistryBiochemistry

Phone: (314) 516-5311 Fax: (314) 516-5342 ST.LOUIS

The St. Louis metropolitan region, located around the ence Center has many educational interactive exhibits confluence of the Missouri and Mississippi Rivers, has including an Omnimax theatre. And finally the St. Louis evolved through the centuries from the homes of ancient Zoo, home to more than 18,000 exotic animals, many of Native American civilizations to major fur trading cen- them rare and endangered, and set in the rolling hills, ter to the "Gateway to the West," marked by lasting lakes and glades of Forest Park, is a great place to visit. French, Spanish and African influences. Today the area is a town with hospitable people rooted in a myriad of Activities and attractions are many, and St. Louis has regional, ethnic, and cultural traditions reflective of our a great variety of night life choices. Blues clubs and complex world, well supported by easy access to parks, restaurants are tucked away in the red brick buildings of educational centers, sports venues, museums, and histor- the historic Soulard neighborhood, while Dixieland and ic sites. blues dinner cruises are available through the port of St. Louis. Clubs and restaurants are alive until early morn- Great ethnic and classic neighborhoods characterize ing hours in the converted warehouses of the Landing, the region. A cross-section of the area can provide ex- north of the Arch, and along the newly-developed "loft" amples of wonderful Victorian architecture, museum, neighborhood of Washington Avenue. Visitors to The gallery, and arts districts, farmers' markets, antique Loop in University City can enjoy a game of darts be- shops, boutiques and classic coffee houses, jazz clubs, tween eating appetizers and dinner. The Fox Theatre, great restaurants, and amazing ethnic foods, a world across the street from Powell Hall, the home of the Saint class botanical garden, and old warehouse buildings Louis Symphony Orchestra, hosts traveling Broadway converted into lofts, shops and restaurants. musicals. There are special concerts at Riverport, the Peabody Opera House, the Pageant, Chaifetz Arena and, Forest Park, the urban St. Louis facility that is much at Webster University, the summer season of Opera larger than New York's Central Park, is home to bike Theater, presented in English. Finally our own Touhill trails, tennis courts, and golf courses. The Missouri His- Performing Arts Center is the major newcomer to the torical Society is a place to learn about interesting St. cultural scene in St. Louis. Louis history including the Lewis and Clark Expedition. The St. Louis Art Museum, designed by Cass Gilbert for Sports of all sorts are an obsession in St. Louis. Cardi- the 1904 World's Fair, has a collection of art which is nal baseball is a religion to many, the hockey Blues, and representative of the best of world art, its strengths being the NFL's Rams have large numbers of loyal and enthu- in Pre-Columbian and German art. The St. Louis Sci- siastic fans, and indeed all sports are available in town. THE UNIVERSITY

The University of Missouri-St. Louis is one of four campuses that constitute the University of Missouri. Estab- lished in Columbia in 1839 on the ideals of Thomas Jefferson, the University of Missouri became a land-grant institution upon passage of the Morrill Act by Congress in 1862.

The university remained a single-campus institution until 1870, when the Rolla campus was opened as the Mis- souri School of Mines and Metallurgy. In the 1960s a movement began across the country toward creation of public universities located within metropolitan centers. That movement marked the most significant change in higher education in the twentieth century, and the University of Missouri-St. Louis is a product of that educational development. Two campuses were added in 1963. The private University of Kansas City became the university's Kansas City campus, and an entirely new campus was started in St. Louis.

The notion of a major public institution serving the St. Louis area evolved from a dream to a solid reality, which today exceeds the expectations of those who created it. Since the doors of the old Administration Building opened more than 50 years ago, UM-St. Louis has become the largest university serving St. Louisans and the third largest university in the state and the largest in the St. Louis metropolitan area. The university has grown from 30 faculty in 1963 to more than 1300 faculty members and more than 1,000 staff members, committed to the future of the St. Louis area through teaching, research, service and economic development.

One of the keys to this university's development as an outstanding institution has been the careful selection of faculty over the years. UM-St. Louis has attracted some of the top authorities in many fields. More than 90 percent of the full-time regular faculty members hold doctoral degrees, a figure that far exceeds the national average. These professionals develop new theories and new procedures, and in so doing attract millions of dollars each year in research funding.

Student enrollment, on and off-campus, has grown from 600 in 1963 to more than 17,000 in 2014. The numbers have changed, but not the spirit. Faculty and students are still most concerned with the education of new talent, which is the basis for the future social, intellectual, and economic health of Missouri's largest metropolitan area. From its beginning on what was once the site of a country club with a single building, UM-St. Louis has grown to a large modern campus of more than 320 acres with more than 60 buildings used to support academic and other University activities. In addition major construction projects, including a Wellness Center, a Science Learning Center among others, are underway on campus.

The curriculum has grown to include 54 undergraduate programs, 37 master's programs, seven pre-professional programs, 2 education specialists programs, 15 doctoral programs, and the only professional degree in optometry in Missouri. Programs address the particular needs of older students returning to school; of students pursuing pre- architecture, pre-law, pre-medicine, pre-pharmacy, pre-engineering, or pre-journalism courses, and of students interested in urban careers. THE DEPARTMENT

THE CHEMISTRY & BIOCHEMISTRY DEPARTMENT was the first at the University to establish a Ph.D. program. That was in 1971-2, and in 1974 the M.S. program began. The first Ph.D. in chemistry was awarded in 1977 and in 2007 the department celebrated the 30th anniversary of the first MS and PhD graduates and the 40th anniversary of the first BS graduates. Through 2014 we have graduated 1,682 degree recipients including approximately 1,091 baccalaureates, 419 masters and 172 doctoral graduates. Included in the latter are graduates from the recently developed Biochemistry and Biotechnology Program run jointly with the Department of Biology. To date the program has generated almost 214 BS and 72 MS graduates. The Department of Chemistry & Biochemistry is housed in Benton Hall, the Research Building, and the William L Clay Center for Nanoscience, all within the Sci- ence Complex. In 2014 ground was broken for the Science Learning Center, a new 75,00 square foot building; part of the $32 million renovation of Benton and Stadler Hall, which will contain new teaching laboratories, some research and general-use space.

There are currently 18 faculty members, offering research opportunities in organic chemistry, inorganic chemistry, physical & analytical chemistry and biochemistry, and several active emeritus, research and adjunct professors. Recent faculty recruitment efforts have changed the demographics of the department and thus there are new opportunities in research for potential graduate students. There are more then 60 graduate students and postdoctoral fellows augmented by several undergraduate students involved in a broad range of research efforts.

The Chemistry & Biochemistry Department has developed a program that makes research and teaching excel- lence its top priorities. Papers and publications documenting departmental research are frequently presented at conferences and symposia and published in scientific journals throughout the world. The faculty serve on national and international committees and editorial boards. Several faculty members have written introductory textbooks and advanced specialized monographs and reviews. Advanced undergraduate and graduate classes are relatively small, allowing for considerable interaction between faculty and students. Undergraduate research is strongly advised for majors providing an opportunity for graduate students and postdoctoral fellows to assist in mentoring undergraduates thereby providing them all with valuable experience. GRADUATE STUDY

THE DEPARTMENT OF CHEMISTRY & BIOCHEMISTRY offers programs of study leading to the Ph.D. and M.S. degrees including a non-thesis M.S. for persons working full time. The Ph.D. degree is offered in the areas of Biological, Inorganic, Organic and Physical & Analytical Chemistry, and research on topics of current interest in these areas is being carried out by faculty, postdoctoral associates, graduate students and undergraduates. In addition, opportunities for research in interdisciplinary and materials related areas exist in a number of research groups. Incoming graduate students are free to undertake research toward an advanced degree with any faculty member of their choosing, depending on space and availability, and are encouraged to select their advisor and start research within their first year. Graduate courses covering more than two dozen subject areas are regular- ly offered by the Chemistry faculty. For persons working full time, there is convenient scheduling of courses in the late afternoon and early evening hours. A complete listing of Chemistry offerings is found in the University of Missouri-St. Louis Bulletin and online at https://apps.umsl.edu/webapps/courseschedules/search_basic.cfm. . Fellowships, teaching or research assistantships are held by almost all full-time PhD students. Stipends for assistantships are competitive. Non-resident tuition fees are waived for all students on assistantships, although resident incidental fees must be paid. Research fellowships are also awarded on a competitive basis, and research assistantships are available, funded by research grants awarded to individual faculty members. Faculty Research Interests

Biological and Inorganic Chemistry: Research involving the interface of chemistry and biology, including metabolism, "chemical genomics" and the design of antiviral and anticancer agents. Chemical synthesis and biochemical testing of sequence-specific DNA binding molecules designed to control gene expression. [email protected]. 314-516-7352 James K. Bashkin

Analytical, Computational and Biophysical Chemistry. Structure, reactivity and chemistry of biologically- and industrially-important chemicals; mass spectrometry and mass spectrometry-related techniques; application of information gained in fundamental studies to practical problems. [email protected]. 314-516-5314

Benjamin Bythell

Organic, Organometallic. Investigation of transition metal based catalysts systems; development of environmentally friendly iron based catalyst systems; new catalytic methods to activate propargylic alcohols; Green Chemistry. [email protected] . 314-516-5340

Eike Bauer

Supramolecular and Materials Chemistry: Synthesis of inorganic and organic molecular building blocks and their use in solid state synthesis; catalysis and molecular transport in porous solids; synthesis of clusters and nanoparticles using crystal engineering methods; chiral separations and magnetic solids. [email protected] . 314-516-4383 .Alicia M. Beatty

Inorganic and Organometallic Chemistry; NMR Spectroscopy. Synthesis and characterization of compounds containing transition metal to heavier group 14 element bonds. Cluster complexes containing Si, Ge, Sn and transition metals, NMR spectroscopy of organometallic and inorganic complexes. [email protected]. 314-516-6436

.Janet Braddock-Wilking

Organic Chemistry. Synthesis of chiral organo-deuterium compounds, thermal reactions of hydrocarbons, stereochemistry, heats of sublimation, isotope effects,; physical properties; measurement and estimation. [email protected]. 314-516-5377 James S. Chickos

Bioorganic Chemistry; Organic Chemistry. Bioorganic chemistry, kinetics, mechanisms and structure-function relationships of organic reactions, particularly of biological processes; enzyme mechanisms, mimics and catalysis; cyclodextrin and modified cyclodextrin chemistry. [email protected]. 314-516-5324

Valerian T. D’Souza.

Organic Chemistry; Carbohydrate Chemistry. Novel synthetic methods, 1,2-cis- glycosylation, oligosaccharide synthesis, synthetic vaccines, synthetic glycopolymers and glycodendrimers, sialic acid containing glycoconjugates, chemo-enzymatic synthesis, solid phase chemistry, combinatorial chemistry. [email protected]. 314-516-7995

Alexei V. Demchenko

Biochemistry. Enzyme structure-function relationships; inhibition of enzymatic drug targets; nucleic acid-ligand interactions . [email protected]. 314-516-4392

Cynthia Dupureur

Organic, Biological Chemistry, Supramolecular. Chemical biology, synthesis of novel compounds that can serve as supramolecular receptors , cation channels in phospholipid bilayers or as mediators of anion transport through membranes. Exami- nation of weak intermolecular ("supramolecular") forces that pervade chemical and biological phenomena. [email protected]. 314-516—5321

George W. Gokel

Bioinorganic Chemistry; Inorganic Chemistry. Complexation equilibrium with proteins and low molecular weight ligands. Metal ion exchange kinetics with serum transferrin. Linear free-energy relationships in coordination chemistry. [email protected]. 314-516-5331

Wesley R. Harris.

Inorganic, Organometallic, and Materials Science: Synthesis and characterization of polymerization catalysts, magnetic and photo-responsive materials, electron transfer, and molecule-based devices. [email protected]. 314-516-4382

Stephen M. Holmes Biochemistry. Peptide/protein assembly mechanisms, macromolecular characterization, quantitative light scattering, atomic force and electron microscopy, cellular studies of inflammatory processes induced by protein assemblies. [email protected] . 314-516-7345

Michael R. Nichols

Materials Science; Physical Chemistry. Gaseous species important in quantitative meas-

urements obtained using plasma-assisted chemical vapor deposition processes studied

by intracavity laser spectroscopy; techniques in intracavity laser spectroscopy; laborato-

ry spectra of species important in planetary atmospheres.

[email protected]. 314-516-5717

James J. O’Brien.

Organic Chemistry. Organic synthesis; new synthetic methods; chiral phosphonate and

phosphonamides in asymmetric synthesis; asymmetric synthesis of heterocycles; total

synthesis of marine natural products.

[email protected]. 314-516-5437

Christopher D. Spilling.

Physical Chemistry. Surface modification of nanomaterials for life science applications; interactions in model membrane systems; supramolecular ordering in thin films and monolayers. [email protected]. 314-516-5346

Keith J. Stine.

Computational Biochemistry. Development and application of computational methods for studying biomolecular structure, dynamics, and function. Computer-aided drug design. Protein kinases and phospatases. [email protected] . 314-516-5218

Chung F. Wong.

Materials Science. Physical Chemistry. Nonlinear optics, solid-liquid interfacial chemistry; molecular electronics and optical switch storage devices. . [email protected] 314-516-5328

Zhi Xu. Emeritus, Founders' and Research Faculty

Inorganic Chemistry. Synthesis. Structure and chemistry of borane and metallaborane cage compounds, transition metal borane complexes, organometallic chemistry. [email protected]. 314-516-5334

Lawrence Barton.

Inorganic Chemistry; Organometallics. Synthesis and characterization of organometallic compounds containing elements form Group IV, with emphasis on catalyzed formation of polysilane oligomers and polymers from hydrosilanes. [email protected]. 314-516-5360 Joyce Y. Corey.

Chemical Education; Physical Chemistry. Chemical education; structure of self- organizing flames; electrically perturbed flames; computer simulations of molecular energy transfer; chaos and fractals in chemistry. [email protected]. 314-516-5344 Harold H. Harris

NMR spectroscopy The use of NMR for generating three-dimensional structural and dynamical information on biological macromolecules and organometallic complexes. Collaboration with scientists in chemistry, biochemistry, biology, medicine, physics and materials science. Development of techniques and implementation of new NMR experiments. [email protected] . 314-516-5330 Rensheng Luo

X-ray Crystallography. Structural chemistry; X-ray crystallography; crystallographic databases; organometallic chemistry. [email protected]. 314-516-5333

Nigam. P. Rath.

Organic chemistry: The chemistry of secondary plant metabolites, in particular ter-

penes and alkaloids. Isolation and identification of novel biologically significant com-

pounds and biosynthesis and chemical ecology of plant materials. Mass spectrometry.

[email protected]. 314-516-5337

Rudolph E. K. Winter THE FACULTY

signed potential antiviral agents that that eliminated toxic waste associated successfully eliminate HPV16 DNA with traditional processes. from human cells in culture, with pseudo JAMES K. BASHKIN -IC50 values as low as 27 nM. Pyrrole- Selected Publications imidazole polyamides are used to target Professor Bashkin, B.A. California- viral DNA sites such as the one shown ″DNA binding polyamides and the im- Irvine, D.Phil. Oxford, England, NIH portance of DNA recognition in their use postdoc at Harvard, was with Monsanto, below, bound to a DNA target. We have expanded our work to HPV18; all drug as gene-specific and antiviral agents″, K. Washington University in St. Louis, and J. Koeller, G. D. Harris, K. Aston, G. He, discovery and development have been again Monsanto (later Pharmacia and C. H. Castaneda, M. A. Thornton, T. G. Pfizer) prior to joining the faculty at collaborations with Dr. Chris Fisher of Edwards, S. Wang, R. Nanjunda, D. W. UMSL in 1999. He established a re- NanoVir LLC. Studies of the biophysics Wilson, C. Fisher and J. K. Bashkin, search program here in 2003 and started of polyamides interacting with HPV Med. Chem. 2014, 4, 338 the biotech company NanoVir, LLC DNA have been collaborations with Dr. with Chris Fisher, and in 2012 was ap- Cynthia Dupureur of this department. “Binding studies of a large antiviral pol- pointed Professor of Chemistry and Bio- yamide to a natural HPV sequence”’ G. chemistry. All of our antiviral polyamides have He, E. Vasilieva, G. D. Harris, K. J. Ko-

been rather large molecules. To study eller, J. K. Bashkin and C. M. Dupureur, Research Interests the biophysics of smaller polyamides, Biochimie 2014, 102, 83.

both to help understand the larger poly- My group’s research has recently been amides and to design better leads for directed to the interface of chemistry and ″Modulation of DNA-polyamide interac- other human diseases, we have collabo- biology, in areas such as "chemical ge- tion by β-alanine substitutions: a study of rated with biophysicist W. David Wilson nomics," the design of antiviral and anti- positional effects on binding affinity, of Georgia State University for several cancer agents and Green Chemistry. kinetics and thermodynamics″, S. Wang, years. Much of this work involves the chemical K. Aston, K. J. Koeller, D. G. Harris, N. synthesis and biochemical testing of P. Rath J. K. Bashkin and W. D. Wilson, Earlier work was concerned with the sequence-specific DNA binding mole- Org. & Biomol. Chem. 2014, 12, 7523. design of ribozymes mimics: molecules cules designed to control gene expres- capable of sequence specific cleavage of sion. Our main goals are the invention of "Differential thermodynamic signatures RNA by the natural transesterification/ new chemical methods to treat and diag- for DNA minor groove binding with hydrolysis process. Applications include nose diseases and the invention of new changes in salt concentration and temper- catalytic antisense agents that destroy chemical reactions to eliminate toxic ature," S. Wang, A. Kumar, K. Aston, B. target messenger RNA without requiring Nguyen, J. K. Bashkin, D. W. Boykin waste and other undesirable features of RNase H activation. We reported the first and D. W. Wilson, Chem. Commun. traditional chemistry. ribozymes mimic. 2013, 8543.

