Biochemistrychemistry &

A n A ly t i c A l

B i o l o g i c A l

i n o r g A n i c

o r g A n i c

P h y s i c A l

2010–2011

w w w . c h e m . s c . e d u

tA B l e o f c o n t e n t s

The University of South Carolina ..........................1

Department of Chemistry and Biochemistry ....2

The Graduate Program in Chemistry and Biochemistry .........................................................3

Ph.D. Profiles ................................................................4

Research Facilities .......................................................6

Faculty and Research Interests ...............................9

Seminar Program .......................................................41

Society for the Advancement of the Chemical Sciences ........................................41

Financial Support ...................................................... 42

Student Services ....................................................... 43

Recreational and Cultural Opportunities......... 44

c o v e rThe cover picture shows well-defined cobaltocenium-containing polymers and their self-assembly into nano-tubes, which can find applications as sensors or as templates for catalytic nanoparticles, nanolithography, etc. This figure was designed by Dr. Lixia Ren, Christopher Hardy, and Profes-sor Chuanbing Tang at the Depart-ment of Chemistry and Biochemistry of the University of South Carolina.

D e PA r t m e n t h i g h l i g h t s

P e o P l e• We maintain a friendly and highly collabora-tive research environment.

• We currently have 30 active research faculty members, 30 postdoctoral and other senior researchers, 130 graduate stu-dents, and 23 staff members.

r e s e A r c h• We were recently ranked 17th in

the nation in the production of Ph.D. chem-ists and 34th in the nation in total dollars spent on research.

• We publish approximately 120 research papers every year.

f A c i l i t i e s• We occupy the $36-million Graduate Science Research Center, dedicated in 2000.

• Research facilities include the Nuclear Magnetic Resonance Center, the Mass Spectrometry Laboratory, the X-ray Diffraction Facility, and the College of Arts and Sciences Stockroom. The Electron Microscopy Center is located in an adjacent building.

l o c At i o n• Columbia is one of the nation’s “10 most livable mid-sized cities” according to the Partnership for Livable Communities, with a metro area population of more than 700,000.

• Kayaking, boating, hiking, and bicycling are popular outdoor pastimes. Metropolitan Columbia has three major rivers running through it and has been listed as one of the top 10 canoe towns in the country by Paddler Magazine. The Appalachian Mountains are a three-hour drive, and the Atlantic Ocean is just two hours away.

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t h e U n i v e r s i t y o f s o U t h c A ro l i n A

Chartered in 1801 as South Carolina College, the University of South Car-olina was the first state university supported continuously by annual state appropriations. By the 1850s, it had achieved a reputation as one of the best endowed and most distinguished colleges in the United States. Hard hit by the Civil War and Reconstruction, the school struggled for many years to survive.

Its renaissance as a modern university began in the 1950s. Since then, dynamic academic expansion has produced highly diverse and innovative educational programs. A commitment to graduate education and involvement in major research initiatives have attracted an outstanding faculty. Today, in addition to the Columbia campus, the University includes seven other campuses around the state. Enrollment on all campuses totals more than 43,000. Of these, more than 27,000 students are on the Columbia campus, about one-third of whom are enrolled in graduate and professional programs.

The University offers myriad degree programs, including master’s degrees in 124 areas, Ph.D. degrees in 63 fields, and first-professional degrees in law, medicine, and pharmacy. Many programs are nationally and internationally ranked. Graduate courses are also offered at more than 50 sites throughout the state through Distance Education, on the Columbia campus. More than 1,500 master’s degrees and about 270 Ph.D. degrees are awarded annually.

USC libraries hold more than 8 million items. The Thomas Cooper Library, the main campus library, seats about 2,500 readers and features study rooms, seminar rooms, computer labs, and individual lockable carrels for research-

ers. An integrated computer information system allows access to holdings from any computer terminal. Its newest addition, the Ernest F. Hollings Spe-cial Collections Library, opened in summer 2010. It houses South Carolina Political Collections, the Irvin Department of Rare Books and Special Col-lections, and Digital Collections. There are separate libraries for medicine, law, mathematics, music, and business.

In addition to extensive faculty and graduate student research conducted through various academic departments, the University operates several per-manently established research facilities, including the Belle W. Baruch Insti-tute for Marine and Coastal Sciences, the Institute for Public Service and Policy Research, the Earth Sciences and Resources Institute, the S.C. Insti-tute of Archaeology and Anthropology, and the Richard L. Walker Insti-tute of International and Area Studies. Grants of more than $218.8 million were received in fiscal year 2010 in support of research and other sponsored programs at the University.

In keeping with both its 19th-century and 20th-century heritage, the Uni-versity continues to promote academic excellence. USC has committed itself to earning a place among the finest institutions of higher learning in Amer-ica. Such ambitions and ideals were cornerstones of the original college and remain fundamental to the University of South Carolina today.