Recently, we have worked toward pre- In addition to this biological chemistry, I "DNA Damage Repair Genes Control- vention of cervical cancer. Most cervical have maintained a strong interest in envi- ling Human Papillomavirus (HPV) Epi- cancer is caused by certain "high-risk" ronmentally-benign organic chemistry, some Levels under Conditions of Stabil- forms of Human Papillomavirus (HPV), known as Green Chemistry. This work ity and Extreme Instability," T. G. Ed- primarily HPV16 and 18. We have de- involved developing organic reactions wards, T. J. Vidmar, K. Koeller, J. K. Bashkin and C. Fisher, PLoS One, 2013, 8, e75446. NNNNAAGATTATTA TTATTAAGTATAAAA AGAACAAT   IPP PPP R IPP PPP R TaPPPPPP TaPPPPPP "Mapping small DNA ligand hydroxyl NNNNTTCTAATAAT AATAATTCATATTTTT CTTGTTA radical footprinting and affinity cleavage products for capillary electrophoresis," Code for building blocks: I = imdazole, P = pyrrole, Ta = triamine,  =betaalanine, G. He, E. Vasilieva, J. K. Bashkin and C. and the hairpin turn is indicated by:R , where R= H or NH2. M. Dupureur, Analytical Biochem. 2013, 439, 99. THE FACULTY phinooxazoline ligands. As a new class "Ruthenium complexes of the general of ligands, thio derivatives of phospho- formula [RuCl2(PHOX) 2] and their cata- ramidites were synthesized. These lig- lytic activity in the Mukaiyama aldol ands were subsequently converted to a reaction," N. Curvey, A. K. Widaman, N. variety of ruthenium, rhodium, iridium P. Rath and E. B. Bauer, Tetrahedron and iron complexes. The impact of the Lett. 2014, 55, 3033. ligand structure on the physical and chemical properties of its respective "Etherification reactions of propargylic metal complexes was investigated. alcohols catalyzed by a cationic rutheni-

um allenylidene complex," D. F. Alkha- The Bauer group has shown that phos- leeli, K. J. Baum, J. M Rabus and E. B. phoramidite containing half sandwich Bauer, Catalysis Comm. 2014, 47, 45. complexes of ruthenium are catalytically active in the formation of -oxo esters "Polydentate pyridyl ligands and the EIKE BAUER from propargylic alcohols and carboxylic acids (see graphics). The ligand structure catalytic activity of their iron(II) com- has a profound impact on the catalytic plexes in oxidation reactions utilizing Professor Bauer received his Vordiplom activity of the corresponding metal com- peroxides as the oxidants," M. Lenze, S. (B.S. degree) 1995, University of Erlan- plex. Structurally related chiral at metal Sedinkin and E. B. Bauer, J. Mol. Catal. gen-Nuremberg (Germany); ruthenium complexes have exhibited A: Chem. 2013, 373, 161 Hauptdiplom (Thesis M.S. degree) 1999, catalytic activity in the Mukaiyama aldol University of Erlangen-Nuremberg; reaction. Ph.D., 2003, University of Erlangen- "Iron(III) a-Aminopyridine Complexes and their Catalytic Activity in Oxidation Nuremberg. He did a postdoc 2004-2005 Allenylidene complexes are cumulene- at the University of California – River- Reactions: A comparative Study of Ac- type compounds, which are readily activity and Ligand Decomposition," M. side and was Visiting Assistant Professor cessible from propargylic alcohols and 2005-2006 at Illinois Wesleyan Universi- Lenze, E. T. Martin, N. P. Rath and E. B. appropriate precursor metal complexes. Bauer, ChemPlusChem 2013, 78, 101. ty prior to joining the Chemistry Depart- The allenylidene complexes are of inter- ment in the fall 2006. . est as possible intermediate in catalytic propargylic substitution reactions. Dr. "Transition-metal-catalyzed functionali- Research Interests Bauer has also demonstrated a route to zation of propargylic alcohols and their chiral at metal allenylidene complexes, derivatives," E. B. Bauer, Synthesis Dr. Bauer’s research interests are in the which were obtained from corresponding 2012, 44, 1131 P. Shejwalkar, N. P. Rath area of Organic and Organometallic precursors with chirality transfer. Cata- and E. B. Bauer, Chemistry. Organometallic chemistry is lytic investigations are currently under- the study of compounds having metal- way. carbon bonds. Organometallic com- ″Chiral-at-metal complexes and their pounds often have unique geometries and Iron is a cheap and non-toxic alternative catalytic applications in organic synthe- exhibit reactivities as a result of the elec- to well-established, catalytically active sis," E. B. Bauer, Chem. Soc. Rev. 2012, tronic properties of the metal. Organo- transition metals. The Bauer group has 41, 3153. metallic compounds are important in demonstrated for the first time that phos- catalysis, medicine, and the construction phinooxazoline complexes of iron are "New five-coordinate Ru(II) phospho- of molecular scale devices (nanoscience). catalytically active in the oxidation of ramidite complexes and their catalytic benzylic methylene groups to ketones activity in propargylic amination reac- Phopshoramidite and phosphinooxazo- utilizing t-BuOOH as the oxidant. tions", A. K. Widaman, N. P. Rath and line ligands have recently attracted con- E. B. Bauer, New J. Chem. 2011, 35, siderable interest as ligands for a variety Selected Publications 2427 of transition metal catalyzed organic transformations. These ligands are easy ″New bis(imino)pyridine complexes of "New iron(II) a-iminopyridine complex- to synthesize and can be sterically and iron(II) and iron(III), and their catalytic- es and their catalytic activity in the oxi- electronically modified at several posi- activity in the Mukaiyama aldol reac- dation of activated methylene groups and tions in their molecular framework. tion″, P. Shejwalkar, N. P. Rath and E. Dr. Bauer designed and synthesized sev- secondary alcohols to ketones", P. B. Bauer, Synthesis, 2014, 46, 57 eral novel, electronically and sterically Shejwalkar, N. P. Rath and E. B. Bauer, fine-tuned phosphoramidite and phos- Dalton Trans. 2011, 7617.

"Synthesis and Structural Characteriza- tion of a Series of New Chiral-at-Metal Ruthenium Allenylidene Complexes", S. Costin, A. K. Widaman, N. P. Rath and E. B. Bauer, Eur. J. Inorg. Chem. 2011, THE FACULTY Cowin and A. M. Beatty, Acta Crystal- logr. E,2010, 66, o1777.

"Synthesis and Control of Single Layer and Polar 2-D Layered Architectures in a Series of Organic Layered Solids", O. Ugono, N. P. Rath and A. M. Beatty, Cryst, Growth & Design 2009, 9, 4595.

"Guest Inclusion and Structural Dynam- ics in 2-D Hydrogen-Bonded Metal- Organic Frameworks" C-L. Chen and A. ALICIA M. BEATTY M. Beatty, J. Am. Chem. Soc. 2008, 130, 17222

Professor Beatty received her B.S. de- "Reverse engineering: toward 0-D cad- gree from UM-St. Louis in 1989 and a Why crystalline solids? It is important mium halide clusters" C. E. Costin- Ph.D. from Washington University in St. to note that crystalline solids can, in Hogan, C-L. Chen, E. Hughes, A. Louis, in 1994. She held positions as a some cases, be uniquely useful materials. Pickett, R. Valencia, N. P. Rath, and A. director of X-ray diffraction facility at By definition, single crystals are ordered, M. Beatty, Cryst. Eng. Comm., 2008, 10, Washington University, Research Asso- which means that structure-function (e.g. 1910 ciate and Senior Research Scientist at electronic or magnetic behavior) rela-

Kansas State University, and Research tionships can be determined by measur- "From Crystal Engineering to Cluster Associate Professor at the University of ing the effect of systematic changes in Engineering: How to Transform Cadmi- Notre Dame. She joined the faculty at the components of the crystal. In addi- um Chloride from 2-D to 0-D," C-L. Mississippi State University in 2003 and tion, channels or cavities organized in Chen and A. M. Beatty, Chem. Com- returned to UM-St. Louis in 2008. crystalline solids have equivalent envi- mun., 2007, 76. ronments, therefore the relative orienta-

tions of guest ions, molecules, or reac- Research Interests "Metal-Containing Dicarboxylic Acids tants are also constant, which is essential as Building Blocks for Lamellar Inorgan- The goal of our research is to create new, for: 1) uniform signaling in chemical ic-Organic Hybrid Networks," A. M. useful solid or polymeric materials sensors, 2) asymmetric catalysis, 3) ste- Beatty, B. A. Helfrich, G. A. Hogan and through use of organic, inorganic and reochemically controlled solid state reac- B. A. Reed, Crys. Growth Des. 2006, 6, supramolecular synthesis especially us- tivity. 122. ing techniques developed through crystal engineering. These new materials will Selected Publications "Open-framework coordination complex- provide a foundation for systematic es from hydrogen-bonded networks: structure-property studies, initially focus- ″Solid phase microextraction (SPME) toward host/guest complexes," A. M. ing on: electroactive polymers, catalysis, combined with TGA as a technique for Beatty, Coord. Chem. Rev. 2003, 246, chiral separations, magnetic solids. Pro- guest analysis in crystal engineering,″ M. 131. jects will utilize common synthetic J. Fischer and A. M. Beatty, routes and methods of characterization in CrystEngComm, 2014, 7313 "Do polymorphic compounds make good solution and the solid state. cocrystallizing agents? A structural case

Synthesis of some aminopicolinic acids," study that demonstrates the importance We have demonstrated that, despite the R. Bawa and A. M. Beatty, J. Chem. & of synthon flexibility," C. B. Aakeröy, A. competing intermolecular forces that Chem. Eng. 2012, 6, 372 M. Beatty, B. H. Helfrich and M. Nieu- exist in solutions of coordination com- wenhuyzen, Cryst. Growth. Des. 2003, 3, plexes, hydrogen-bonding substituents "Stable Hydrogen-Bonded Coordination 159. on ligands may be used to predictably Network with Removable Guests", G. A. assemble coordination complexes. We Hogan, N. P. Rath and A. M. Beatty, "Crystal engineering of organic clay can control the solid-state assembly of Crys. Growth Des. 2011, 11, 3740 mimics from 3,5-pyrazoledicarboxylic inorganic/organic hybrid materials either acid and amines," A. M. Beatty, K. E. by changing the metal ion (thus the pre- "Exceptions to the rule: new hydrogen- Grange and A. E. Simpson, Chem. Eur. ferred coordination geometry) or by syn- bonded networks from an old reliable", J. 2002, 8, 3254. thesizing ligands with hydrogen bonding O. Ugono, N. P. Rath and A. M. Beatty, substituents. For example, the figure CrystEngComm 2011, 13, 753 "Pillared clay mimics from dicarboxylic above shows that square planar Pt(II) acids and flexible diamines," A. M. Beat-

"2,2',5,5'-Tetrachlorobenzidine" O. ty, C. L. Schneider, A. E. Simpson and J. (isonicotinic acid)2(isonicotinate)2 com- Ugono, M. Douglas Jr, N. P. Rath and A. L. Zaher, Cryst. Eng. Comm. 2002, 4, plexes are linked through carboxylic acid M. Beatty,Acta Crystallogr. E, 2010, 66, 282. -carboxylate OH---O hydrogen bonds to o2285. form a square grid in the solid state. "2,4,6-Triphenylaniline", O. Ugono, S. THE FACULTY aggregation-induced quenching which is Selected Publications commonly observed in the solid state with luminescent planar aromatic organic ″Bis(alkynyl) PTA and DAPTA Com- molecules. plexes of Pt(II) and Pd(II)″, J. Braddock- Wilking, S. Acharya and N. P. Rath, They are also investigating the synthesis Polyhedron 2014, submitted. of related systems that incorporate linker groups that can bind to transition-metal ″Synthesis and Characterization of Pt(II) centers for the preparation of novel fluo- and Pd(II) PTA and DAPTAcomplexes″, rescent metal containing complexes as J. Braddock-Wilking, A. Sitaram and N. well as for applications in chemical sens- P. Rath, Polyhedron 2014, 79, 16. JANET BRADDOCK WILKING ing. Figure 3 shows two macrocyclic diplatinum complexes linked to a silole "Synthesis of 2,5-substituted siloles and Professor Braddock-Wilking received unit through an alkynyl group. Related optical study of interactions with mercu- her B.A. degree from the University of structures are being examined with dif- ry(II), copper(II), and nickel(II) cations," Missouri-St. Louis and her Ph.D. from ferent chelating phosphines and nitrogen- J. B. Carroll and J. Braddock-Wilking, Washington University. She joined the based donors (Figure 4). Organometallics 2013, 32, 1905. UM-St. Louis faculty in 1993 following postdoctoral fellowships at Harvard Uni- T. L. Bandrowsky, J. B. Carroll, J. Brad- versity and Mallinckrodt Medical, Inc. dock-Wilking, Synthesis, Characteriza- tion, and Crystal Structures of 1,1- Research Interests Disubstituted-2,3,4,5-tetraphenyl- Fig. 1. General metallole and metalla-fluorene germoles That Exhibit Aggregation- Dr. Braddock-Wilking’s research focuses structures (M = Si, Ge) Induced Emission," Organometallics on the synthesis, characterization, and 2011, 30, 3559. reactivity of compounds containing heavier Group 14 elements (E = Si, Ge). ″Luminescent Platinum Complexes Con- A major area of interest involves the taining Phosphorus-Linked Silole Lig- chemistry of heterocyclopentadienes ands″, J. Braddock-Wilking, L. Gao, N. containing Group 14 elements, also P. Rath, Dalton Trans. 2010, 39, 9321. known as metalloles (Figure 1), and related metallafluorenes and germafluores- ″Preparation and Photophysical Proper- ceins (Figure 1). These heavy Group 14 ties of Phosphino- and Phosphine Oxide- molecules are known to exhibit unusual linked Siloles″, J. Braddock-Wilking, L. optoelectronic properties and high elec- Gao, N. P. Rath, Organometallics 2010, tron affinity and mobility and thus have 29, 1612. potential application as components for Fig. 2. Molecular structure of a germafluorene electronic devices such as OLEDs and as chemical and biological sensors. Many of these molecules are weakly emissive in solution but show enhanced emission- in the solid state due to the phenomenon of aggregation induced emission render- ing them suitable for solid-state applications.

The research group is studying the structure-property relationship of these luminescent Group 14 molecules by exploring synthetic pathways that will allow for the incorporation of a variety of p- conjugated organic groups on the ring system enabling a range of emission Fig.3. Solid state fluorescence of a Fig.4. Solid state fluorescence of a germafluorene on a TLC plate . colors (blue to red) and to promote ag- germafluorene as crystals. gregation-induced emission in the solid state. Figure 2 shows the molecular structure of an exceptionally stable germafluorene prepared in our laboratory that exhibits strong blue emission in solution and the solid state. The phenyl groups at the germanium center provide steric crowding that prevents close contact of adjacent molecules preventing Fig. 5. Luminescent diplatinum macrocyles containing alkynyl-linked siloles. THE FACULTY putational methods (molecular dynamics, Y. E. Corilo, L. Nyadong, V. V. Lo- density functional theory, ab initio, and bodin, B. J. Bythell, W. K. Robbins, A. RRKM calculations). In so doing, stu- M. McKenna, A. G. Marshall, and R. P. dents acquire a wide variety of valuable Rodgers, Energy Fuels, 2013, 27, 1268. skills, and are exposed to multiple approaches to problem-solving. ″To Jump, or Not to Jump? Cα Hydrogen Atom Transfer in Post-Cleavage Radical- Cation Complexes,″ B. J. Bythell, J. Phys. Chem. A., 2013, 117, 1189.

″Vapors from Ionic Liquids: Reconciling Simulations with Mass Spectrometry Data,″ B. A. D. Neto, E. C. Meurer, R. Galav-erna, B. J. Bythell, J. DuPont, R. G. Cooks, and M. N. Eberlin, J. Phys. Chem. Lett., 2012, 3, 3435.

BENJAMIN J. BYTHELL ″Tyrosine Side-chain Catalyzed Proton Transfer in the YG a2 Ion Revealed by Professor Bythell received his MChem. Theory and IR Spectroscopy in the degree from the University of Bath, UK, ‘Fingerprint’ and X-H (X=C, N, O) in 2002 and Ph.D. from Oregon State Stretching Regions,″ B. J. Bythell, O. University in 2007. He held postdoctoral Hernandez, V. Steinmetz, B. Paizs, and fellowships at the German Cancer Re- P. Maître, Int. J. Mass Spectrom., 2012, search Center in Heidelberg (2008-2010) 316-318, 227. and at the National High Magnetic Field Selected Publications: Laboratory at Florida State University ″Targeted Petroleomics: Analytical In- ″Relative Stability of Peptide Sequence (2010-2013). He joined the faculty in vestigation of Macondo Well Oil Oxida- Ions Generated by Tandem Mass Spec- the fall of 2013. tion Products from Pensacola Beach, B. trometry,″ B. J. Bythell, C. L. Hendrick- M. Ruddy, M. Huettel, J. E. Kostka, V. son, and A. G. Marshall, J. Am. Soc. Research Interests V. Lobodin, B. J. Bythell, A. M. McKen- Mass Spectrom., 2012, 23, 644. Dr. Bythell works at the interface be- na, C. Aeppli, C. M. Reddy, R. K. Nel- tween analytical, computational and son, A. G. Marshall and R. P. Rodgers,″ ″Diagnosing the Protonation Site of b2 biophysical chemistry where he strives to Energy and Fuels, 2014, 28, 4043. Peptide Fragment Ions using IRMPD in understand the structure, reactivity and the X-H (X = O, N, and C) Stretching gas-phase behavior of biologically- and "Ion molecule reaction H/D exchange as Region,″ R. K. Sinha, U. Erlekam, B. J. industrially important chemicals. Funda- a probe for isomeric fractionation in Bythell, B. Paizs, P. Maître, J. Am. Soc. mentally, chemical structure determines chromatographically separated natural Mass Spectrom., 2011, 22, 1645. the properties and potential functions of organic matter”, A. C. Stenson, B. M. any given molecule. Consequently, the Ruddy and B. J. Bythell, Int. J. Mass gas-phase structures occupied by an ana- Spec. 2014, 360, 45. lyte ion have direct influence on which fragmentation pathways are populated, "Insight into the Mechanism of graph- and thus, on the resulting mass spectrum. eme Oxide Degradation via the Photo- The ability to decipher both the ele- Fenton Reaction”, H. Bai, W. Jiang, G. mental composition (CcHhNnOoSsPp) and P. Kotchey, W. A. Saidi, B. J. Bythell, J. structural information on unknown com- M. Jarvis, A. G. Marshall, R. A. S. Rob- pounds is highly desirable. To accom- inson and A. Star, J. Phys. Chem. C plish this successfully, an understanding 2014, 118, 10519. of the gas-phase fragmentation chemistries in play is of substantial benefit. "Unequivocal Determination of Site- Specific Protein Disulphide Bond Reduc- He and his students work on how and tion Potentials by Top Down FTICR MS why different analyte ions form particu- Characterization of the N and C Termi- lar conformations, and what effect this nal Redox-Active Sites in Human Thi- has on their gas-phase fragmentation oredoxin-1", J. Scotcher, B. J. Bythell chemistry. They utilize a wide assort- and A. G. Marshall, Anal. Chem. 2013, ment of analytical approaches based 85, 9164. around mass spectrometry (accurate mass identification, HPLC, isotopic ″Heavy Petroleum Composition. 5. Com- Bruker Maxis Plus (maXis HD) quadru- labeling, tandem mass spectrometry, positional and Structural Continuum of pole time-of-flight mass spectrometer hydrogen/deuterium exchange, “action” Petroleum Revealed,″ D. C. Podgorski, and UHPLC. IR spectroscopy), and cutting edge com- THE FACULTY physical properties requires extensive Miranda, J. S. Chickos, J. C. G. Esteves databases and a constant updating of Da Silva and J. F. Liebman, J. Chem. these databases. As a result, we have Thermodynamics, 2014, 73, 69. developed a collaborative interaction with the National Institutes of Standards "Vapor Pressures and Vaporization En- and Technology in Washington DC in thalpies of a series of c- and d-lactones which physical property data flow freely by correlation gas chromatogrhaphy", M. in both directions. We currently supply Kozlovskiy, C. Gobble and J. S. Chick- NIST with sublimation enthalpies of os, J. Chem. Thermodynamics 2014, 73, organic compounds. 262

"Vapor Pressures and Vaporization En- Coupled with our interest to develop thalpies of a series of Dialkyl Phthalates models for such properties is the need to JAMES S. CHICKOS by Correlation Gas Chromatography", C. obtain experimental data. A variety of Gobble, J. S. Chickos and S. P. Verev- Professor Chickos has been a member of physical properties are measured in our kin, J. Chem. Eng. Data. 2014, 59, 1353 the UM-St. Louis faculty since 1969. He research laboratories that include meas- received his undergraduate degree from urements of vaporization, sublimation the State University of New York- and fusion enthalpies. We are also exam- "Vapor Pressures, Vaporization, Subli- Buffalo, and his Ph.D. from Cornell Uni- ining new simpler methods of making mation and Fusion Enthalpies of Some versity. He was an NIH Postdoctoral these measurements. One such process Fatty Acids," J. A. Wilson and J. S. Fellow at Princeton University and the recently developed, correlation gas chro- Chickos, J. Chem. Eng. Data. 2013, 58, University of Wisconsin. matography, affords the vaporization 322 enthalpy and vapor pressure of a solid or Research Interests liquid at 298 K by simply using retention "Some thermodynamic properties of time measurements of knowns and un- benzocaine," C. Gobble, A. Gutterman All scientific endeavors are dependent on knowns. and J. S. Chickos, Struct. Chem., 2013, the availability of reliable thermodynam- 24, 1903. ic and physical property data. These data Selected Publications form the foundations on which our current understanding of the physical world "Vapor Pressures and Vaporization En- is based. The measurement and collec- thalpies of a series of - and -lactones tion of such data are a fundamental sci- by correlation gas chromatogrhaphy", M. entific task, common to all who practice Kozlovskiy, C. Gobble and J. S. Chick- the discipline. os, J. Chem. Thermodynamics 2014, 73,

262. We have had an interest in developing simple algorithms to model some of ″Feeling and investigating blue: On the these physical properties. The purpose enthalpy of formation of indigo″, M. S. for doing so is to provide data in the Miranda, J. S. Chickos, J. C. G. Esteves absence of experiment and to provide a Da Silva and J. F. Liebman, J. Chem. basis for the selection of a particular Thermodynamics, 2014, 73, 69 measurement in the presence of two or "Vaporization Enthalpies and Vapor more discordant values. In addition, the Pressures of Two Insecticide Compo- process of distilling these physical data nents, Muscalure and Empenthrin, by using these algorithms can sometimes Correlation Gas Chromatography″, J. produce parameters that can be used to Spencer and J. Chickos, J. Chem. Eng. evaluate molecular properties that cannot Data 2013, 59, 3513. be measured directly.

"Thermochemistry of Uracils. Experi- Simple models have been developed to mental and Computational Enthalpies of estimate condensed phase properties Formation of 5,6-Dimethyl-1,3,5- such as vaporization enthalpies, heat Trimethyl-, and 1,3,5,6-Tetramethyl- capacities, fusion entropies and en- uracils", R. Notario, V. N. Emelyanenko, thalpies, vapor pressures and sublimation M. V. Roux, F. Ros, S. P. J. S. Chickos enthalpies of small molecules. The pa- and J. F. Liebman, J. Phys. Chem. A rameters generated by these algorithms ″Vapor pressures and vaporization en- 2013, 117, 244. have also been useful in estimating fu- thalpies of a series of dialkyl phthalates sion enthalpies of polymers and confor- by correlation gas chromatography″, C. "Thermochemical and structural study of mational entropy changes in globular Gobble, J. S. Chickos and S. P. Vererkin, a dibenzocycloheptane cyanoenamine," proteins. Models to estimate mp have J. Chem. Eng. Data. 2014, 59, 1353. S. Perisanu, I. Contineanu, A. Neacsu, N. also been developed. P. Rath, J. S. Chickos, R. Notario and J.

″Feeling and investigating blue: On the F. Liebman. Struct. Chem., 2013, 24, The development of models to mimic enthalpy of formation of indigo″, M. S. 1975. THE FACULTY

Research Interests Selected Publications (135 total)

Novel glycosylation reactions, methods ″Hydrogen bond mediated aglycone and approaches. Stereocontrolled synthe- delivery: Synthesis of linear and sis of 1,2-cis-glycosidic bond formation. branched α-glucans,″ J. P. Yasomanee and A. V. Demchenko, Angew Chem. Mechanistic aspects of glycosylation. Intl Ed. 2014 (n press).

Thioimidates as glycosyl donors for ste- "Hydrogen-bond-mediated aglycone reoselective glycosylation and versatile delivery: Focus on β-mannosylation," S. building blocks for expeditious oligosac- G. Pistorio, J. P. Yasomanee and A. V. charide synthesis. Demchenko," Org. Lett. 2014, 16, 716 Novel expeditious strategies for the synthesis of complex oligosaccharides and “Regenerative glycosylation under nucle- glycoconjugates: reactivity, selectivity, ophilic catalysis”, S. S. Nigudkar, K. J. chemoselectivity, and orthogonality of Stine and A. V. Demchenko, J. Am. Chem. Soc., 2014, 126, 921. ALEXEI V. DEMCHENKO modern glycosyl donors.

Transition metal complexes in synthetic "Super-arming of glycosyl donors by Professor Alexei Demchenko received carbohydrate chemistry: direction of the combined neighboring and conforma- his Diploma from the Mendeleev Univer- stereoselectivity of glycosylation, tempo- tional effects.," M. Heuckendorff, H. D. sity of Chemical Technology of Russia, rary deactivation, and activation for gly- Premathilake, P. Pornsuriyasak, A. O. Moscow (1988) and his PhD in from the cosylation. Madsen, C. M. Pedersen, M. Bols and A. Zelinsky Institute of Organic Chemistry, Fully synthetic glycotherapeutics (anti- V. Demchenko, Org. Lett. 2013, 15 4904 Russian Academy of Sciences, Moscow cancer, anti-inflammatory, antiseptic, (1993). He was a BBSRC post-doctoral antibacterial, etc.). Synthetic glycopro- ″Effect of remote picolinyl and picoloyl teins, glycopeptides, glycopolymers, substituents on the stereoselectivity of research fellow at the School of Chemis- chemical glycosylation,″ J. P. Yaso- try, University of Birmingham (UK) and glycolipids, glycoheterocycles, glycoam- inoacids and combinations thereof. Syn- manee and A. V. Demchenko. J. Am. a research associate at the Complex Car- thetic glycoconjugate vaccines. Chem. Soc., 2012, 134, 20097. bohydrate Research Center, University of Solid phase and surface chemistry: appli- ″HPLC-assisted automated oligosaccha- Georgia before joining the UM-St. Louis ride synthesis,″ N. V. Ganesh, K. Fujika- faculty in 2001. He was recipient of the cation to stereoselective glycosylation and rapid assembly of complex oligosac- wa, Y. H. Tan, K. J. Stine, A. V. Dem- Chancellor’s Award for Research and charides and glycoconjugates. New plat- chenko. Org. Lett., 2012, 14, 3036. creativity in 2013 and was appointed forms and technologies for automated S. J. Hasty, M. Kleine, A. V. Demchen- Curators' Professor of Chemistry in oligosaccharide synthesis: STICS and ko. S-benzimidazolyl glycosides as a 2014. HPLC-based approaches. platform for oligosaccharide synthesis by an active-latent strategy. Angew. Chem. Int. Ed., 2011, 50, 4197 Edited Books" ″Frontiers in Modern Carbohydrate Chemistry″ Oxford Univ. Press, 2007. " Handbook of Chemical Glycosylation." Wiley-VCH, 2008.

Research Group Members (09/2014) Dr. Abhijeet Kayastha (post-doc) Dr. J. Prithika Yasomanee (post-doc) Xiao G. Jia (doctoral) Saltvatore G. Pistorio (doctoral) Satsawat Visansirikul (doctoral) Tinghua Wang (doctoral)

Current Funding 08/11-07/15 NSF CHE-1058112 08/12-07/15 Pfizer Inc. (8500124946) 04/13-03/15 Mizutani Foundation 08/14-07/18 NIH R01GM111835 THE FACULTY

artificial redox enzymes which should A. R. Khan, P. Forgo, K. J. Stine and V. have enhanced catalytic ability. These T. D'Souza, "Selective modifications of enzymes are designed using computa- cyclodextrins,"Proc. 9th Int. Symp.on tional chemistry techniques. Cyclodextrins, Santiago de Comostela, Spain, 1999, 33. In the process of developing the methodology to build these artificial enzymes, P. Forgo and V. T. D'Souza,"The Use of we have also produced a method to syn- High Resolution NMR Spectroscopy in thesize custom-designed cyclodextrins. Supramolecular Systems," Org. Lett., Cyclodextrins are cyclic oligosaccharides 1999, 1, 1543. which have gained prominence in the last two decades as complexing agents for P. Forgo and V. T. D'Souza "An NMR various organic molecules in artificial Approach for Determination of the Sub- enzymes, foods, flavors, etc. However, stitution Pattern in Supramolecular Sys- VALERIAN T. D’SOUZA the main shortcoming of this, otherwise tems," Tet. Letters, 1999, 40, 8533. remarkable, molecule is that the func- Professor. D'Souza received his M.Sc. tionalities available for useful chemical K. J. Stine, D. M. Andrauskas, A. R. from Bombay University, and his Ph.D processes are limited to simple hydroxyl Khan, P. Forgo, V. T. D'Souza, R. M. from the University of Detroit. He held a groups. The new method developed by Friedman and J. Liu, "Structure and postdoctoral position at Northwestern us enables us to synthesize cyclodextrins Electrochemical Behavior of a Flavin University prior to joining the UM-St. with various desired functionalities. We Sulfide Monolayer Adsorbed on Gold," Louis faculty in 1987. are presently investigating the binding J. Electroanal. Chem. 1999, 472, 147. and catalytic properties of these new Research Interests cyclodextrins K. J. Stine, D. M. Andrauskas, A. R. Khan, P. Forgo and V. T. D'Souza, The main goal of our research project is Selected Publications "Electrochemical Study of Self- to build redox catalysts based on the Assembled Monolayers of a ß- chemistry of biological redox enzymes. O. V. Shulga, K. Jefferson, A. R. Khan, cyclodextrin Methyl Sulfide Covalently The incredible power of the enzymes to V. T. D'Souza, J. Liu, A. V. Demchenko Linked to Anthraquinone," J. Electro- bring about chemical transformations and K. J. Stine. "Preparation and Charac- anal. Chem. 1999, 465, 209. with large acceleration and high specific- terization of Porous Gold and Its Appli- ity has been mainly attributed to their cation as a Platform for Immobilization P. Forgo and V. T. D'Souza "Application ability to bind the substrate and catalyze of Acetylcholinene Esterase." Chem. of Selective HSQC Experiment to Meas- specific reactions of the bound substrate. Materials 2007, 19, 3902. ure Interglycosidic Heteronuclear Long- Thus, these redox catalysts are designed range Coupling Constants in Cyclodex- to have a binding site to bind particular J. N. Swamy, R. E. K. Winter, C. R. trins," J. Nucl. Magn. Res. 1999, 37, 48. molecules and a catalytic site to catalyze Jeffreys and V. T. D'Souza, "Synthetic redox enzymes. We have synthesized the methodology for cyclodextrin- P. Forgo and V. T. D'Souza first generation of these artificial en- dipyrromethane conjugates," Tet. Lett., "Unambiguous Identification of Regioi- zymes using cyclodextrins as a binding 2004, 45, 7595. somers in Selectively Modified ß- site and flavin derivatives as catalytic cyclodextrins," J. Org. Chem., 1999, 64, site shown in the figure. V. T. D'Souza, "Modification of Cy- 306. clodextrins for Use as Artificial En- zymes," Supromolecular Chemistry, A. R. Khan, P. Forgo, V. T. D'Souza, R. 2003, 15, 221. M. Friedman and J. Liu "Structure and Electrochemical Behavior of a Flavin V. T. D'Souza, "Artificial redox en- Sulfide Monolayer Adsorbed on Gold," zymes," Biologicheskii Zhurnal Armenii, J. Electroanal. Chem., 1999, 472, 147. 2001, 53, 105. P. Forgo and V. T. D'Souza, "The Use of A. R. Khan, P. Forgo, S. Tian and V. T. High Resolution NMR Spectroscopy in D'Souza, "Synthesis and properties of Supramolecular Systems," Org. Lett., modified cyclodextrins," Proceedings, 1999, 1, 1543. 10th International Cyclodextrin Symposi- um, Ann Arbor, MI, 2000, 673. P. Forgo and V. T. D'Souza, "An NMR Approach for Determination of the Sub- This artificial enzyme can accelerate S. Tian, H. Zhu, P. Forgo and V. T. stitution Pattern in Supramolecular Sys- oxidation of benzyl alcohols up to 650- D'Souza. "Selectively Mono-Modified tems," Tet. Lett., 1999, 40, 8533. fold over that catalyzed by riboflavin. Cyclodextrins. Synthetic Strategies,"J. We are in the process of designing and Org. Chem., 2000, 65, 2624 . synthesizing the second generation of THE FACULTY a wide array of techniques including O. Sabaa-Srur, K. Tran. P. S. Shejwalker fluorescence and NMR spectroscopies, and R. E. Smith, Nat. Prod. J. 2012, 2, mass spectrometry, calorimetry, enzyme 99 kinetics, and capillary electrophoresis, among others. This provides excellent "Fluorescence assay of polyamide-DNA opportunities to master a number of bio- interactions," C. M. Dupureur, J. K. physical and mechanistic approaches. Bashkin, K. Aston, K. J. Koeller, K. R. Gaston and G. He, Anal. Biochem. 2012, Recent Publications 423, 178.