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D e PA rt m e n t o f c h e m i s t ry A n D B i o c h e m i s t ry

The Department of Chemistry and Biochemistry began offering a research-oriented Master of Science degree in 1948. In 1954 the graduate program was expanded to include the Doctor of Philosophy. Since then the grad-uate research effort has broadened and intensified. Today the department counts 130 graduate students, about 30 postdoctoral fellows, and 30 full-time faculty members.

The department’s staff includes three undergraduate laboratory supervi-sors, a full-time staff crystallographer, several technicians and operators in the biochemical instrumentation core facilities, and four staff scientists in the NMR and Mass Spectrometry laboratories. In addition, the department has access to the College of Arts and Sciences machine shop and the USC Electron Microscopy Center.

The quality and promise of the graduate program in chemistry and bio-chemistry has been recognized outside the University as well as within. Eigh-teen times in the past 48 years the University of South Carolina’s Russell and Educational Foundation Research Awards for Science, Mathematics, and Engineering have gone to a member of the chemistry and biochem-istry faculty. Six faculty members have been named research fellows of the Alfred P. Sloan Foundation, and five faculty members have won the Uni-versity’s highest honor for excellence in teaching, the Amoco Foundation Award. The University’s Michael J. Mungo Award for Excellence in Under-

graduate Teaching has been won by seven faculty members from our depart-ment. Our biochemistry faculty have joint appointments with the School of Medicine; eight have received that school’s Basic Science Research Award. Our faculty have also received national and international recognition from American Chemical Society awards and by serving as editors and edito-rial advisory board members for prestigious chemical journals. Eight fac-ulty members from the department have received the Governor’s Award for Excellence in Science, awarded annually to the top research scientist in the state of South Carolina. Since its inception in 2005, three faculty mem-bers from the department have received the Governor’s Award for Scientific Awareness and for excellence in science in 2009–2010.

The department continues to hire and develop outstanding new faculty. Two new hires have recently been made. Physical chemistry faculty Drs. Andrew Greytak and Hui Wang joined the department in summer 2010.

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t h e g r A D UAt e P ro g r A m i n c h e m i s t ry A n D B i o c h e m i s t ry

The Department of Chemistry and Biochemistry offers a graduate program leading to the Doctor of Philosophy with concentrations in analytical, bio-logical, inorganic, organic, and physical chemistry. The course and research requirements are flexible and can be tailored to the background and interests of each student. Multidisciplinary areas such as nanoscience, environmen-tal science, materials science, and optics/spectroscopy are well-represented in the department. Collaborative research between research groups is pos-sible and encouraged.

Advanced degree programs in the department are designed to produce skilled, broadly educated, and creative scientists. While students will con-centrate their studies and research in a particular specialty area, it is the phi-losophy of our department that all students should receive a well-rounded, graduate-level education in several areas of chemistry. Specialization in a particular area, coupled with advanced training in other areas, provides our graduates with flexibility and a broad base of knowledge from which to tackle research problems.

A D m i s s i o n r e q U i r e m e n t s

Prospective graduate students should complete a baccalaureate program that includes one year each of general chemistry, organic chemistry, calcu-lus-based physical chemistry, and analytical chemistry (one-half year instru-mental). Given the diverse background of many of our faculty, applications from students from allied programs in the molecular sciences are also strongly encouraged. All components, including a final transcript acknowledging the degree, are required for admission to the graduate program. Additional course work in inorganic and biological chemistry may be helpful.

The general portion of the Graduate Record Examination (GRE) is required for admission. The GRE advanced chemistry scores are not required, but are encouraged, especially for students with an interest in additional fellowships.

t h e P h . D. P ro g r A m

First year: You and your faculty advisors will work out a program of study appropriate to your background, interests, and abilities, taking into consid-eration your performance on the qualifying examinations (taken prior to registration). First-year students take five advanced graduate courses (three in the major area) during the first two semesters. All required Ph.D.-level course work is normally completed by the end of the second semester. You must maintain a grade point average of “B” or better in order to continue beyond the first year. A foreign language is not required.

In August and September of your first year, you will attend seminars in which each faculty member makes a brief presentation about his or her research. These seminars will help you select a research director and a lab group to join. You may choose your research director in mid-November; at the lat-est, you must join a lab group by the first day of your second semester.

By the end of your first academic year, you must qualify in two of the five areas of graduate-level chemistry (analytical, biological, inorganic, organic, and physical), either by passing the qualifying examination or by receiving a grade of “B” or better in a designated qualifying course. One of the two areas must be your major area of interest.

All summers in the program are dedicated to research.

Second year: Early in your third semester, you will write and orally defend a report describing progress to date on a research project and your plans for continuing the project. Successful completion of the report satisfies The Graduate School’s requirement for an oral comprehensive exam.