″Structural Insights into the Interaction "DNA targeting and cleavage by an engi- between a Potent Ant-inflammatory Pro- neered metalloprotein dimer," S. W. tein, Viral CC Chemokine Inhibitor Wong-Deyrup, C. Prasannan, C. M. (vCC), and the Human CC Chemokine Dupureur and S. J. Franklin, J. Biol. Eotaxin,″ N-W. Kuo, Y-G. Gao, M. Inorg. Chem. 2012, 17, 387. Schill, N. Isern, C. M. Dupureur and P. J. Li Wang, J. Biol. Chem. 2014, 289, "Metal ion and DNA binding by single- CYNTHIA DUPUREUR 6592. chain PvuII endonuclease: lessons from the linker," G. A. Papadakos and C. M. Professor Dupureur received her B.S. "Binding studies of a large antiviral poly- Dupureur, J. Biol. Inorg. Chem. 2011, degree from Southwest Missouri State amide to a natural HPV sequence,” G. 16, 1269. University, and her Ph.D. from Ohio He, E. Vasilieva, G. D. Harris, K. J. Ko- State University. She joined the UM-St. eller, J. K. Bashkin and C. M. Dupureur, "The First Total Synthesis of ()- Louis Chemistry faculty in 2001. She Biochimie 2014, 102, 83. Cyclophostin and ()-Cyclipostin P: In- held a faculty position at Texas A&M hibitors of the Serine Hydrolases Acetyl following postdoctoral fellowship at the "Mapping small DNA ligand hydroxyl Cholinesterase and Hormone Sensitive California Institute of Technology. radical footprinting and affinity cleavage Lipase", R. K. Malla, S Bandyopadhyay, products for capillary electrophoreses," C. D. Spilling, S. Dutta and C. M. Dupu- Research Interests G. He, E. Vasilieva; J. K. Bashkin, C. M. reur, Organic Lett. 2011, 13, 3094. Dupureur, Anal. Biochem. 2013, 439, 99 My group is interested in structure- "One is enough: insights into the two- function relationships, which is how the "Promoter scanning of the human COX- metal ion nuclease mechanism from structure of a biomolecule dictates its 2 gene with 8-ring polyamides: Unex- global analysis and computational stud- behavior. For many years, we focused pected weakening of polyamide–DNA ies", C. M. Dupureur, Metallomics, 2010, on metallonucleases, exploring aspects of binding and selectivity by replacing an 2, 609. DNA binding specificity and metal ion internal N-Me-pyrrole with β-alanine," J. dependent behavior using various bio- K. Bashkin, K. Aston, J. P. Ramos, K. J. "Nucleophile activation in PD...(D/E)xK physical techniques. More recently, this Koeller, R. Nanjunda, G. He, C. M. metallonucleases: An experimental and had led to two newer collaborative drug Dupureur and W. D. Wilson, Biochimie, computational pKa study", F. Xie, J. M. discovery projects. Taking advantage of 2013, 95, 271. Briggs and C. M. Dupureur, J. Inorg. our long term experience in enzyme Biochem. 2010, 104, 665. kinetics, we are evaluating synthetic "Fluorescence assay of polyamide-DNA inhibitors of esterases which are linked interactions," C. M. Dupureur, J. K. "Synthesis and kinetic analysis of some to Alzheimer’s disease and diabetes. A Bashkin, K. Aston, K. J. Koeller, K. R. phosphonate analogs of cyclophostin as project involving the conformational Gaston and G. He, Anal. Biochem. 2012, inhibitors of human acetylcholinester- behavior of hormone sensitive lipase has 423, 178. ase". S. Dutta, R. K. Malla, S. Bandyo- evolved from this effort. The other pro- padhyay, C. D. Spilling, and C. M. ject involves examining polyamide-DNA "ORAC Values and Anthocyanin content Dupureur, Bioorg. & Med. Chem. 2010, interactions in an effort to develop better of Brazilian and Floridian Acia (Euterpe 18, 2265. HPV drugs. The group has experience in oleraceae Mart," C. M.Dupureur, A. U. THE FACULTY have developed a chloride-selective branes mediated by pyrogallol[4] channel in an attempt to model anion arenes ," S. Negin, R. Li, O. V. Kulikov, transport and explore these cellular re- M. M. Daschbach and G. W. Gokel, quirements. Using known protein chlo- Inorg. Chim. Acta 2014, 417, 177. ride channels as a guide, we have synthesized a chloride-selective transporter that "Morphologies of branched-chain pyro- is active in phospholipid bilayers. We gallol[4]arenes in the solid state," O. V. use a broad range of biophysical methods Kulikov, S. Negin, N. P. Rath and G. W. to characterize the behavior of channels. Gokel, Supramolecular Chem. 2014, 26, These include dynamic light scattering, 506. fluorescence techniques, ion selective electrodes, calorimetry, NMR, the Lang- "Synthetic ion channels: From pores to muir trough, and Brewster angle micros- biological applications," G. W. Gokel copy. The cation (left) and anion (right) and S. Negin, Acc. Chem. Res., 2013, 46, channels are shown in the figure below. 2024.

Properties of Long Alkyl-chained Resor- GEORGE W. GOKEL cin[4]arenes in Bilayers and on the Lang- muir Trough," P. Ogirala, S. Negin, C. Professor Gokel attended Tulane Univer- Agena, C. Schäfer, T. Geisler, J. Mattay, sity, New Orleans, LA, B.S. chemistry, and G. W. Gokel, New J. Chem. 2013, 1968, University of Southern California, 37, 105. Los Angeles, CA, Ph.D. chemistry with I. K. Ugi, 1971 and UCLA, where he did "Anion Complexation and Transport by a postdoctoral fellowship with D.J. Molecular Capsules and Nanotubes Isophthalamide and Dipicolinamide De- Cram, 1972-1974. He served on the fac- rivatives: DNA Plasmid Transformation ulty at Penn State, Maryland and Miami It has been known for more than a centu- in E. coli," J. L. Atkins, M. B. Patel, M. prior to heading the Program in Chemi- ry that phenols and aldehydes react to M. Daschbach, J. W. Meisel, and G. W. cal Biology, Washington University form macrocycles. We have been devel- Gokel, J. Am. Chem. Soc., 2012, 134, School of Medicine, St. Louis. He oping the chemistry of amphiphilic 13546 joined UM-St. Louis as Distinguished nanocapsules and nanotubes for drug Professor in 2006 and was recently ap- delivery. The pyrogallol[4]arene com- “Aggregation and Supramolecular Mem- pointed Director of the Center for Nano- pounds have a unique and nearly unex- brane Interactions that Influence Anion science. plored chemistry. We have found that Transport in Tryptophan-Containing they form ion channels and exhibit very Synthetic Peptides.," M. M. Daschbach, Research Interests unusual amphiphilic properties. The S. Negin, L. You, M. Walsh and G. W. figure below shows a section of nanotube Gokel, Chem. A Eur. J. 2012, 18, 7608. Synthetic Cation and Anion channels along with the adjacent tubes interlocked During the past decade, our lab has de- with it. "Rapid acyl migration between pyrogal- veloped and elaborated a class of syn- lyl 1,2- and 1,3-dipivaloates," Y. Shan, J. thetic ion channels called hydraphiles. Liu, N. P. Rath and G. W. Gokel, Nat. We use diaza-18-crown-6 macrocycles Prod. Commun. 2012, 7, 333. as head groups and entry portals for ion conduction. Hydrophobic spacer chains "Synthetic memberane active am- connect the headgroups and impart the phiphiles," G. W. Gokel and S. Negin, appropriate length for the hydraphile to Adv. Drug Delivery Rev. 2012, 64, 784. span the bilayer. A third, central macro- cycle acts as an "ion relay." This subunit "Pyrogallo[4]arenes show highly Varia- serves the same purpose as the recently Selected Publications ble Amphiphilic Behavior at the Air- discovered "water and ion-filled capsule" Water Interface Dependent Upon side identified in the solid state structure of ″Improved Syntheses of Benzyl Hy- draphile Synthetic Cation-Conducting Chain Length and Branching", M. M KcsA channel of Streptomyces lividans. Daschbach, O. V. Kulikov, E. F. Long A side arm of varying identity extends Channels″ N. S. Curvey, S. E. Luderer, J. K. Walker and G. W. Gokel, Synthesis, and G. W. Gokel, Chem. A Eur. J. 2011, from the distal crown, providing anchor- 17, 8913 ing and stabilization in the bilayer. These 2014 (in press). ion channels show antibacterial activity and we are currently developing this “Hydraphile synthetic ion channels alter "In vivo cell death mediated by synthetic important aspect of their chemistry. root architecture in Arabidopsis thali- ion channels", B. A Smith, M. M.; ana,” M. B. Patel, A. Stavri, N. S. Cur- Daschbach, S. T Gammon, S. Xiao, S. E Anion, particularly chloride, permeabil- vey and G. W. Gokel, Chem. Commun. Chapman, C. Hudson, M. Suckow, D. ity is essential for volume, pH, and mem- 2014 (in press). Piwnica-Worms, G. W Gokel and W. M. brane potential regulation in all cells. We Leevy, Chem. Commun. 2011, 79779. "Ion transport through bilayer mem- THE FACULTY

below, pyrophosphate (PPi ), which can A collaborative effort to develop a new substitute for the carbonate, removes iron chelating resin is underway. Selective more rapidly than tripolyphosphate ligands are covalently attached to poly- (TPP), which cannot. mer beads for the removal of metal ions from solution. The relationship between In collaboration with Dr. Spilling’s lab, the ligand binding affinity on and off the new ligands are being designed and eval- resin is being evaluated. uated for their ability to remove iron at pharmacologically relevant ligand con- Selected Publications centrations. ″Immobilized ligands for the removal of In addition to its role in iron metabolism, metal ions and methods thereof,″ C. D. transferrin also acts as the primary serum Spilling, W. R. Harris, S. Dawadi and B. transport agents for a variety of toxic and Hamper, PCT Int. Appl. 2014, WO WESLEY R. HARRIS therapeutic metal ions. Dr. Harris’ group 2014130809 A1 20140828. has reported the binding constants for Professor Harris joined the UM-St. Louis transferrin with a number of other metal ″Flow-through filter to remove alumi- faculty in the Fall of 1988. He received ions. This include physiological metal 2+ 2+ num from medical solutions,″ R. A. Yo- both his B.S. and his Ph.D. from Texas ions such as Zn and Mn , pharmaceu- kel, W. R. Harris, C. D. Spilling, R. J. A&M University, and was a Postdoctoral tical metal ions such as Ga3+, In3+, and 3+ 3+ Kuhn, P. V. Abramov and J. M. Lone, Associate at the University of California- Gd and toxic metal ions such as Al . U.S. Pat. Appl. Publ. 2014, US Berkeley. Prior to joining UM-St. Louis, Recent work has focused on the binding 20140231321 A1 20140821. he held faculty positions at the Universi- of Al3+ to transferrin and to the low- ty of California at Davis and the Univer- molecular-weight ligands citrate and ″Crystal structure of pyridoxal amino sity of Idaho. He also serves as Associ- phosphate in order to construct an accu- methyl phosphonic acid (PYRAMPA) ate dean of the Graduates School. rate computer model for the speciation of 3+ 3+ and its stability constants with Al ,″ Y. Al in human serum. Z. Hamada, W. R. Harris and N. P. Rath, Research Interests Int. J. Green Nanotech, 2013, 5, 1.

Although iron is an abundant element, 3+ "Computer Simulation of the Interactions the insolubility of Fe at physiological Tyrosine of Glyphosate with Metal Ions in Phlo- pH requires specialized molecules to Tyrosine Histidine em," W. R. Harris, R. D. Sammons, R. bind and transport this essential metal. Tyrosine C. Grabiak, A. Mehrsheikh, and M. S. The key iron transport agent in mammals Tyrosine Bleeke, J. Ag. Food. Chem. 2012, 60, is the serum protein transferrin. This Histidine Carbonate 6077. protein binds iron as it enters the blood Glutamate Phosphate from the intestinal mucosal cells and Aspartate "Anion binding properties of the trans- controls the delivery of the metal to cells Transferrin FBP ferrins. Implications for function," W. R. that need iron. Harris, Biochim. Biophys. Acta, General Subjects, 2012, 1820, 348 The Harris group studies the kinetics of The studies on the mammalian protein iron release from transferrin to low- "Chelating compounds and immobilized molecular-weight ligands. This process transferrin have recently been expanded tethered chelators," R. A. Yokel, W. R. is relevant to the design of new ligands to include work on the binding and re- for treating iron overload. The rate of lease of ferric ion from a bacterial iron Harris, C. D. Spilling, R. J. Kuhn and S. iron release appears to depend on the transport protein known as FBP. This Dawadi, U.S. Pat. Appl. Publ. 2012, US ability of the incoming ligand to displace periplasmic transport protein is half the 2012-0061325 A120120315 the synergistic carbonate anion from the size of transferrin, but shares the key transferrin metal-binding site. As shown requirement for a synergistic anion in "Allosteric effects of sulphonate anions order to bind iron. While transferrin uses on the rates of iron release from Serum a carbonate anion, FBP uses phosphate 0.15 Transferrin", R. Sharma and W. R. Har- as the synergistic anion. The metal binding sites for the two proteins are shown ris, J. Inorg. Biochem., 2011, 105, 1148 below. ) 0.10 "The influence of citrate, maltolate and

-1 New studies are underway on the binding fluoride on the gastrointestinal absorp-

(min of other trivalent metal ions to FBP. It tion of aluminum at a drinking water-

obs may be possible to develop antbiotics k 0.05 relevant concentration: A Al-26 and C- based on the ability of other trivalent 14 study", Y. Zhou, W. R. Harris and R. metal ions to block the uptake or iron by the pathogenic organisms that rely on A. Yokel, J. Inorg. Biochem. 2008, 102, 0.00 FBP for iron uptake. 798. 0 50 100 150 200 250 [Ligand] mM THE FACULTY clusters. Y-Z. Zhang, U. P. Malik, R. Clérac, N. P. Rath and S. M. Holmes, "Structure- Photoresponsive Materials: property trends in cyano-bridged tetra- Compounds that change their optical, nuclear FeIII/NiII single-molecule mag- magnetic, and electrical properties as a nets," Polyhedron, 2013, 52, 115. function of external stimuli is an excit- ing area of study in materials science. We recently reported that two polynu- A. Panja, P. Giuionneau, I-R Jeon, S. M. clear cyanometalate complexes exhibit Holmes, R. Clerac and C. Mathoniere, reversible changes their optical and "Synthesis, Structures, and Magnetic magnetic properties with temperature Properties of a Novel mer-[(bbp)FeIII 2- (up to 250 K) and light. If this is a gen- (CN)3] Building Block (bbp:bis(2- eral phenomenon, then substitution of benzimidazolyl)pyridine dianion) and Its the metal ions and ligands present may Related Heterobimetallic Fe(III)-Ni(II) extend the operable switching tempera- Complexes," Inorg. Chem. 2012, 51, tures of these materials above 300 K. 12350 STEPHEN M. HOLMES Current efforts are directed at understanding the factors necessary for tuning Professor Holmes received his B.S. the photoresponsive behavior in these Y-Z. Zhang, U. P Mallik, N. P Rath, R. degree from Southwest Texas State clusters and one-dimensional networks. Clérac and S. M Holmes, University in 1992 and Ph.D. from the "Pyrazolylborates and their Importance University of Illinois at Urbana- in tuning Single Molecule Magnet Prop- Molecule-Based Devices: The in- III II Champaign in 1999. He was a Postdoc- erties of (Fe 2Ni } Complexes," Inorg. creasing demand for higher information toral Scholar at Cornell University from Chem. 2011, 50, 10537 density and circuit miniaturization is 1999-2001. He served on the faculty at rapidly approaching the limits of device the University of Kentucky before join- scaling technologies, with potential cost D. Siretanu, D. Li, L. Buisson, D. M. ing the Department of Chemistry & and performance limits being realized Bassani, S. M Holmes, C. Mathonière Biochemistry at UM-St. Louis in 2008. within a decade. An overarching goal of and R. Clérac, "Controlling Thermally He is currently an NSF CAREER molecule-based electronics is to insert Induced Electron Transfer in Cyano- Awardee (2007-2012). easily modified molecules that function Bridged Molecular Squares from Solid as switching elements into electronic State to Solution," Chem. A Eur. J. Research Interests devices, in principle allowing for infor- 2011, 17, 11704. mation storage at the molecular level. Magnetic Materials: Understanding Key challenges of this collaborative Y-Z, Zhang, U. P. Malik, R. Clérac, N. the physical origins of single-molecule research effort are to (1) fabricate nm- P. Rath and S. M. Holmes, "Irreversible magnetic behavior in a series of struc- scale electrode gaps that correspond to solvent-driven conversion of cyano- turally related cyanometalate clusters is molecular length scales and (2) engineer metallate{Fe2Ni}n (n = 2,3) single mole- an active area of study. Cyanometalates tunable molecules for study. Recent cule magnets," Chem. Commun. 2011, are excellent building blocks for con- measurements suggest that we have 47. structing molecule-based clusters be- successfully integrated a series of mag- cause cyanides generally form linear M netic clusters into electrical junctions. M. Tang, D. Li, U. P. Mallik, Y-Z. (-CN)M´ linkages between two metal Future efforts will investigate how the Zhang, R. Clérac, G. T. Yee, M. H. centers, stabilize a variety of transition clusters and metal ions present tune the Whangbo, A. Mungalimane and S. M. metal centers and oxidation states, and electrical transport behavior of assem- Holmes, "Synthesis and Characteriza- efficiently communicate spin density bled devices. tion of Di- and Trivalent Pyrazol- information. Furthermore the sign and ylborate β-Diketonates and Cyanomet- magnitude of the local exchange interac- Selected Publications alates," Inorg. Chem. 2011, 50, 5153. tions can be controlled via substitution and predicted using simple orbital sym- Y-Z. Zhang, D-F. Li,R. Clerac and S. Y. Zhang, D. Li, R. Clérac, M. Kalisz, metry arguments. We have developed a C. Mathonière and S. M. Holmes, M. Holmes, "A cyanide-bridged trinu- synthetic methodology for preparing III II "Reversible Thermally and Photo- several well-defined clusters containing clear {Fe 2Ni } complex decorated induced Electron Transfer in a Cyano- with organic radicals," Polyhedron a variety of tricyanide complexes Bridged {Fe2Co2} Square Complex," (building blocks). The building blocks 2013, 60, 110. Angew. Chem. Int. Ed. 2010, 49, 3752. exhibit significant orbital contributions

to their magnetic moments, apparently a C. C. Beedle, Y-Z. Zhang, S. M. necessary feature for the observation of Holmes and S. Hill, "EPR studies of a Y.-Z. Zhang, U. P. Mallik, N. Rath, G. slow magnetic relaxation. Current ef- cyano-bridged {FeIII NiII) coordination T. Yee, R. Clérac and S. M. Holmes, "A 2 III II forts are focused on how late transition complex and its corresponding FeIII cyano-based octanuclear {Fe 4Ni 4} metal centers alter the magnetic (and single-molecule magnet," Chem. Com- mononuclear building block," Polyhe- optical) properties of structurally related mun. 2010, 46, 4953. dron 2013, 59, 48. THE FACULTY α, interleukin-1β. We are studying these among memantine, amantadine and effects in monocyte/macrophage cells rimantadine", K. Middleton, G. P. and primary microglia cells with the Zhang, M. R. Nichols, and T. F. George, goal of understanding the cause of the Mol Physics, 2012, 110, 685. inflammatory response, how it relates to cell toxicity, and identification of novel "Isolated amyloid-β(1-42) protofibrils, ways to regulate cytokine release. but not isolated fibrils, are robust stimu-