During your fourth or fifth semester, you will write and orally defend a proposal focusing on an original research idea. Satisfactory performance on the proposal meets The Graduate School’s requirement for a written com-prehensive exam.

Completion of the program: After completing the proposal, the faculty will evaluate your overall academic record to determine whether you may continue as a Ph.D. candidate. Once you have been admitted to candidacy, you will continue your research and prepare your thesis.

Candidates for the Ph.D. are required to present three seminars during the course of their thesis studies. The last of these is the thesis defense; the ear-lier seminars are on literature or research topics.

Our graduate students currently average a little less than 4 and a half years to complete the Ph.D. program.

s e m e s t e r 1 2 3 4 5 6 7 8 9

Graduate Classes ■ ■

Teaching Assistantships ■ ■

Choose Advisor ■

Conduct Research ■ ■ ■ ■ ■ ■ ■ ■

Literature Seminar ■

Research Plan ■

Research Proposal

Ph.D. Candidacy

Divisional Seminar ■

Ph.D. Thesis Defense ■

P h . D. tA s k s B y s e m e s t e r

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P h . D. P ro f i l e s

i r i n A P. ro o f ( i n o r g A n i c c h e m i s t ry )

First Year■Copenhaver Fellow in the lab of Dr. Hans-Conrad zur Loye■Took one undergraduate-level course, Inorganic Chemistry, and four gradu-

ate-level courses: The Chemistry of the Representative Elements, Separation Methods in Analytical Chemistry, Physical-Inorganic Chemistry, and Special Topics in Physical Chemistry

■Teaching Assistant for Honors General Chemistry (fall and spring) ■Selected Dr. Hans-Conrad zur Loye as research advisor (fall) and began research

(spring)■Presented an inorganic divisional literature seminar: Photocatalysis and Photo-

catalytically Active Compounds

Second Year■Took one graduate-level course: The Chemistry of Transition Elements■Passed oral comprehensive and research plan (fall): Synthesis of Novel Photocat-

alytically Active Oxides■Oral presentation, the 58th Southeast Regional Meeting of the ACS (Augusta,

Ga.)■Oral presentation, the 233rd ACS National Meeting (Chicago, Ill.)■Passed written comprehensive and original research proposal (spring): Synthesis

and Characterization of Novel Oxides and Phosphates of Uranium■Presented an invited career seminar at Newberry College: Novel Oxides, Syn-

thesis, and Graduate School

Third Year■Presented an inorganic divisional seminar: Flux Synthesis of Complex Photocat-

alytically Active Oxides of Niobium and Tantalum■Oral presentation, the 59th Southeast Regional Meeting of the ACS (Greenville,

S.C.)■Served as a judge for the South Carolina Academy of Sciences high school research

competition■Awarded James R. Durig Graduate Student Travel Award■Presented a poster at the Gordon Research Conference on Solid State Chem-

istry, I (New London, N.H.)

Fourth Year■Oral presentation at the North American Solid State Conference (Columbus, Ohio)■Oral presentation at the 17th American Conference on Crystal Growth and

Epitaxy (Lake Geneva, Wisc.)

Fifth Year■Guy F. Lipscomb Award for Excellence in Chemistry and Biochemistry■1st place winner in oral presentations at the USC Graduate Student Day■Wrote and defended Ph.D. dissertation: Materials Discovery by Crystal Growth:

Synthesis, Structure Determination, and Physical Properties of Complex Oxides of Niobium, Tantalum, Iron, and Uranium

Representative Publications“Crystal growth of two new niobates, La2KNbO6 and Nd2KNbO6: structural, dielec-

tric, photophysical, and photocatalytic properties,” Chem. Mater. 2008, 20(10), 3327.“EuKNaTaO5: Crystal growth, structure and photoluminescence property,” J. Am.

Chem. Soc. 2009, 131(12), 4202.“Crystal growth of a new series of complex niobates, LnKNaNbO5 (Ln = La, Pr,

Nd, Sm, Eu, Gd, and Tb): Structural Properties and Photoluminescence,” Chem-istry of Materials. 2009, 21(9), 1955.

“Crystal growth of a series of lithium garnets Ln3Li5Ta2O12 (Ln = La, Pr, Nd): Structural properties, Alexandrite effect and unusual ionic conductivity,” J. Solid State Chem. 2009, 182(2), 295.

After GraduationPostdoctoral fellow at the University of South Carolina, in the lab of Dr. Thomas

Crawford (Department of Physics and Astronomy)

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P h . D. P ro f i l e s

yAg A n g Z h A n g ( o r g A n i c c h e m i s t ry )

First Year■Took five graduate courses: Mechanistic and Synthetic Organic Chemistry,

Special Topics in Organic Chemistry, The Chemistry of Transition Elements, Structural and Mechanistic Organic Chemistry, and Special Topics in Molec-ular Biochemistry

■Teaching assistant for General Chemistry (fall and spring)■Selected Dr. Ken D. Shimizu as research advisor (fall) and began research

(spring)■Awarded Joseph W. Bouknight Teaching Award

Second Year■Passed oral comprehensive and research plan (fall): Multi-armed Functional

Monomer for Molecular Recognition and Imprinting■Presented an organic divisional seminar (fall): Total Synthesis and Absolute Ste-

reochemistry of Polygalolides A and B■Passed written comprehensive and original research proposal (spring): Novel

Ladder Type Polymer Material Based on Selective Side Chain Metal Coordina-tion

■Presented an organic divisional seminar (spring): A Total Synthesis of Xestode-calactone A and Proof of Its Absolute Stereochemistry

■Poster presentations at the 233rd ACS National Meeting, Chicago, Ill.■Awarded J.R. Durig Graduate Student Travel Award

Third Year■Teaching assistant for Organic Chemistry (fall and spring)■Awarded the Lauren Brubaker Carolina Award, University of South Carolina

Fourth Year■Poster presentations at the 237th ACS National Meeting, Salt Lake City, Utah■Awarded Graduate Student Travel Award, College of Arts and Sciences■Awarded Excellence in Graduate Polymer Research Symposium Award, Ameri-

can Chemical Society

Fifth Year■Awarded Hiram and Lawanda Allen Award for Excellence in Chemistry and

Biochemistry■Wrote and defended Ph.D. dissertation: Molecularly Imprinted Polymers—New

Insights and Strategies

Representative Publications“Solvent Programmable Polymers Based on Restricted Rotation,” J. Am. Chem. Soc.

2009. 131, 12062–12063.“Importance of Functional Monomer Dimerization in Molecular Imprinting,” Lang-

muir. 2010 (paper in preparation).“Solvent programmable polymer based on restricted rotation—a mechanistic and

optimization study,” Macromolecules. 2010 (paper in preparation). “Reduction of the number of background sites in molecular imprinting by func-

tional monomer aggregation,” Analytica Chimica Acta. 2010 (paper in preparation).

After GraduationPostdoctoral fellow at the University of Illinois at Urbana-Champaign, in the lab

of Prof. Steven C. Zimmerman

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r e s e A r c h fAc i l i t i e s

Good research demands excellent facilities and equipment, and the Depart-ment of Chemistry and Biochemistry at the University of South Carolina is especially fortunate. In addition to facilities described below and on the following pages, the department maintains an electronics shop and a wide variety of standard and specialized equipment. The department’s physical facilities are outfitted with the latest spectrometers as well as instrumenta-tion for kinetics studies, inert atmosphere studies, proteomics, and mate-rials synthesis.

g r A D UAt e s c i e n c e r e s e A r c h c e n t e r

The Graduate Science Research Center opened in May 2000. The $36 million building totals 158,000 square feet and, except for the basement, is occupied solely by the faculty, staff, and graduate students of the Depart-ment of Chemistry and Biochemistry.

The building was designed from the ground up as a chemistry and biochem-istry research building and features a state-of-the-art system to control fume hoods and other ventilation apparatus. Sensors determine whether a hood is in use, how high the sash is raised, exhausts, and other information about air quality, which is used by a controller to ensure that flow rates match exact-ing health and safety standards. The GSRC uses 100 percent outside air; there are no air returns, which also increases safety. To help conserve energy, the hoods alert researchers to lower sashes when leaving their labs at night. The engineered airflow patterns make the building not only much safer but also much more efficient than previous designs.

This leading-edge facility provides space for about 250 scientists. It has 32 faculty offices, 64 four-person labs, 16 two-person labs, and approxi-mately 70 support areas, including instrument space, student and postdoc-toral offices, cold rooms, computer areas, and conference rooms. The core facilities of the department—the Mass Spectrometry Center, NMR Cen-ter, departmental offices, and stockroom—are located on the first floor for easy access by all researchers.

B i o c h e m i c A l i n s t rU m e n tAt i o n

Eleven of the research groups in the department are pursuing studies in bio-chemistry or related areas. A broad range of major instruments supports these investigations. For example, tissue culture facilities are available in several laboratories with sterile hoods, incubators, and microscopes.

n Oligonucleotide Synthesis Facility: Uses an Applied Biosystems 380B DNA Synthesizer to provide investigators with oligonucleotides (short segments of DNA) of any sequence needed.

n Enzyme Kinetics and Thermodynamics Facility: Features a HighTech double mixing rapid scan stopped flow spectrophotometer and a Micro-cal isothermal titration microcalorimeter.