Selected Publications lators of microglia," G. S. Paranjape, L. K. Gouwens, D. C. Osborn, and M. R. ″CD47 does not mediate amyloid-β(1- Nichols, ACS Chem Neurosci, 2012, 3, 42) protofibril-stimulated microglial 302. cytokine release,″ S. Karki and M. R. Nichols, Biochem Biophys Res Com- "Substituted tryptophans at amyloid-β(1 MICHAEL R. NICHOLS mun, 2014, in press -40) residues 19 and 20 experience different environments after fibril for- ″Amyloid-β(1-42) protofibrils stimulate Professor Nichols received his B.S. mation," R. T. McDonough, G. a quantum of secreted IL-1β despite degree from Lindenwood College and Paranjape, F. Gallazi, and M. R. Nich- significant intracellular IL-1β accumula- Ph.D. from Purdue University. Prior to ols, Arch. Biochem. Biophys. 2011, 514, tion in microglia,″ S. E. Terrill-Usery, joining the UM-St. Louis faculty in Fall 27 M. J. Mohan, and M. R. Nichols, BBA- 2004, he completed a postdoctoral fel- Mol Bas Dis, 2014, 1842, 2276 lowship at the Mayo Clinic in Jackson- "Development of LPS antagonistic ther- ville, FL. ″The influence of gold surface texture apeutics: synthesis and evaluation of

on microglia morphology and activa- glucopyranoside-spacer-amino acid Research Interests tion,″ Y.H. Tan, S.E. Terrill, G.S. motifs," S. Kaeothip, G. Paranjape, S. E. Paranjape, K.J. Stine, and Nichols, M.R. Terrill, A. F. G. Bongat, M. L. D. Udan, Protein assembly or aggregation is wide- Biomater Sci, 2014, 2, 110 T. Kamkhachorn, H. L. Johnson, M. R. ly recognized as a significant contrib- Nichols and A. V. Demchenko, RSC uting factor to a number of neurodegen- "Stability of early-stage amyloid-β(1- Advances, 2011, 1, 83. erative diseases including Alzheimer’s 42) aggregation species,″ K. A. Coalier, disease (AD), Parkinson’s disease, Hun- G. S. Paranjape, S. Karki, and M. R. "Probing the amyloid-β(1-40) fibril tington’s disease, and others. Remarka- bly, the proteins or peptides implicated Nichols, Biochimica et Biophysica Ac- environment with substituted tryptophan in these diseases, while possessing dif- ta, 2013, 1834, 65 residues,"J. C. Touchette, L. L. Wil- ferent amino acid sequences, all self- liams, D. Ajit, F. Gallazi, and M. R. assemble to form similar fibrillar struc- “Amyloid-β(1-42) protofibrils formed in Nichols Arch. Biochem. Biophys, 2010, tures termed amyloid. One such peptide modified artificial cerebrospinal fluid 494, 192. is amyloid-β (Aβ), a 40-42-residue pep- bind and activate microglia,” G. S. tide and the primary component of the Paranjape, S. E. Terrill, L. K. Gouwens, "Amyloid-β(1-42) fibrillar precursors senile plaques found in AD brains. The B. M. Ruck, and M. R. Nichols, J Neu are optimal for inducing tumor necrosis leading hypothesis in AD research main- roimmune Pharmacol, 2013, 8, 312 factor-α production in the THP-1 human tains that accumulation of aggregated monocytic cell line,” D. Ajit, M. L. D. Aβ is the primary cause of the disease. "A comparative first-principles study of Udan, G. Paranjape, and M.R. Nich- One research area in my laboratory in- structural and electronic properties ols, Biochemistry, 2009, 48, 9011. volves mechanistic studies of Aβ aggregation. Objectives include isolation and characterization of aggregation intermediates and investigation of conditions that influence aggregation. These studies utilize a variety of biophysical techniques to probe mechanistic and structural questions.

The other major research thrust in my laboratory addresses the question of how Aβ aggregates interact with, and are detrimental to, cells. One hypothesis is induction of a sustained inflammatory response causing the release of harmful (Left) Electron microscopy image (59k magnification) of isolated Aβ42 protofibrils. (Right) Binding of Aβ42 protofibrils (green) to BV-2 microglia. Cell nuclei are shown in blue. cytokines such as tumor necrosis factor- THE FACULTY

Selected Publications Section of NiH absorption spectrum NiH (Discharge at 0.26 Amps, 1.46 Torr H2), Leff = 775 meters I2 Reference Spectrum “High resolution electronic spectroscopy 100

of the A2Σ- - X2Π1/2 transition of PtN,” 62NiH 64 64 K. Womack, L. C. O'Brien, S. Whitte- 75 NiH NiH 60NiH 58NiH more, J. J. O’Brien, A. Li, and T. C. 62 50 62NiH NiH Qd(9.5) Steimle, J. Chem. Phys. 2014, 141, P (7.5)

Transmittance (%) 25 d 084304/1 60NiH 60NiH Pc(7.5) 58 NiH 58NiH 100 ″Methane line parameters in the HI- TRAN2012 database,″ L. R. Brown, J. J. 95 90 O'Brien et al., J. Quant. Spectrosc. Radi- I2 Transmittance (%) ative Transfer, 2013, 130, 201. 15756.0 15757.0 15758.0 15759.0 15760.0 15761.0 Wavenumber (vacuum cm-1) 2 2 JAMES J. O’BRIEN ″Reanalysis of the [12.3] Σ - X Π 3/2, 4 2 2 2 2 2 + Gold oxide (2-0) П3/2 – X П3/2 spectrum [12.3] Σ - X Π1/2, and [12.3] Σ - B Σ 100 Professor Jim O’Brien received his B.Sc. electronic transitions of nickel mono- (1st class Honors) from James Cook Uni- chloride, NiCl,″ T. Dahms, K. Womack, 95 versity and his Ph.D. from the Australian L. C. O’Brien and J. J. O'Brien, J. Mol. 90 Spectrosc.2013, 292, 5. National University in Canberra. He had 85 post-doctoral positions at the University 80 of California-Berkeley (CSIRO Australia "Improved experimental line positions (%) Transmittance AuO P(J") Fellowship), the National Research for the (1, 1) band of the b1S+-X3S tran- 75 14.5 13.5 12.5 11.5 10.5 9.5 R(J") Council of Canada, Ottawa (NRC Re- sition of O ," J. J. O'Brien, E. C. O'Brien 24.5 23.5 22.5 21.5 20.5 19.5AuO 2 70 search Associate), and the University of and L. C. O'Brien, J. Mol. Spectrosc. 17908.5 17910.5 17912.5 17914.5 17916.5 17918.5 17920.5 Wavenumber (cm-1) Arizona, Tucson. 2012, 273, 34. Wavenumber (cm-1) 13162 13164 13166 100 Research Interests "Intracavity laser absorption spectrosco- 80 py of platinum fluoride, PtF," K. Han- Jim O’Brien is an experimental physical dler, R. A. Harris, L. C. OBrien, and J. J. 60 chemist who specializes in fundamental OBrien, J. Mol. Spectrosc. 2011, 265, 39. 40 20 33 31 RR(J") and applied, high-resolution laser spec- (%) Transmittance 34 32 23 25 R 0 Q(J") troscopy and gas phase analytical chem- "The Pt2 (1,0) Band of System VI in the 20 24 28 100 istry. The primary tool employed is Near Infrared by Intracavity Laser Ab- Intracavity Laser Spectroscopy. ILS sorption Spectroscopy," L. C. O'Brien 95 techniques provide tremendously en- and J. J. O'Brien, J. Chem. Phys. 2011, 90 hanced sensitivity for measuring absorp- 134, 184304/1 85

Transmittance (%) Transmittance I tion spectra quantitatively. 80 2 100 Research areas include: (1) determining "The 5-0 overtone band of HCl" J. J. 80 O’Brien, S. A. Ryan and L. C. O’Brien, 60 absorption spectroscopy parameters (e.g., 40 J. Mol. Spectrosc. 2011, 265, 110. Intensity absorption coefficients) for methane and 20

ammonia in the visible to near IR spec- /ch) 1.5996% difference between ch. 1 & ch. 1024 1

- 9.60 b[0]=9.4785245455 "Intracavity laser absorption spectrosco- b[1]=2.0303866719e-4 9.55 b[2]=-2.9291913039e-8 tral region to assist in interpreting re- (cm b[3]=-2.2492847268e-11 3 py of platinum sulfide in the near infra- 9.50 r ²=0.9936852569 flected spectra from the outer planets x10 200 400 600 800 1000 (e.g., Neptune); (2) high-resolution elec- red," K. Handler, L. C. O'Brien and J. J. Channel tronic spectroscopy of small transition- O'Brien,J. Mol. Spectrosc. 2010, 263, 78. ILS spectra of methane at 3 temperatures metal diatomics (e.g., AuO, NiCl, NiH) 100 with a view to locating excited electronic "Spectroscopy of NiF by intracavity laser 90 states in these species and comparing spectroscopy: Identification and analysis 80 of the (1,0) band of the [11.1] 2P -X 70 trends in bonding; (3) determining mo- 3/2 60 2 -112 oC 50 lecular constants from precisely meas- P3/2 electronic transition," R. A. Harris, (%) Transmittance ured line positions of species of atmos- L. C. O'Brien and J. J. O'Brien, J. Mol. 100 Spectrosc. 2010, 259, 116. 90 pheric (e.g., O2) and environmental rele- 80 vance (4) the gas phase chemistries and 70 60 "Laboratory measurements of the (2,0) -142 oC species involved in a variety of plasma 50 2 2 (%) Transmittance initiated chemical vapor deposition B D5/2-X D5/2 transition of nickel hydride 100 (CVD) processes; and (5) developing the using intracavity laser absorption spec- 90 troscopy," S. Shaji, A. Song, M. Li, J. J. 80 intracavity laser spectroscopy technique 70 O'Brien and L. C. O'Brien, Can. J. Phys. 60 for analytical purposes (e.g., in acquiring -174 oC 50 spectra at ultra high spectral resolution) 2009, 87, 583 (%) Transmittance 11025 11026 11027 11028 11029 and extending its spectral range of appli- Wavenumber (cm-1) cation (e.g., use of other types of lasers that work in the IR). THE FACULTY should undergo similar chemistry. How- Pharmacol.& Therapeutics 2014, 19, ever, the presence of the phosphonate 189. significantly alters the electronics of the system, and enables control of both regi- ″Support of academic synthetic chemis- ochemistry and stereochemistry. Our try using separation technologies from initial work focused on the palladium the pharmaceutical industry¸″ E. L. Re- catalyzed addition of amines to the car- galado, M. C. Kozlowski, J. M. Curto, T. bonate derivatives of allylic hydroxy Ritter, M. G. Campbell, A. R. Mazzotti, phosphonates, and several examples of B. C. Hamper, C. D. Spilling, M. P. this reaction have performed. The rear- Mannino, L. Wan et al. Org. & Bio- rangement proceeds with complete reten- molecular Chem. 2014, 12, 2161 tion of chirality. A number of 3,3 sig- matropic rearrangements and alkene ″Relay Cross Metathesis Reactions of addition reactions have been studied. Allyl Vinyl Phosphonates¸″ R. J. K. Mal- The newly developed chemistry of the la, J. N. Ridenour and C. D. Spillng, CHRISTOPHER D. SPILLING hydroxy phosphonates is being applied Beilstein J. Org. Chem. 2014, 10, 1933. towards the synthesis of heterocyclic and Professor. Spilling received his B.Sc. carbocyclic natural products and enzyme "Enantioselective Inhibition of Microbial (Hons.) degree and Ph.D. degree from inhibitors. Lipolytic Enzymes by Nonracemic Mon- the University of Technology, Loughbor- ocyclic Enolphosphonate Analogues of ough, England. He was a Postdoctoral Psammapsylin, fistularin, and the basta- cylcophostin," V. Point, R. K. Malla, F. Associate at Northwestern University dins are related metabolites isolated from Carriere, S. Canaan, C. D. Spilling and J- before joining the UM-St. Louis faculty sponges found worldwide. This family F. Cavalier, J. Med. Chem. 2013, 56, in 1989. He became department chair in of highly brominated compounds possess 4393. 2004. wide ranging biological activity, including anti-HIV activity, and anti-tumor "Synthesis and Kinetic Evaluation of Research Interest properties. They are related in their bio- Cyclophostin and Cyclophostins Phos- synthetic origin, as oxidation products of phonate Analogs as Selective and Potent The last decade has seen a rapid expan- tyrosine. We are exploring biomimetic Inhibitors of Microbial Lipases," V. sion in the interest in the asymmetric approaches to the synthesis of several of Point, Vanessa; R. K. Malla, S. Dioman- synthesis of 1-substituted phosphonates. these metabolites. The development of de, B. P. Martin, V. Delorme, F. Carri- The unique properties of phosphorus new methodology is guided by the bio- ere, S. Canaan, N. P. Rath, C. D. Spilling provide a fascinating and challenging synthetic pathway proposed for the for- and J-F. Cavalier, J. Med. Chem., 2012, approach to stereoselective reactions. mation of the tyrosine metabolites. As 55, 1024. Our goal is to examine the use of chiral an extension of this project, we recently phosphonamides and phosphonates in initiated research into methods for the "An Expeditious Total Synthesis of Both stereoselective reactions. We reported facile synthesis of unsymmetric biaryl Diastereomeric Lipid Dihydroxytetrahy- the first example of a lathanide chiral ethers. drofurans from Noptheia Anomala," S. catalyst in the addition of simple phos- Roy and C. D. Spilling, Org. Lett., 2012, phites to achiral aldehydes. More recent- Selected Publications 14, 2230. ly, we discovered some promising titanium alkoxide systems. We are attempting ″A filtration System that greatly reduces "The First Total Synthesis of (±)- to expand the chemistry of allylic hy- aluminum in Calcium Gluconate Injec- Cyclophostin and (±)-Cyclipostin P: droxy phosphonamides and phospho- tion USP used to prepare parenteral nu- Inhibitors of the Serine Hydrolases Ace- nates formed in the chemistry discussed trition solutions¸″ R. A. Yokel, W. R. tyl Cholinesterase and Hormone Sensi- above. Allylic hydroxy phosphonates Harris, C. D. Spilling, V. P. Abramov, J. tive Lipase," R. K. Malla, S Bandyo- are similar to regular allylic alcohols and M. Lone and R. J. Kuhn, J. Pediatric padhyay, C. D. Spilling, S. Dutta and C. O O M. Dupureur, Org. Lett. 2011, 13, 3094. OMe RHcatalysed RP1,3 transposition RPOMe OMe OMe "Concise synthesis of 1,3-di-O- O Addition 1 OH X substituted tetrahydropyran derivatives Stereoselective as conformationally stable pyranose alkene addition mimetics," L. K. Mydock, C. D. Spilling Y Y O Z and A. V. Demchenko, Comptes Rendus OMe Y RP Chim. 2011, 14, 301. R OMe CO2H O oxidation and R = CH2OH X hydrolysis X Z O "A Formal Synthesis of the C1-C9 Frag- anion + electrophile ment of Amphidinolide C Employing the Tamaru Reaction," M. P. Paudyal, Y Y R Y N. P. Rath and C. D. Spilling, Organic R RR' R' Lett. 2010, 12, 2954. X O X Z X O

THE FACULTY kinds (SEM, TEM, AFM) with UM-St. anal. Chem. 2014, 717/718, 47. Louis Center for Nanoscience is a strong interest. The bioanalytical application of "The influence of gold surface texture on these materials is pursued using primari- microglia morphology and activtion," Y. ly surface plasmon resonance and elec- H. Tan, S. Terrill, G. S. Paranjape, K. J. trochemical methods. The application of Stine and M. R. Nichols, Biomat. Sci. nanostructured materials in the supported 2014, 2, 110. organic synthesis of carbohydrates is an interest in collaboration with the Dem- "Surface-Tethered Iterative Carbohydrate chenko lab. Monolayers can serve as Synthesis: A Spacer Study," V. N. model systems providing insight into the Ganesh, K. Fujikawa, Y-H. Tan, S. S. physical properties of membranes and Nigudkar, K. J. Stine and A. V. Dem- can be used to model molecular recogni- chenko, J. Org. Chem. 2013, 78, 6849. tion processes occurring at membrane surfaces. Monolayers of surface-active "O-Benzoxazolyl imidates as versatile KEITH J. STINE molecules at the air-water interface glycosyl donors for chemical glycosyla- (Langmuir monolayers) are studied using tion," S. S. Nigudkar, A. R. Parameswar, Professor Stine graduated with special fluorescence microscopy, Brewster angle P. Pornsuriyasak, K. J. Stine, and A. V. honors with a B.S. in Chemistry from microscopy, and surface pressure versus Demchenko, Org. and Biomol. Chem Fairleigh Dickinson University and re- molecular area isotherm measurements. 2013, 11 4068. ceived his Ph.D. from Massachusetts The transfer of these monolayers onto Institute of Technology. He was a post- solid supports for examination by mi- "Lectin-Carbohydrate Interactions on doctoral fellow at UCLA and joined the croscopy, spectroscopy, or electrochem- Nanoporous Gold Monoliths," Y.-H. UM-St. Louis Chemistry Department in istry is another area of interest. Aggre- Tan, K. Fujikawa, P. Pornsuriyasak, A. J. the Fall of 1990. gates of biological relevance such as Alla, A. V. Demchenko and K. J. Stine, micelles, liposomes, and supported bi- New J. Chem., 2013, 37, 2150 Research Interests layers are of interest. The surface properties and membrane activity of selected "Nanoporous gold as a solid support for Dr. Stine's research effort focuses on natural products in the saponin family is protein immobilization and development studies of monolayer-modified surfaces a specific recent focus in this area. of an electrochemical immunoassay for and nanostructures, and on model sys- Selected Publications prostate specific antigen and carcinoem- tems relevant to understanding the be- bryonic antigen", B. Pandey, A. V. Dem- havior of cell membranes. The surface ″Regenerative Glycosylation under Nu- chenko and K. J. Stine, Microchimica modification of nanostructures is pursued cleophilic Catalysis″, S. S. Nigudkar, K. Acta, 2012, 179, 71.. with a focus on their prospective applica- J. Stine and A. V. Demchenko, J. Am. tions in bioanalytical chemistry such as Chem. Soc., 2014, 126, 921. "Comparative Study of the Binding of in immunoassays for protein biomarkers Concanavalin A to Self-Assembled of disease. Immobilization of proteins "Square-wave voltammetry assays for Monolayers Containing a Thiolated α- onto nanostructures of gold and other glycoproteins on nanoporous gold," B. Mannoside on Flat Gold and on Nanopo- materials is pursued by adsorption or by Pandey, J. K. Bhattarai, P. Pornsuri- rous Gold," B. P. Pandey, Y-H. Tan, K. covalent linkage to self-assembled mon- yasak, K. Fujikawa,R. Catania, A. V. Fujikawa, A. V. Demchenko and K. J. olayers. The characterization of these Demchenko and K. J. Stine, J. Electro Stine, J. Carbohydrate Chem. 2012, 31, nanostructures by microscopy of various 466.