“ I chose USC for my graduate career because the environment here fosters cooperative research, and it’s not so large that students get lost in the masses. The department is large enough to have the equipment needed to advance my research and of a personable size to make it easy to have access to any of the faculty here for conversations about research, not just my advisor.” —Michael Geer, organic chemistry

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e l e c t ro n m i c ro s c o P y c e n t e r

The Electron Microscopy Center (EMC) was established in 1970 as the University’s central analytical microscopy and imaging facility and has since supported the research activities of more than 2,500 faculty members, grad-uate students, and undergraduate students. With increased research and educational activities, the EMC has expanded to occupy more than 30,000 square feet in a multi-user, multi-instrument facility on the lower level of the Coker Life Sciences Building.

The EMC also assisted local industries with service to expand and support product development. The EMC currently has three research faculty and staff members and two student assistants, with oversight by a faculty committee.

The EMC’s major instrumentation consists of two transmission electron microscopes (TEMs), two scanning electron microscopes (SEMs), a wave-length dispersive electron microprobe analyzer (EMPA), and a large variety of sample preparation equipment, including ultramicrotomes, vacuum evap-orators, a low temperature plasma etcher/asher, plasma cleaner, ion mill, and assorted light microscope and photographic instrumentation detailed below.

n JEOL JEM-2100F high resolution transmission electron microscope (HRTEM) has field emission gun (FEG) with a maximum accelerating voltage of 200 kV and is equipped with a spherical aberration corrector, scanning transmission detector (STEM), high angle angular dark field detector (HAADF), electron energy loss spectrometer (EELS), energy dis-persive spectrometer (EDS), and complete tomography system.

n Hitachi H-8000 TEM has accelerating voltages from 75 to 200 kV. It can provide a magnification from three thousand to one million with resolu-tion of 0.14 nm. The Hitachi is primarily used for materials research and is an analytical microscope that is equipped with a side entry goniometer and digital AMT CCD Camera.

n FEI Quanta 200 environmental SEM (ESEM) is equipped with an inte-grated EDAX X-ray energy dispersive analysis system, heating and cooling stages, and backscattered electron detector. With optimum performance for both imaging and microanalysis of specimens, the instrument is an excellent tool for both conductive and nonconductive samples.

n FEI XL30 ESEM is equipped with backscattered electron detection, cathodoluminescence, and a TSL electron backscatter diffraction system.

n Hitachi 2500 Delta SEM is an integrated model equipped with a quad-raplex electron backscatter detector, an IXRF digital imaging and micro-analysis processing system, an IXRF X-ray fluorescence system, a Kevex/IXRF X-ray microanalysis system with Gresham light element detector, and an electron beam lithography system (NPGS).

n Cameca SX 50 EMPA is equipped with four wavelength dispersive detec-tors and a PGT energy dispersive system. It is used primarily for nonde-structive, quantitative chemical analysis. The EMPA has high sensitivity (0.01 wt % detection limit), high speed (seconds to minutes per analysis), high precision and accuracy (1–2 % errors), and high spatial resolution (0.001 mm analysis area); can be used to obtain images that show the dis-tribution and variation of chemical components in materials.

For more detailed information, please visit the facility’s Web page at www.emc.sc.edu.

m Ag n e t i c r e s o n A n c e fAc i l i t i e s

The departmental NMR facilities consist of four multinuclear Fourier transform spectrometers that are equipped for routine variable temperature operation. These instruments are connected to the departmental computer network, and data collected on any of the systems can be processed offline and archived on either a UNIX workstation or researchers’ PCs. Each of the instruments is student-operated and available to any trained depart-mental researcher.

n Varian Mercury 300 NMR: Fully multinuclear, high-resolution solution instrument equipped with z-axis field gradients for gradient shimming and multidimensional coherence selection experiments.

n Bruker Avance/DRX 400 NMR: Equipped with both triple-axis field gradients and 60-sample auto-changer, this is a fully multinuclear high-resolution system.

n Varian Mercury 400 NMR: A broad-band probe allows walk-on access to proton, fluorine, and phosphorous data collection. It is a fully multi-nuclear, high-resolution solution instrument with z-axis field gradients.

n Varian Inova 500 NMR: Equipped with three RF-channels and triple-axis field gradients, this is a fully multinuclear, high-resolution solution instrument with capabilities for solid-state analysis.

For more detailed information please visit the facility’s Web page at http://homer.chem.sc.edu/nmr.

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m A s s s P e c t ro m e t ry l A B o r Ato ry

The Mass Spectrometry Laboratory is located in GSRC room 018 and is equipped with nine mass spectrometers. It is open to researchers through-out the University. The instrumentation was funded, in part, by the NSF and NIH, as well as a gift from Glaxo-Welcome. A number of additional instruments are located in individual research labs.

n Finnigan TSQ: Triple quadrupole instrument dedicated to trace analysis by GC/MS/MS using either electron impact ionization or electron cap-ture negative ionization.

n VG 70S: Double-focusing magnetic sector mass spectrometer. Used to obtain EI and CI spectra of compounds introduced by either GC, direct probe, or direct exposure probe. Available fast atom bombardment (FAB) ion source for nonvolatile or ionic compounds. Used for high-resolution mass measurement in EI, CI, and FAB modes.

n VG 70S: Identical to the 70S above, this instrument is used primarily for high-resolution, quantitative GC/MS.

n Micromass QTOF: Tandem quadrupole-time of flight mass spectrome-ter for low- and high-resolution MS and MS/MS by electrospray ioniza-tion (ESI) and atmospheric pressure chemical ionization (APCI). Sample introduction by direct injection or liquid chromatography. Used primarily for qualitative organic analysis of polar/ionic compounds.

n Micromass QTOF API-USA is a newer version of the QTOF above. It is dedicated to protein/peptide analysis by capillary/nano liquid chro-matography and nanospray ionization.

n Micromass Quattro-LC: Triple quadrupole mass spectrometer with ESI/APCI. Used primarily for quantitative LC/MS and LC/MS/MS analyses.

n Micromass Quattro-Premier: A newer, more sensitive version of the Quat-tro-LC above, this triple quadrupole mass spectrometer is also dedicated to quantitative LC/MS and LC/MS/MS analyses. The liquid chromato-graph is the new Waters Acquity UPLC, which is specially designed for high-resolution liquid chromatography using columns packed with 1.7 micron particles.

n Bruker Ultraflex MALDI tandem time-of-flight mass spectrometer (TOF/TOF): This instrument allows molecular mass determination of large bio-molecules and synthetic polymers using matrix-assisted laser desorption ionization. In addition, it is specifically designed to perform rapid, highly sensitive protein microsequencing and identification in support of pro-teomics research.

n Thermo-Finnigan Element XR ICP-MS: This instrument consists of an inductively coupled argon plasma interfaced to a high-resolution magnetic sector mass spectrometer. It is used for trace metals analysis. A restricted access, class 1000 clean room is available for sample preparation.

For more detailed information, please visit the facility’s Web page: www.chem.sc.edu/mslab.

X - r Ay D i f f r Ac t i o n fAc i l i t i e s

The department maintains a Bruker SMART APEX single crystal diffrac-tometer with a 4K CCD area detector and low-temperature capabilities for small molecule and extended inorganic solid crystal structure determination. The USC NanoCenter, closely affiliated with the department, has recently acquired another SMART APEX system. In addition, the following X-ray diffraction instruments are housed in professors’ research labs and are avail-able to departmental researchers: a Rigaku R-Axis IV area detector for studies of biological macromolecules, one Rigaku Ultima IV Powder X-ray diffrac-tometer, and one Rigaku D/Max 2100 powder X-ray diffractometer, which has a 1400oC hot stage for variable temperature powder X-ray diffraction studies. The department is also a founding member of the Southeast Region Collaborative Access Team (SER CAT) and has regular access to its X-ray beamlines, which are devoted to biological crystallography. This facility is at the third generation synchroton (Advance Photon Source) located in the Argonne National Laboratory (Chicago area).

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fAc U lt y A n D r e s e A r c h i n t e r e s t s

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Adams ■ ■ ■ ■ ■ ■

Angel ■ ■ ■ ■ ■ ■

Benicewicz ■ ■

Berg ■ ■ ■ ■ ■ ■ ■ ■

Chen ■ ■ ■ ■ ■ ■ ■ ■

Dawson ■ ■ ■ ■ ■ ■ ■

Ferry ■ ■ ■ ■ ■ ■ ■

Garashchuk ■ ■ ■

Goode ■ ■ ■ ■

Greytak ■ ■ ■ ■ ■ ■ ■

Kistler ■ ■

Lavigne ■ ■ ■ ■ ■ ■ ■ ■

Lebioda ■ ■ ■

Morgan ■ ■ ■ ■ ■ ■ ■

Myrick ■ ■ ■ ■ ■ ■ ■

C. Outten ■ ■ ■ ■

F.W. Outten ■ ■ ■ ■ ■

Rassolov ■ ■ ■ ■

Reger ■ ■ ■ ■ ■

Shaw ■ ■ ■

K. Shimizu ■ ■ ■ ■ ■ ■

L. Shimizu ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

Sodetz ■ ■ ■

Tang ■ ■ ■ ■ ■ ■

Vogt ■ ■ ■ ■ ■ ■ ■ ■ ■ ■

H. Wang ■ ■ ■ ■ ■ ■

Q. Wang ■ ■ ■ ■ ■ ■

Wiskur ■ ■ ■ ■

Wuthier ■ ■ ■ ■

zur Loye ■ ■ ■ ■ ■ ■ ■

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r i c h A r D D. A D A m sC A R O l I N A d I S T I N G U I S H e d p R O F e S S O Radams@chem.sc.edu

i n o r g A n i c

Research Areas: Inorganic chemistry for cataly-sis and energy conversion; studies of the synthesis, structures, and catalytic properties of unsaturated bimetallic clusters and nanoparticles for hydrogen activation and catalysis; studies of metal chalco-genide quantum dots and related nanomaterials for solar energy conversion.