SEM micrograph of nanoporous gold useful for Tapping Mode Atomic Force Microscopy Image of Bovine assay development. Serum Albumin Immobilized on a Rough Gold Surface. THE FACULTY Selected Publications Z"Docking flexible peptide to flexible protein by molecular dynamics using two "Molecular simulation of drug-binding implicit-solvent models: An evaluation kinetics″, C. F. Wong, Molecular Simu- in protein kinase and phosphatase sys- lation, 2014, 40, 889 C. tems," . Huang and C. F. Wong, J.Phys. Chem. B 2009, 113, 14343. "Drug design for Protein Kinases and Phosphatases: Flexible-Receptor Dock- "Beyond Thermodynamics: Drug Bind- ing, Binding Affinity and Specificity, ing Kinetics Could Influence Epidermal and Drug-Binding Kinetics," F. Wong Growth Factor Signaling," M. Goyal, M. and S. Bairy, Curr. Pharm. Design 2013, Rizzo, F. Schumacher and C. F. Wong, J. Med. Chem. 2009, 52, 5582. 19, 4739.

"A Computational Study of the Phos- "SRmapper: a fast and sensitive genome- phorylation Mechanism of the Insulin hashing alignment tool,″ P. M. Gontarz, CHUNG F. WONG Receptor Tyrosine Kinase" B. Zhou and J. Berger and C. F. Wong, Bioinformat- C. F. Wong, J. Phys. Chem. A, 2009, Professor Chung F. Wong received his ics 2013, 29, 316. B.Sc. (Hons.) degree from the Chinese 113, 5144. University of Hong Kong and his Ph.D. "A case study of scoring and rescoring in degree from the University of Chicago. peptide docking," Z. Huang and C. F. He did his postdoctoral work at the Uni- Wong, Methods Mol. Biol 2012, 819 versity of Houston. Before joining the (Computational Drug Discovery and faculty of UM-St. Louis in the Fall of 2004, he held positions at the University Design), 269 of Houston, Mount Sinai School of Med- icine, SUGEN, Inc., University of Cali- "Simulation reveals two major docking fornia-San Diego, and the Howard pathways between hexapeptide Hughes Medical Institute. GDYMNM and the catalytic domain of the insulin receptor protein kynase," Z. Research Interests Huang and C. F. Wong, Proteins: Struc- ture, Function, and Bioinformatics, The Wong laboratory, situated in the 2011, 79, 2275 Center for Nanoscience, utilizes a combination of quantum mechanics, statistical "Influence of Kinetics of Drug Binding mechanics, computer simulation, molec- on EGFR Signaling: A Comparative ular modeling, and informatics tech- Study of Three EGFR Signaling Pathway niques to study biological macromole- Models," S. Bairy and C. F. Wong, Pro- cules and their interactions with other teins: Structure, Function, Bioinformat- molecules. Current projects include: ics, 2011, 79, 2941..

1. Computer-aided design of therapeu- "Supplementing the pbsa approach with tic drugs targeting protein kinases quantum mechanics to study the binding and phosphatases. between CDK2 and N2-substituted O6- 2. Elucidating the enzymatic mecha- cyclohexylmetho-xyguanine inhibitors," nisms of protein kinases and phos- J. Shi, Z. Lu, Q. Zhang, M. Wang, C. phatases. F.Wong and J. Liu, J. Theor. Comput. 3. Understanding the molecular mech- Chem. 2010, 9, 543. anisms of MALDI processes. 4. Development of computational tools "Derivatives of salicylic acid as inhibi- that can help address the above tors of YopH in Yersinia pestis,"Z, problems. Huang, Y. He, X. Zhang, A. Gunawan, L. Wu, Z-Y Zhang and C. F. Wong, Chem. Biol. and Drug Design, 2010, 76, 85.

complex complex complex complex G   r  d3r   r  d3r   solvent r  solvent d3r bind  ligand protein  ligand ligand  ligand ligand complex g complex g   H   solvent H solvent  Gdesolv A ligand ligand ligand ligand protein A fixed - conformation QM/MM/PBSA model for rank - ordering protein - ligand binding affinity THE FACULTY

blood or body fluid need for clinic anal- electrochemistry, catalysis, and corrosion yses could be reduced to less than 1% of inhibition. By using a novel technique - what is need today, and disease could be nonlinear optical molecular probing diagnosed much earlier and with better (NOMP) method, we are able to extract accuracy. In drug discovery, the time the information of chemical interactions needed for identifying an efficient syn- and chemical reactions in an interfacial thetic route could be significantly re- region within 20 - 50 Å from the solid duced. This could lead to the develop- surface. This has created new research ment of better and more economic medi- opportunities to understand the actual cine for decease treatment and preven- separation processes in HPLC and elec- tion. In environmental protection, most trophoresis, and to develop new station- chemical analyses can be carried out ary phases that are highly selective for with unprecedented speed and accuracy, the separation of large organic and bio- which could help to create a clearer liv- molecules. ing environment. ZHI XU Selected Publications New Photonoc Materials: The research Professor Xu received his B.S. degree in is aimed at developing new photonic ″New spectroscopic method for the de- Chemistry, an M.S. degree in Electrical materials that have applications in optical termination of optical rotatory disper- Engineering from Tsinghua University, data storage, nonlinear optical conversion,″ Z. Han, Z. Xu and L. Chen, Chi- Beijing, China, and his Ph.D. in Chemis- sion, and two-photon absorption. In par- nese Optics Lett., 2014, 12, 081202. try from the University of Pittsburgh. He ticular, we are interested in the infor- held a postdoctoral position at the Uni- mation storage by individual molecules ″A three-spectrum method for accurate versity of Illinois, Urbana, prior to join- and the structure-function relationship calibration of bi-plate zero-order retard- ing the UM-St. Louis faculty in 1994. that governs the two-photon absorption er,″ Z. Han, Z. Xu and L. Chen, Chinese (TPA) behavior of organic molecules. Optics Lett., 2014, 12, 031202. Research Interests Our earlier study has demonstrated the feasibility of information storage by ″External/internal optical adapter with Development of new optical analytical individual molecules in liquid phase reverse biased photodiodes for FTIR instrumentation, investigation of new based on intermolecular charge transfer. spectrophotometry,″ Z. Xu, U.S. photonic materials, and study of solid- Our current investigation in this direction 8,830,474, U.S. Patent issued to the Cu- liquid interfacial chemistry are three is to translate our successful model sys- rators of the University of Missouri, major research areas in our group. tem from liquid phase into solid phase. 2014. In the research front of two-photon ab- “External/Internal Optical Adapter for Development of New Optical analyti- sorption, we have developed new transition theory based on quantum mechanics. FTIR Spectrophotometer,” Z. Xu, U.S. cal Instrumentation: Our basic re- 8,766,191, U.S. Patent issued to the Cu- search in optical spectroscopy has led to A series of new molecular structures have been developed according to the rators of the University of Missouri, the invention of a new spectroscopic 2014. technology. The new technology has the prediction of the new theory. These new potential to increase the sensitivity of molecules have increased the TPA cross- “Optical Spectroscopy Device for Non- most commonly used optical analytical section over 2000 times in comparison to Invasive Blood Glucose Detection and instruments 100 to 1000 fold over that of traditional organic molecules with long Associated Method of Use,” Z. Xu, U.S. state-of-the-art commercial instruments. electron conjugations. The extremely 8,552,359, U.S. Patent issued to The Our current research is focused on the large TPA cross-sections of these new Curators of the University of Missouri, implementation of the new technology to molecules make it possible to develop 2013 new optical media/devices for three- a wide range of instrumentations includ- ″Optical Device Components,” Zhi Xu, ing UV-Vis Spectrophotometry, Infrared dimension optical storage, up-conversion of light to create blue and UV lasers, and Hong Kong Patent No. HK1151351, (IR) Spectrophotometry, High Perfor- Hong Kong Patent issued to The Cura- mance Liquid Chromatography (HPLC), the protection of human eyes and optical tors of the University of Missouri, 2013 Atomic Absorption (AA), Inductively sensors from the permanent damage by Coupled Plasma Atomic Emission (ICP- lasers. “Optical Device Components,” Zh. Xu, AE), and Circular Dichroism (CD). This Australian Letters Patent No. research could dramatically improve Chemistry at Solid-Liquid Interfaces: 2008307505, Australia Patent issued to both qualitative and quantitative analyti- The goal is to achieve molecular level The Curators of the University of Mis- cal capability in a broad range of chemi- understanding of phenomena such as souri, 2013. cal, biological, medical and other appli- adsorption, molecular interaction, and ″Liquid Chromatography Detector and cations. Analyses from life science re- chemical reactions occurring in solid- Controller Therefor," Z. Xu, R. Bose and search to clinical diagnoses and from liquid interfacial systems of fundamental J. M. Anderson, U.S. 8,397,553, U.S. environmental analyses to forensic inves- and industrial importance. Some of the Patent issued to The Curators of the Uni- tigations will be favorably impacted. In industrial application areas for such stud- healthcare, for example, the amount of ies are separation science, surfactants, versity of Missouri, 2013. EMERITUS AND RESEARCH FACULTY Research Interests and L. Barton. "Degradation and Modifi- cation of Metallaboranes Part 4: Synthe- Dr Barton and his students had several sis and Characterization of a series of areas of research interest, as briefly de- hybrid bimetallaborane clusters of the scribed below. The work involves study type [2,2,2-(PPh ) (CO)-nido-2-OsB H - of borane and metallaborane clusters. 3 2 4 7 3-(BH PPh )C H PPh RuCl (p-cym)]," 2 2 x y 2 2 A main group-element project led to the Inorg. Chim. Acta. 2005, 358/5, 1545. preparation of a series of metalloboranes based on B6H10 and B5H9 using the main P. McQuade, R. E. K. Winter and L. group metals Sn, Si, Zn, Cd and Hg. Barton. "Degradation and Modification Another area involved the preparation of Metallaboranes Part 3, Reactions of bimetallaboranes based on small metal- the Hexaborane(10) Analogue nido- laborane templates. To this end they (PPh3)2(CO)OsB5H9 with Bidentate have thus far concentrated on the tem- Phosphines Containing a Rigid Back- plates B H , B H , (PPh ) (CO)OsB H 5 9 6 10 3 2 5 9 bone: Formation of Linked Cluster Sys- and (PPh3)2(CO)IrB5H8 and prepared a series of species containing the metal- tems." J. Organometal. Chem. 2003, 688, 82. boron combinations IrFeB2, IrOsB3, LAWRENCE BARTON IrOsB4, OsRuB4, IrOsB5, IrPtB5, IrFeB5, Ir2B5, Zr2B5, Hf2B5, Ti2B6 and Pt2B7. O. Volkov, N. P. Rath and L. Barton, Professor Barton, B.Sc. (Hons) Liverpool "Metal insertion into the open face of an University 1961, Ph.D. 1964, did a post- Additional work on reactions of larger isonido-metallathiaborane cluster: For- doc at Cornell University and joined the cage metallaboranes and boranes with mation and characterization of [2-PPh3- faculty at UM-St. Louis in 1966. He small main group-containing molecules 2,3-Cl -2,3-(-Cl)-3,7-(-dppm)-closo- served as Department Chair from 1980 was a productive activity. For example 2 until 1998, Interim Director of the Center formation of metallaheteroboranes from 2,3,1-Rh2SB9H8] from [1-PPh3-{1,3-(- for Nanoscience from 1998-06, assumed reactions of the unsaturated clusters [8,8- dppm)}-closo-1,2-RhSB9H8]," Organo- Emeritus status in March 2007 and is no (PPh3)2-nido-8,7-RhSB9H10] and [9,9- metallics 2003, 22, 2548. longer taking students. (PPh3)-nido-9,7,8-RhC2B8H11] and reactions of phosphines with these species. L. Barton, O. Volkov, M. Hata, P. PPh 2 Related studies involving reactions of H McQuade and N. P. Rath, "Reactions of B H bases with small cage metallaboranes has boranes and metallaboranes with phos- PPh revealed some novel reaction mecha- C C 2 phines," Pure. Appl. Chem. 2003, 75, H Rh nisms and has led to the formation of 1165. H linked cluster systems and hybrid bimetallaboranes. Some of this work is illustrated herein. O. Volkov, Ramón Macías, N. P. Rath and L. Barton "Phosphine-boranes as Selected Publications bidentate ligands: Formation of [9,9-2- 2 { -(BH3)dppm}-nido-9,7,8-RhC2B8H11] O. Volkov, K. Radacki, R. Ll. Thomas, 2 2 Ir and [8,8- -{ -(BH3)dppm}-nido-8,7- Cl PPh2 N. P. Rath and L. Barton "Another look RhSB9H10] from [8,8-(PPh3)2-nido-8,7- Cl at the nido-undecaborate system," J. 2 1 S RhSB9H10 and [9,9-(h -dppm)-9-(h - H Rh Organomet. Chem. 2005, 690/11, 2736 dppm)-nido-9,7,8-RhC B H ],". Inorg. PPh 2 8 11 2 Chem. 2002, 41, 5837 P. McQuade, R. E. K. Winter, N. P. Rath

PPh2 PPh2 B PPh2 PPh2 H H Rh PPh Rh PPh2 2 B S PPh B S 3 H B H H CO Os H B PPh H 2 PPh PPh3 3 H H H H CO H H Os B PPh Fe B H 3 H H B H B B H + PPh Cl H B 2 H B H B Cp B  Cp H H H H H B Zr SiO2 B Zr B H Zr B H H Cp B H H H B Cp - [B11H14] H EMERITUS AND RESEARCH FACULTY statistical ratio of meso and rac forms Wiley, Chichester, United Kingdom, (1:1) exhibit a novel spontaneous isomer- 2014, Chap. 1, 1-38. ization of the rac-isomer to the meso- isomer. The meso-form can be returned J. Y. Corey, "Siloles: part 1: synthesis, to the statistical mixture by adding cata- characterization, and applications," Adv. lytic quantities of fluoride ion. The Organomet. Chem. 2011, 59, 1. spontaneous isomerization is a case of crystallization induced "asymmetric J. Y. Corey, "Siloles: part 2: silaindenes transformation" (AT) and is under cur- (benzosiloles) and silafluorenes rent investigation. (dibenzosiloles): synthesis, characterization, and applications," Adv. Organomet. Condensation of primary silanes with Chem. 2011, 59, 181 metallocene halides plus RLi provides polysilanes whose molecular weights J. Y. Corey, "Reactions of hydrosilanes vary with the structure of the metallo- with Transition Metal complexes and cene. The mechanism for this condensa- JOYCE Y. COREY characterization of the Products," Chem. tion process is not entirely clear but Rev. 2011, 111, 863 probably involves sigma-bond metathesis Professor Corey received her Ph.D. de- steps and possibly radical processes. gree at the University of Wisconsin fol- J. Y. Corey, K. A. Trankler, J. Braddock- Strategies that will lead to an increase in lowing a B.S. and M.S. at the University Wilking and N. P. Rath, "Reactions of molecular weight are under study and of North Dakota. She has held visiting (Et CH CH NEt ).H SiCl with Selected include modification of the basic metal- 2 2 2 2 2 2 faculty positions at the University of Diorganometallic Reagents of Magnesi- locene structure as well as the develop- Wisconsin, and the Universite des Sci- um and Lithium," Organometallics 2010 ment of new catalyst systems. Although ences et Techniques du Languedoc. She 29, 5708. earlier reports suggested that syndiotactic has been at UM-St. Louis since 1968. polysilanes were produced from metallo- Dr. Corey assumed emeritus status in J. Braddock-Wilking, Y. Zhang, J. Y. cene catalysts, our recent studies have 2008 and is no longer taking students. Corey and N. P. Rath "Preparation of 1,1 demonstrated that this is not the case and -disubstituted silacyclopentadienes," J. that the polymers are atactic. New chal- Research Interests Organomet. Chem. 2008, 693, 1233 lenges are to find catalysts that improve

the molecular weights and control the Unlike CH bonds in hydrocarbon chem- C. P. White, J. Braddock-Wilking, J. Y. microstructure of the polymer. istry, the SiH bond in hydrosilanes may Corey, H. Xu, E. Redekop, S. Sedinkin, be viewed as a functional group. How- and N. P. Rath, "Activation of Group 14 Metals from across the entire transition ever, transformations of SiH to other Si- El-H Bonds at Platinum(0)," Oganome- metal series will initiate a variety of reac- element bonds usually require a catalyst. tallics 2007, 26, 1996. tions of SiH bonds although not by the Typical coreactants are HEl species and same mechanism for electron poor met- if El represents another silicon unit, then J. Braddock-Wilking, J. Y. Corey, L. M. als vs. electron rich metals. In general homodehydrocoupling occurs to give French, E. Choi, V. J. Speedie, M. F. the earlier transition metals promote silicon oligomers and polymers with H2 Rutherford, S. Yao, H. Xu, and N. P. metathesis reactions whereas oxidative as the only by-product. Titanium triad Rath, "Si-H Bond Activation by (Ph P) addition of SiH to the metal probably 3 complexes are particularly effective for Pt(η2-C H ) in Dihydrosilicon Tricycles initiates the reactions with electron rich 2 2 4 this transformation. Silicon analogs of that also contain O and N Heteroatoms," metals. We are currently investigating substituted ethanes, propanes and bu- Organometallics 2006, 25, 3974. the reaction pathways of secondary tanes can be formed through the reaction silanes that are also heterocyclic silicon of secondary silanes such as PhMeSiH2 J. Braddock-Wilking, J. Y. Corey, K. A. compounds with electron rich metals in the presence of the combination, Trankler, H Xu, L. M. French, N. with the objectives of building [(Si-TM)] Cp2MCl2 (M = Ti, Zr, Hf) and n-BuLi. Praingam, C. White, and N. P. Rath, units (TM = transition metals; x >2) With the availability of this simple dehy- x "Spectroscopic and Reactivity Studies of and determining the primary reaction drogenative coupling reaction, the chem- Pt-Si Monomers and Dimers," Organo- events of these silanes. Studies also istry of short chains can be studied and metallics 2006, 25, 2859. include the reactions of the correspond- developed. Examples include the remov- ing germanes and stannanes as the ease al of phenyl groups in H(PhMeSi)xH J. Braddock-Wilking, J. Y. Corey, C. of oxidative addition increases through withl to x equivalents of triflic acid to White, H. Xu, and N. P. Rath, "Reaction give the corresponding silyl triflates, H the sequence Si < Ge < Sn. of Diphenylgermane with (Ph P) Pt(2- [(Ph) (OTf) Si Me ]H. Replacement of 3 2 x-y y x x C H ): Generation of Mono- and Dinu- the triflate group by reaction with a num- Selected Publications 2 4 clear Complexes Containing Pt-Ge ber of nucleophiles may then take place Bonds. X-ray Crystal Structure Determi- to provide new oligomers. Oligomers ″Synthesis of Siloles (and Germoles) that 2 nation of [(Ph P)Pt(- -H-GePh )] ," with fluorosilane end groups have also Exhibit the AIE Effect,″ J. Y. Corey, In 3 2 2 Organometallics 2005, 24, 4113. been prepared through reaction with Aggregation-Induced Emission: Funda-

CuF2 or CuCl2/KF/KI. The disilanes, F mentals; Qin, A., Tang, B. Z., Eds.