The high costs of crude oil have stimulated inter-ests in alternative energy sources. One of the most

important of these is solar energy. Solar energy is abundant, free, and environmentally friendly. Much research is being focused on developing new chemis-try for converting light into electricity and for split-ting water into hydrogen and oxygen. For our solar energy project, we are currently investigating the potential of metal chalcogenide (MC) nanoparticles called “quantum dots” to convert light into elec-tronic excited states known as excitons and subse-quently into photocurrents by charge separation. These MC nanoparticles are being used to create low-cost hybrid organic-inorganic solar cells hav-ing higher energy conversion efficiencies.

Although hydrogen is not a primary energy source, it can be synthesized and can serve as a means to store energy. Because of its high reactivity, the safe and efficient release of the energy stored in hydro-gen is a major challenge. The safe utilization of hydrogen will require the use of catalysts in any future “hydrogen economy.” For this reason, we are investigating the chemistry of unsaturated polynu-clear metal complexes for the purpose of activating hydrogen under mild conditions. For example, we have recently prepared a number of new unsaturated bimetallic cluster complexes containing the steri-cally crowded ligand P(t-Bu)3 by using the reagents Pd[P(t-Bu)3]2 and Pt[P(t-Bu)3]2. For example, we have obtained the new compound Re2Pt3[P(t-Bu)3]3(CO)6, 1 from the reaction of Pt[P(t-Bu)3]2 with Re2(CO)10. Compound 1 is electron defi-cient by the amount of 10 electrons. It readily adds three equivalents of hydrogen to form the hexahy-drido complex H6Re2Pt3[P(t-Bu)3]3(CO)6, 2 at room temperature, see Figure. The gray hydrido ligands bridge each of the six green Pt-Re bonds in the trigonal bipyramidal product. When irradi-ated (Uv-vis), compound 2 also releases four of the six hydrido ligands in the form of H2. Reversible hydrogen addition reactions could also be useful for hydrogen storage applications.

The chemical industry also relies on the use of reaction catalysts derived from the elements of the transition series for the economical production of many of the great variety of petro- and commod-ity chemicals in use today. We have recently shown that transition metal cluster complexes containing tin ligands are precursors to superior multimetal-lic, nanoscale heterogeneous catalysts for the hydro-genation of unsaturated organic compounds. For example, we have shown that our new heteroge-neous ruthenium-tin nanocatalysts selectively hydro-genate 1, 5, 9-cyclododecatrene to cyclododecene, an important chemical feedstock for the produc-tion of polymers such as nylon-12.

R e p R e s e n tat i v e p u b l i c at i o n s

Adams, R.D., and E. Trufan, “Ruthenium-Tin Cluster Complexes and their Applications as Bimetallic Nanoscale Heterogeneous Hydrogenation Cata-lysts,” Phil. Trans Royal. Soc., (2010); 368, 1473–1493.

Raja, R., R.D. Adams, D.A. Blom, W.C. Pearl Jr., E. Gianotti, and J.M. Thomas, “A New Catalytic Liquid-Phase Ammoxidation Approach towards the Preparation of Niacin (Vitamin B3),” Langmuir, (2009); 25, 7200–7204.

Adams, R.D., and B. Captain, “Unusual Structures and Reactivity of Mixed Metal Cluster Complexes Containing the Palladium/Platinum Tri-t-butylphos-phine Grouping,” Accts. Chem. Res., (2009); 42, 409–418.

Yang, F., E. Trufan, R.D. Adams, and D.W. Goodman, “The Structure of Molecular-Sized Ru3Sn3 clusters on a SiO2 Film on Mo(112),” J. Phys. Chem. C., (2008); 112, 14233–14235.

Adams, R.D., D.A. Blom, B. Captain, R. Raja, J.M. Thomas, and E. Tru-fan, “The exceptional benefits of tin in bimetallic nanocluster catalysts for the solvent-free hydrogenation of cyclododecatriene (CDT) to cyclodode-cene (CDE),” Langmuir, (2008); 24, 9223–9226.

Adams, R.D., and B. Captain, “Hydrogen Activation by Unsaturated Mixed Metal Cluster Complexes: New Directions,” Angew. Chem. int. Ed., (2008); 47, 252–257.

Adams, R.D., B. Captain, M.B. Hall, E. Trufan, and X. Yang, “The Synthe-sis, Characterization and Electronic Structures of a Novel Series of 2-Dimen-sional Trimetallic Cluster Complexes, Ru3(CO)9(u-SnPh2)3[Pt(PBut

3)]x, x = 0 – 3,” J. Am. Chem. Soc., (2007); 129, 12328–12340.