(PhMeSi)2F, which are formed as the THE FACULTY tives to commercial products and other (Book review) "Entropy Demysti- inventive ways to teach chemistry fied" (Arieh Ben-Naim) J. Chem. Educ. through laboratories and demonstrations. 2009, 86 1037. The feature was discontinued when JCE became co-published with the ACS and B. P. Coppola, C. B. Frech, H. H. Harris the Division of Chemical Education, but and R. M. Pagni, "Summer Reading" J. Professor Harris continues to review and Chem. Educ. 2009, 86, 792 edit articles with similar characteristics that appear intermittently in the Journal. H. H. Harris "Feature Editor's Comments

and Editor's Note Prefacing Electronic For nearly twenty years, Professor Harris HAROLD H. HARRIS taught and advised all of UMSL’s stu- Homework Management Systems: Re- dents seeking certification to teach either views of Popular Systems" J. Chem. Professor Harris received his B.S. degree chemistry or physics in Missouri high Educ. 2009, 86, 691 from Harvey Mudd College, and his schools, and has worked closely with the Ph.D. from Michigan State University. science teachers in many of the region’s (Book review) "Introduction to Molecu- He joined the UM-St. Louis Chemistry school districts. His work has been hon- lar Thermodynamics" (Robert M. Han- faculty in 1970 following a postdoctoral ored with the St. Louis Area Physics son and Susan Green) J. Chem. Educ. fellowship at the University of California Teachers’ “Gene Fuchs Memorial -Irvine. He has spent leaves at University Award” and the St. Louis Academy of 2008, 85, 1349 of Chicago, the Solar Energy Research Sciences’ “Science Educator of the Year Institute (Golden, Colorado), and Wright 2010”. B. P. Coppola, C. B. Frech, H. H. Harris -Patterson Air Force Base (Dayton, and R. M. Pagni, "Summer Reading," J. Ohio). In fall 2012 he was appointed With his appointment as a Founders Chem. Educ. 2008, 85, 904 Founders' Professor of Chemistry and Professor, Harris will be teaching a lim- Biochemistry. ited selection of courses in physical and H. H. Harris, R. M. Pagni, C. Frech, B.

introductory chemistry. Coppola and J. Kovac, "Summer Read- Research Interests ing," J. Chem. Educ. 2007, 84, 916.

Selected Publications Professor Harris has published in diverse M. E. Harris and H. H. Harris, "Sorting areas of physical chemistry and chemical Recycled Trash: An Activity for Earth (Book Review) “Essentials of Chemical education, including experimental stud- Day 2007" J. Chem. Educ. 2007, 84, Education” by Hans-Dieter Barke, Gün- ies of collision-induced dissociation of 204. ther Harsch, and Siegbert Schmid, trans- ions, chemical kinetics at suprahigh pres- lated by Hannah Gerdau, J. Chem. sure, experimental and theoretical dy- (Book review) H. H. Harris, "Fritz Ha- Educ., 2012, 89 (11) (in press). namics of molecular collisions, spectros- ber: Chemist, Nobel Laureate, German, copy in supersonic jets, and the dynamics Jew: A Biography (Dietrich Stoltzen- C. B. Frech, B. P. Coppola, H. H. Harris, of cellular flames. berg)," J. Chem. Educ. 2006, 83, 1605. and C. M. Woodbridge, “Summer 2012 He originated and managed for nearly Book and Media Recommendations” J. (Book review) "Elegant Solutions: Ten twenty years “The Chemical Education Chem. Educ., 2012, 89 , 825 Beautiful Experiments in Chemistry Resource Shelf”, a unique bibliographic (Philip Ball) J. Chem. Educ., 2006, 83, resource for textbooks and software, for H. H. Harris, "Review of Selected Prob- 41. the Journal of Chemical Education. This lems in Physical Chemistry: Strategies archive provided information about over and Interpretations," J. Chem. Educ. H. H. Harris and M. E. Harris, "Hands on 1600 chemistry textbooks and their pub- 2011, 88, 1457. Plastics" J. Chem. Educ. . 2005 82 209. lishers, as well as sources for molecular models, computer interfacing of experi- C. B. Frech, B. P. Coppola, H. H. Harris L. Y. Mao, H. H. Harris and K. J. Stine, ments, and chemistry software. Associat- and C. M. Woodbridge, "Summer 2011 "Simple Lattice Simulation of Chiral ed with the Resource Shelf was “Hal’s Book and Media Recommendations," J. Discrimination in Monolayers" J. Chem. Picks of the Month”, his recommenda- Chem. Educ. 2011, 88, 851. Inf. Comp. Sci. 2002, 42, 1179. tion of books and articles of interest to teachers of science. Over the years, well H. H. Harris, (Book Review) "Absolutely over two hundred items have appeared in Small" (Michael D. Fayer) J. Chem. this feature, which is archived and con- Educ. . 2010 88, 145. tinues with his “Picks” in JCE ChemEd Xchange, http://www.chemedx.org. (Book Reviews) Cheryl Frech, Hal Har- Professor Harris also edited over one ris, C. M. Woodbridge, and Brian Cop- hundred articles for his “Cost-Effective pola "Summer 2010 Books and Media Teacher” feature of the Journal of Chem- Recommendations" J. Chem. Educ. ical Education. This feature emphasized 2010, 87, 665 the construction of economical alterna- EMERITUS AND RESEARCH FACULTY

drugs and other compounds in organic Research Interests solvents," J. Pharm. Sci. 2010, 99, 1500. Q. Wang, R. E. Robert R. Luchtefeld, A. Dr. Luo's research interests involve the Y. Sun, A. Simonyi, R. Luo and G. Y. use of NMR techniques for generating Sun, "Bioavailability of apocynin through three-dimensional structural and dynam- its conversion to glycoconjugate but not ical information on biological macromol- to diapocynin," Phytomedicine 2008, 15, ecules, organic compounds, and organo- 496 metallic complexes. NMR is being in- creasingly applied in chemistry, biochem- M. S. Dasari, K. M. Richards, M. L. Alt, istry, biology, medicine, physics and ma- C. F. P. Crawford, A. Schleiden, J. In- terials science. Currently, Dr. Luo is the gram, A. A. A. Hamidou, A. Williams, P. Director of the Nuclear Magnetic Reso- A. Chernovitz, R. Luo, G. Y. Sun, R. nance Facility. Current research interests Luchtefeld and R. E. Smith, "Synthesis of RENSHENG LUO also include collaboration with scientists diapocynin," J. Chem. Ed. 2008, 85, 411. in solving problems on all these and relat- rmation Professor. Luo received his Ph.D. degree ed subjects using NMR spectroscopy, as from the Chinese Academy of Sciences. well as development of techniques and R. Luchtefeld, R. Luo, K. J. Stine, M. L. He was a Postdoctoral Fellow at the Uni- implementation of new NMR experiments Alt, P. A. Chernovitz and R. E. Smith, versity of Illinois at Champaign-Urbana for users at different areas. "Formulation and Analysis of Diapocyn- and St. Jude Children’s Research Hospital in," J. Ag. Food Chem, 2008, 56, 301 prior to joining the UM-St. Louis faculty Selected Publications as Research Assistant Professor in the J. B. Jordan, H. Kovacs, Y. Wang, M. Spring of 2005 and promoted to Research R. Luo, K. Tran, R. A. Levine, S. M. Mobli, R. Luo, C. Anklin, J. C. Hoch, and 13 Associate Professor in 2013.. Nickols, D. M. Monroe, A. U. O. Sabaa- R. W. Kriwacki, "3D C-detected CH3- Srur and R. E. Smith, "Distinguishing TOCSY for selectively protonated pro- Components in Brazilian Acai (Euterpe teins: Facile resonance assignment and oleraceae Mart.) and in Products Obtained global fold determination," J. Am. Chem. in the USA by Using NMR," The Natural Soc., 2006, 128, 9119 Products Journal, 2012, 2, 86 S. W. Buckner, M. J. Fischer, P. A. R. E. Smith, J. Eaker, K. Tran, C. Smith, Jelliss, R. Luo, S. D. Minteer, N. P. Rath, D. M. Monroe, E. M. da Silva Menezes, and A. Siemiarczuk, "dual Fluorescence III A. U. O. Sabaa-Srur, R. Luo, W. Wycoff from an Isonido Re Rhenacarborane and W. H. Fales, "Proposed Benchmark Phosphine Complex, [7,10-µ-H-7CO-7,7- Methods for Analyzing Acai (Euterpe (PPh3)2– isonido-7,8,9-ReC2B7H9]," Inorg. oleraceae Mart.)," The Natural Products Chem., 2006, 45, 7339. Journal, 2012, 2,76 R. Luo, B. Mann, W. S. Lewis, A. Rowe, M. H. Abraham, R. E. Smith, R. R. Heath, M. L. Stewart, A. E. Hamburg- Luchtefeld, A. J. Boorem, R. Luo and W. er, S. Sivakolundu, E. R. Lacy, P. J. E. Acree, Jr., "Prediction of solubility of Bjorkman, E. Tuomanen, and R. W. Kri- wacki, "Solution structure of choline binding protein A, the major adhesion of Streptococcus pneumoniae," The EMBO J., 2005, 24, 1, 34

R. Luo, B. Mann, E. Tuomanen, and R. W. Kriwacki, "NMR assignment of the R2 domain of pneumococcal choline binding protein A (CbpA)," J. Biomol. NMR, 2005, 32, 93.

Y. Wang, I. Filippov, C. Richter, R. Luo, R. W. Kriwacki, "Solution NMR studies of an intrinsically unstructured Protein within a dilute. 75 kDa eukaryotic protein assembly; probing the practical limits for efficiently assigning polypeptide backbone resonances," Chembiochem., 2005, 6, 2242.

EMERITUS AND RESEARCH FACULTY

Selected Publications Br): involvement of palladium(II) and palladium(IV) intermediates," J. Luo, N. ″One pot synthesis of imidazo[2,1-b] P. Rath, and L. M. Mirica, Organometal- thiazoles and benzo[d]thiazolo[3,2-a] lics 2013, 32, 3343 imidazoles″, N. A. Mir, T. A. Shah, S. Ahmed, M. Muneer, N. P. Rath and M. "Late First Row Transition Metal Com- Ahmad, Tet. Lett, 2014, 55, 1706 plexes of a Tetradentate Pyridinophane Ligand: Electronic Properties and Reac- ″New bis(imino)pyridine complexes of tivity Implications," J. R. Khusnutdino- iron(II) and iron(III), and their catalytic- va, J. Luo, N. P. Rath and L. M. Mirica, activity in the Mukaiyama aldol reac- Inorg. Chem. 2013, 52, 3920 tion″, P. Shejwalkar, N. P. Rath and E. B. Bauer, Synthesis, 2014, 46, 57 "Role of Substitution at Terminal Nitro- gen of 2-Oxo-1,2-dihydroquinoline-3- "Ruthenium complexes of the general Carbaldehyde Thiosemicarbazones and formula [RuCl2(PHOX) 2] and their cata- the Coordination Behavior and Structure NIGAM P. RATH lytic activity in the Mukaiyama aldol and Biological Properties of Their Palla- reaction," N. Curvey, A. K. Widaman, dium(II) Complexes," E. Ramachandran, Professor. Rath received B.Sc. (Hons.) N. P. Rath and E. B. Bauer, Tetrahedron D. R. Senthil, N. P. Rath and K. Nata- and M.Sc. degrees from Berhampur Uni- Lett. 2014, 55, 3033. rajan, Inorg. Chem. 2013, 52, 1504. versity in India, and a Ph.D. from Okla- homa State University. He was a Post- ″Syntheses, characterization, and struc- E. Evangelio, N. P. Rath and L. M. Miri- doctoral Fellow and Assistant Faculty tural studies of copper(I) complexes ca, "Cycloaddition reactivity studies of Fellow at the University of Notre Dame containing 1,1′-bis(di-t-butylphosphino) first-row transition metal-azide complex- prior to joining the UM-St. Louis faculty ferrocene (dtbpf) and their application in es and alkynes: an inorganic click reac- as Research Assistant Professor in 1989. palladium-catalyzed Sonogashira cou- tion for metalloenzyme inhibitor synthe- He was promoted to Research Associate pling of aryl halides″ M. Trivedi, G. sis," Dalton Trans. 2012, 41, 8010. Professor in 1996 and a Research Profes- Singh, A. Kumar and N. P. Rath, 2014, sor in 2004. 43, 13620

Research Interests ″Synthesis and Characterization of Pt(II) and Pd(II) PTA and DAPTAcomplexes″, Dr. Rath is a X-ray crystallographer and J. Braddock-Wilking, A.Sitaram and N. he directs the X-ray diffraction facility. P. Rath, Polyhedron 2014, 79, 16. The use of single crystal X-ray diffrac- "A thiocynato-bridged copper(i) cubane tion studies can result in the most unam- complex and its application in palladium- biguous structural information and threes catalyzed Sonogashira coupling of aryl dimensional structure of both small halides,"M. Trivedi, G. Singh, A. Kumar molecules and macromolecules. Dr. Abhinav and N. P. Rath, Dalton Trans. Rath’s research interests involve the use 2013, 42, 12849. of X-ray diffraction techniques for the determination of solid state-molecular Oxidative reactivity of (N2S2)PdRX Neutral Pt Square structure of novel organic and organome- complexes (R = Me, Cl; X = Me, Cl, tallic compounds. His interests also include development of techniques and instrumentation for accurate data collection for small molecules.

Fenofibric Acid EMERITUS AND RESEARCH FACULTY R. Li, R. E. K. Winter, J. Kramer and G. W. Gokel, "Alkali metal and ammonium J. Bould, A. Laromaine, C. Viñas, F. cation-arene interactions with tetra- Teixidor, L. Barton, N. P. Rath, R. E. K. phenylborate anion," Supramolec. Chem. Winter, R. Kivekäs, R. Sillanpää. "The 2010, 221-2, 73. First Derivatives of [NHMe3][-HMeCC (Me)-B10H10]." Organometallics 2004, P. A. Jelliss, S. D. Minteer, M. Patel, A. 23, 3335 Siemiarczuk,M. Watt, Michelle and R. E. K. Winter, "Unique properties of a per- J. N. Swamy, R. E. K. Winter, C. R. fluoroalkyl-modified 2,2'-bipyridyl ru- Jeffreys and V. T. D'Souza, "Synthetic thenium complex in a Nafion membrane: methodology for cyclodextrin- attenuated leaching of a potential biofuel dipyrromethane conjugates," Tet. Lett., cell redox mediator" J. Mat. Chem. 2008, 2004, 45, 7595. RUDOLPH ERNEST K. WINTER 18, 2104. C. M. Ranger, R. E. K. Winter; E. A. Professor Winter received his A.B. de- L. You, R. Ferdani, R. Li, J. P. Kramer, Backus, G. E. Rottinghaus, M. R. gree from Columbia University and M.S. R. E. K. Winter and G. W. Gokel, Ellersieck and D. W. J.son, "Glandular and Ph.D. degrees from The Johns Hop- "Carboxylate anion diminishes chloride trichome extracts from Medicago sativa kins University. He held postdoctoral transport through a synthetic, self- deter settling by the potato leafhopper positions at Karlsruhe Technische assembled transmembrane pore," Chem.- Empoasca fabae," J. Chem. Ecol. 2004, Hochschule and Harvard University and -A Eur. Journal 2008, 14, 382. 30, 927 was a member of the Polytechnic Insti- tute of Brooklyn faculty before joining R. Ferdani, R. Li, R. Pajewski, J. Pajew- P. McQuade, R. E. K. Winter and L. U. M. St. Louis in 1969. He has been a ska, R. E. K. Winter and G. W. Gokel, Barton, "Degradation and Modification Visiting Research Professor at Cornell "Transport of chloride and carboxyfluo- of Metallaboranes Part 3, Reactions of University, Visiting Scholar at the ETH rescein through phospholipid vesicle the Hexaborane(10) Analogue nido- Zürich and was also a Visiting Associate membranes by heptapeptide am- (PPh3)2(CO)OsB5H9 with Bidentate Professor (Biology) at Washington Uni- phiphiles." Org. Biomolec. Chem., 2007, Phosphines Containing a Rigid Back- versity (St. Louis) and now enjoys emeri- 5, 2423. bone: Formation of Linked Cluster Sys- tus status at UM-St. Louis. tems," J. Organomet. Chem. 2003, 688, C. M. Ranger, R. E. K. Winter; E. A. 82 Research Interests Backus, G. E. Rottinghaus, M. R. Ellersieck and D. W. J.son, D. Milanowski, R. E. K. Winter; M. P. F. Dr. Winter's research interests are in the "Discrimination by the potato leafhopper Elvin-Lewis and W. H. Lewis, Organic and Bioorganic Chemistry of (Hemiptera: Cicadellidae) of host vola- "Geographic distribution of three alka- naturally occurring substances. Empha- tiles from resistant and susceptible alfal- loid chemotypes of Croton lechleri," J. sis is on the isolation, structure determi- fa, Medicago sativa L" Envir. Entomol. Nat. Prod. 2002, 65, 814. nation and chemical interconversion of 2005, 34, 271. natural products of biological interest. "Wound-Healing Composition and He also has major interests in the appli- C. M. Ranger, R. E. K. Winter; E. A. Method ," R. E. K. Winter, A. L. Okun- cation of mass spectrometry for charac- Backus, G. E. Rottinghaus, M. R. de, M. P. F. Elvin-Lewis, W. E. Lewis terization and structure determination Ellersieck and D. W. J.son, "Mass spec- and A. Kasiri (WoundFast Pharmaceuti- and collaborates with faculty colleagues tral characterization of fatty acid amides cals assignee), U. S. Patent Number on those problems related to their re- from alfalfa trichomes and their deter- 5932617, Aug 3, 1999. search which are amenable to mass spec- rence against the potato leafhopper." tral measurements. Phytochemistry 2005, 66, 529. "On Guaiol Oxygenation Products," R.E.K. Winter, J.A. Baker, B.V. Lam, Selected Publications P. McQuade, R. E. K. Winter, N. P. Rath A.G. Breite and Nigam P. Rath, Natural and L. Barton. "Degradation and Modifi- Products Letters, 1997, 10, 105. C. M. Ranger, R. E. K. Winter, A. P. cation of Metallaboranes Part 4: Synthe- Singh, M. E. Reding, J. M. Frantz, J. C. sis and Characterization of a series of J. Y. Corey, A. J. Pitts, R. E. K. Winter Locke, and C. R. Krause, "Rare excitato- hybrid bimetallaborane clusters of the and N. P. Rath, "Synthesis and character- ry amino acid from flowers of zonal type [2,2,2-(PPh3)2(CO)-nido-2-OsB4H7- ization of 1,9-difluoro-5-methyl-5- geranium responsible for paralyzing the 3-(BH2PPh2)CxHyPPh2RuCl2(p-cym)]." phenyl-10,11-dihydro-5H-dibenzo[b,f] Japanese beetle," Proc. Nat. Acad. .Sci, Inorg. Chim. Acta. 2005, 358/5, 1545. silepin," J. Organomet. Chem. 1995, 2011 108, 1217. 499, 113. C. M. Ranger, R. E. K. Winter; E. A. C. R. Yamnitz, S. Negin, I. A. Carasel, Backus, G. E. Rottinghaus, M. R. E. J. Kennelly, W. H. Lewis, R. E. K. R. E. K. Winter and G. W. Gokel, Ellersieck and D. W. J.son, "Bioactivity Winter, S. Johnson, M. Elvin-Lewis and "Dianilides of dipicolinic acid function of Lipophilic Metabolites from Glandu- J. Gossling, "Triterpenoid saponins from as synthetic chloride channels," Chem. lar Trichomes of Medicago sativa Gouania lupuloides." J. Nat. Prod. 1993, Commun. 2010, 2838. Against the Potato Leafhopper" J. 56, 402. Chem. Ecol. 2004, 30, 1969. INSTRUMENTATION AND FACILITIES

High Field NMR Facility Two probes are available: a 5-mm three channel inverse gradient broadband and a 5-mm gradient broadband, each of which is capable of variable temperature ex- o The UM-St Louis High Resolution NMR periments (-80 to +130 C). This spectrometer is a research-oriented instrument Facility is located in the Department of and primarily used to investigate the structures and dynamics of macromolecules Chemistry and Biochemistry on the sec- and complex molecular systems as well as implement new NMR experiments for users at different areas. The instrument specifications include: ond floor of Benton Hall (B210) and houses three NMR spectrometers: a  The Agilent preminumCOMPACT magnet (54mm bore) Bruker ARX-500, a Bruker Avance 300  Dell PC with Red Hat Linux and a Varian Unity Plus 300. While  1H-19F/15N-31P, 15N/13C 5mm PFG triple OneNMR probe these instruments are primarily for the 1H-19F/15N-31P 5mm PFG autoX indirect detection probe use of the faculty, postdoctoral, and stu-  dents in the Department of Chemistry and  ProTune accessory Variable temperature capability (-80oC to +130oC) Biochemistry, other users (corporate  other universities, and organizations) are Bruker ARX 500 MHz NMR welcome. The facility staff will provide

NMR services as needed. For more infor- The Bruker ARX-500 spectrometer is operated by a Silicon Graphics INDY mation please contact to Dr. Rensheng R5000 workstation. It has two probes: a 5 mm broadband and a 5 mm inverse Luo at (314) 516-5330. gradient broadband, each of which is capable of variable temperature experiments

(-150 to + 200 ºC for liquids). The Bruker ARX-500 spectrometer is a research- Agilent DD2 600 MHz NMR oriented instrument. It is equipped with dual radiofrequency channels and used With support from NSF MRI-R2 grant for molecules requiring better peak resolution, (complex) structure elucidation (0959360), an Agilent DD2 600 MHz and variable temperature analyses on a wide range of organic, organometallic, NMR spectrometer was purchased and inorganic, and biochemical systems, as well as natural products and host-guest installed in Benton Hall B207 in early systems. Experiments that are typically performed include 2D COSY, NOESY, 2012. This spectrometer is operated by a ROESY, TOCSY, HSQC, HMQC, HMBC and selective excitation. Linux PC with VnmrJ 3.2 software. Bruker Avance 300MHz NMR The Avance 300 spectrometer is currently equipped with a four-nucleus probe (1H, 13C, 19F, and 31P) with z-gradients. An additional 5 mm switchable broadband probe tunable for 1H-19F/15N -31P is also available. This instrument is used primarily for routine walk-on use for monitoring reactions and checking the puri- ty of samples, but it is also used for longer run experiments such as 1D 13C and routine 2D experiments: HMQC, HSQC, and HMBC in the evening and weekends.

Varian Unity Plus 300 MHz NMR The Varian Unity Plus 300 is equipped with a wide bore Oxford superconducting magnet to accommodate probes for running solid state NMR experiments. It has two radiofrequency channels and is capable of broadband detection. This instrument is used primarily for detection of heteronuclei such as 11B, 13C, 31P, 119Sn, and 195Pt, experiments that require long detection time. It has four probes: two 5 mm switchable broadband probes with boron-free glass insert, a 5 mm switchable inverse broadband probe, and a 7 mm magic angle probe for CP-MAS experiments.

INSTRUMENTATION AND FACILITIES

X-ray Diffraction Laboratory Single Crystal X-ray Diffraction Instrumentation

X-ray crystal structure determination is The Bruker APEX II Kappa diffractometer is equipped with an Oxford an important technique for most inorgan- Cryostream low temperature device. Fast data collection can be carried out using ic and organic chemists. The X-ray Dif- this Kappa geometry diffractometer at 10-330K. Currently, most of the structure fraction Laboratory at UM-St. Louis determinations are carried out using this system. supports the research programs of several research groups in the department. Also, we collaborate with a number of groups in the metropolitan St. Louis area and across the USA and in other coun- tries in their solid-state structure determination research. The Laboratory is equipped with state-of-the-art instrumentation and computational facilities for solid state three dimensional crystal and molecular structure determinations. The facility is located in custom-designed laboratory space in the Center for Nano- science, opened in November 1996, and currently houses single crystal and powder diffractometers. For more information please contact Dr. Nigam Rath at (314) 516-5333 or by email: [email protected]

Bruker Kappa Apex II Single Crystal Diffractometer

The Bruker SMART APEX II Diffractometer: This CCD (Charge Coupled Device) area detector system was upgraded recently to the state of the art Apex II detector equipped with a 4K CCD chip and Oxford Cryostream low temperature device for use in small molecule crystallography. Currently, this instrument is primarily used for teaching and training of students and Post-doctoral researchers as well as for data collection by users.

Powder Diffraction Instrumentation

A Rigaku Ultima IV Powder Diffractometer is used primarily for bulk material characterization, including air- and moisture-sensitive samples. This provides a Bruker SMART Apex II Single valuable analytical tool for the identification of single and multi-component sol- Crystal Diffractometer ids by comparison with known published powder patterns. It is also used to de- termine the homogeneity of crystalline samples from which single crystals have been used for crystal structure determination. This instrument is also capable of data collection for small angle x-ray scattering (SAXS) experiments.

Computer Facilities and Other Instrumentation

The X-ray Laboratory Computing Facility has several workstations running crystallographic software. All computers in the lab are integrated with the university computer network. The Cambridge Structural Database is accessible to all university computer system users and is hosted through a Sun server and installed on all PCs.

The preparation laboratory is equipped with stereo microscopes for screening and mounting crystals; a fume hood, refrigerator and freezer for crystallization and Rigaku Ultima IV Powder sample storage, together with other necessary facilities for crystallization and Diffractometer crystal handling. INSTRUMENTATION AND FACILITIES

Mass Spectrometry Facility

The mass spectrometry facility is housed in a 1000 sq ft laboratory located in the UMSL Research Building (R003). In addition to the mass spectrometers described below, there are areas for data processing, instrument maintenance, parts storage and sample preparation. The instrumentation is used primarily for support of research and teaching in the Department of Chemistry and Bio- chemistry, however in years past the MS facility has been a resource for the local business or members of the academic community which lack this instrumentation.. For more information contact Mr. Joseph Kramer: Tel: (314) 516-5120; e- mail: [email protected]

JEOL MStation [JMS-700] Mass Spectrometer

A high-performance magnetic sector mass spectrometer for both high and low resolution mass spectral analysis equipped for:  Fast Atom Bombardment (FAB) ionization, Electrospray Ionization (ESI),  Atmospheric Ion Chemical Ionization (APCI) and EI and CI methods  Positive and negative ion detection  Linked scan measurements

MALDI Micro MX by Micromass/ Waters. This has a mass range >60,000 and resolution 50 µmass

Hewlett Packard GC/MS System Mod- el 5988A Shimadzu 2010A LCMS

For routine mass spectral analysis follow-  LCMS System with 4 solvent pumps, column oven, diode array detector and ing capillary column gas chromatograph- single quad mass-spec. ic (GC) separation with:  Positive and Negative Ion Detection  Electron impact (EI) and chemical ionization (CI) capabilities Bruker Maxis Plus (maXis HD) quadrupole time-of-flight mass spectrometer  Positive and negative ion detection and UHPLC. It comes with Electrospray ionization, atmospheric pressure pho-  An extended-mass quadrupole toionization and a solids probe for ionizing solids directly. It can do m/delta m =  A solids probe 60,000 and collect up to 20 spectra per sec. (Available in Dr. Bythell’s Lab)

INSTRUMENTATION AND FACILITIES

Molecular Modeling and Simulation Software developed or enhanced by UMSL researchers SRmapper: A program for assembling whole genome sequences from next- Computational scientists at UMSL per- generation sequencing experiments. It aligns short reads from such experiments form molecular modeling and simulation to reference genomes. It takes short reads data in fastq format and outputs results to understand chemical and biological in SAM format for analysis by programs such as SAMtools. systems, and to design new materials such as molecular magnets, chemical and UHBD: New features introduced by UMSL researchers and their collaborators biological sensors, and therapeutic include the interface with two quantum mechanical programs — PWSCF and drugs. They also use bioinformatics SIESTA — to perform quantum mechanical calculations in solutions in which tools in drug discovery, in associating solvation effects are described by the Poisson-Boltzmann model, constrained genetic variations with diseases, and in Brownian dynamics simulation of peptides, and charge optimization at the inter- disease diagnostics. The computer labor- face between a protein and a ligand. atories are located in the Center for Na- noscience, next to Benton Hall in which BDI: A program for performing Brownian dynamics simulation of ions surround- the office of the Department of Chemistry ing proteins and DNAs. and Biochemistry is located. The labora- MMTSB toolkit: UMSL researchers have modified this toolkit to perform flexi- tories are equipped with Dell work- ble ligand-flexible receptor docking using a simulated annealing cycling strategy. stations for fast computations and molecular visualization. Computational inten- Other software packages sive calculations are done in the computer clusters in The University of Missouri UMSL computational scientists also use other programs such as: Bioinformatics Consortium. For more information please contact Dr. Chung  Quantum mechanics: Gaussian 03, SIESTA, GAMESS, PWSCF, NWChem. Wong at (314) 516-5318 or [email protected].  Molecular dynamics simulation: CHARMM, NAMD.

 Electrostatics calculations: APBS.  Genomics: BWA, Crossbow, Maq, SAMtools.  Protein modeling: MODELLER

Computer Cluster Clark

An SGI Altix 3700 Bx2 containing 64 Computer Cluster Lewis 1.5GHz Itanium2 processors, 128 GB

RAM, and 4 TB SGI InfiniteStorage. It It contains more than 190 nodes with over 1200 Intel Xeon multi-core processors is operated by the University of Missouri and a collective memory of 5100 GB. The largest computer nodes contain 24 Bioinformatics Consortium, who provid- processor cores and 512 GB of memory. Pictures provided by the University of ed this picture. Missouri Bioinformatics Consortium. INSTRUMENTATION AND FACILITIES

Cell Culture Facility

Cell culture is an important tool for understanding basic biological processes and for analysis of compounds that may have therapeutic potential in a variety of human diseases. The department established a secure cell culture laboratory in 2007 in the Research building. The facility is utilized by multiple users who main- tain and employ numerous mammalian and insect cell lines for research purposes. The facility currently houses three laminar flow hoods, a refrigerator/freezer, a manual defrost freezer, three water- jacketed carbon dioxide incubators, a liquid nitrogen cryosystem, a swinging bucket centrifuge, a multi-mode absorb- ance/fluorescence plate reader with computer, and two inverted microscopes (one with an attached digital camera). The facility is completely outfitted with all necessary items to support cell culture. Regular users of the facility attend semi- annual meetings regarding maintenance of the facility. The multi-user format fosters collaboration, the sharing of research ideas and troubleshooting.

Current cell culture users

Nichols Lab (Chemistry and Biochemistry) Alzheimer’s disease, inflammation, monocyte and microglial cells, neurons Bashkin Lab (Chemistry and Biochemistry) Human papilloma virus, therapeutics, epithelial cells Dupureur/Spilling Lab (Chemistry and Biochemistry) Diabetes, inhibitors/therapeutics, expression of proteins in SF9 insect cells Olivas Lab (Biology) Parkinson’s disease, neurons Steiniger Lab (Biology) Expression of proteins in SF9 insect cells

The Center for NanoScience

The Center for NanoScience (CNS) at the 11,300 square feet for research laborato- Members of the Center currently in- University of Missouri-St. Louis was ries and 2,700 square feet for research clude the following Chemistry Depart- established to both facilitate collabora- support space. In addition, there are 14 ment faculty members. L. Barton, J. K. tion among university and industry scien- offices, and a conference room. The Bashkin, A. M. Beatty, J. Braddock- tists and engineers and provide interdis- CNS also houses the Microscopy Image Wilking, C. M. Dupureur, T. F. ciplinary opportunities for faculty and and Spectroscopy Technology (MIST) George, G. W. Gokel. S. M. Holmes, J. students. Its mission is to enhance the Lab and the X-ray Diffraction Facility. Liu, M. R. Nichols, J. J. O'Brien, N. P. research capacities of its faculty members Rath, C. D, Spilling, K. J. Stine, C. F and students and serve the region Located in the William L. Clay building, Wong and Z. Xu. through research and technology trans- the Center had its beginnings in a feder- fer, cooperative and educational outreach al grant proposal initiated in 1988 by M. programs and workforce development. Thomas Jones, chemistry professor and For more information please contact deputy chancellor. The CNS facility Kendra Perry Ward at (314) 516-4626 or took real shape with the help of Con- [email protected]. gressman William L. Clay and his support of a $10 million funding proposal that was awarded in July 1991 -- $7.5 million was used for building construction and $2.5 million was used for research instrumentation and building furnishings. The building, named in honor of Congressman Clay, was completed in early summer 1997.

Originally named the Center for Molec- ular Electronics, the facility was re- named as the Center for Nanoscience in early 2007 to better encompass the research being conducted by members. A new director, and associate director were hired in 2006 to help facilitate the goals of the Center. Dr. Gokel serves as Director and Dr. Eric Majzoub serves a Associate Director. Single platinum atoms (yellow balls and three bright spots in TEM image) on iron oxide The CNS has approximately 16,000 (purple and gray) mediate conversion of CO square feet of assignable space, including to CO2. This photograph shows the Jefferson National Expansion Memorial, also known as the Gateway Arch or simply the arch, which is located near the starting point of the Lewis and Clark Expedition on the Mississippi River

How to apply to our graduate program

For admission to our graduate program you must apply online on the Department website found at: http://www.umsl.edu/chemistry/

Follow the link to Graduate Program and the instructions are provided. For further information (or an information packet) please contact the department at:

Graduate Admissions Phone 1-314-516-5311 Department of Chemistry and Biochemistry University of Missouri-St. Louis St. Louis, MO 63121-4499, USA

Email: [email protected]

The website contains links to: The Ph.D. Program The M.S. Programs Graduate Brochure Biochemistry Division Handbook Graduate Study Handbook

Current graduate students should address any queries to: Director of Graduate Studies Dr. Ste- phen M. Holmes. Applicants should recognize that, normally, emeritus and research professors do not take doctoral students.