Adams, R.D., E.M. Boswell, B. Captain, A.B. Hungria, P.A. Midgley, R. Raja, and J.M. Thomas, “Bimetallic Ru-Sn Nanoparticle Catalysts for the Solvent-free, Selective Hydrogenation of 1,5,9-Cyclododecatriene to Cyclododecene,” Angew. Chem. int. Ed., (2007); 46, 8182–8185.

Adams, R.D., B. Captain, E. Trufan, and L. Zhu, “The Activation of Metal Hydride Complexes by Tri-t-butylphosphine-Platinum and -Palladium Groups,” J. Am. Chem. Soc., (2007); 129, 7545–7556.

Adams, R.D., B. Captain, Mark D. Smith, C. Beddie, and M.B. Hall, “Unsaturated Platinum-Rhenium Cluster Complexes. Synthesis, Structures and Reactivity,” J. Am. Chem. Soc., (2007); 129, 5981–5991.

B.S., 1969, Pennsylvania State Univer-sity; ph.d., 1973, Massachusetts Insti-tute of Technology.

Alfred P. Sloan Foundation Research Fellow, 1979–83; Russell Research Award for Science, Mathematics, and Engineering, University of South Car-olina, 1989; regional editor, Journal of Organometallic Chemistry; coeditor, Jour-nal of Cluster Science; 1999 American Chemical Society Award in Inorganic Chemistry; Alexander von Humboldt Senior Scientist Award, 1999; Charles Holmes Herty Medal, ACS Georgia Section, 1999; Charles H. Stone Award, ACS Carolina Piedmont Section, 1999; Chemical Pioneer Award, American Institute of Chemists, 2000; Senior Scientist Award, Alexander von Hum-boldt Foundation, 2000; Outstanding South Carolina Chemist, ACS South Carolina Section, 2001; Southern Chemist Award, ACS Memphis Sec-tion; Carolina Trustee professor, 2005; Henry J. Albert Award of the Interna-tional precious Metals Institute, 2005; American Chemical Society Award for Distinguished Service in the Advance-ment of Inorganic Chemistry, 2010.

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Research Areas: Development of in situ charac-terization techniques including fiber-optic chem-ical sensors and remote spectroscopy including Raman, LIBS and REMPI. Of particular inter-est is applying optical spectroscopic techniques to environmental and process-chemical measurement problems and development of fieldable spectro-scopic instrumentation.

We are exploring a number of remote spectro-scopic techniques and sensors for noncontact and in situ measurements. Such techniques allow unique applications in environmental, marine, earth, and space science. For example, microimaging sensors are being used for in situ measurements of analyte diffusion in thin membranes. Resonance enhanced multiphoton laser ionization, REMPI, is used to measure ppb levels of toxic compounds in soil sam-ples. In addition, a unique laser-induced plasma spectroscopy probe is used for remote, noncon-tact elemental analysis (see figure at right). Other techniques being explored include fluorescence and Raman imaging and imaging sensors.

Fiber-optic measurements are made in two ways. In the first, light transmitted to the sample region via the fiber optic is used to perform a direct spec-troscopic measurement. This type of analysis is referred to as remote fiber spectroscopy (RFS) and encompasses many spectroscopic methods, such as Raman, surface-enhanced Raman, absorption, reflectance, LIBS, REMPI, and fluorescence spec-troscopies that have been adapted for use with opti-cal fibers. Often, the choice of a detection method is influenced by the optical properties of the fiber. For example, when using extended lengths of opti-cal fibers in Raman applications it is desirable to use long wavelength light to take advantage of the high transmittance and low background of opti-cal fibers. This is contrary to the normal inclina-tion of using short wavelengths to achieve high Raman cross-sections. In the second category, the transmitted light probes an intermediate material affixed to the terminal end of the fiber that inter-acts with the analyte to produce an optical signal.

Recently our focus has been on deep-ocean appli-cations of LIBS and standoff measurements of haz-ardous materials using Raman spectroscopy. LIBS is difficult in bulk aqueous solution because of plasma quenching by water. The quenching problem can be overcome by using laser pulse pairs, where a water bubble created by the first laser pulse isolates the LIBS plasma that is formed inside the bubble by the second laser pulse. We are extending this dou-ble-pulse technique to higher pressures like those found at hydrothermal vent sites at 2–3 km depths. Standoff Raman has applications to planetary mea-surements and also to homeland defense. Current investigations include the use of standoff Raman and UV resonance Raman to measure high explosive (HE) materials at distances of 10–30 meters. This research emphasizes instrument development including the development of new, high-resolving power, interferometric-based spectrometers, as well

as fundamental studies regarding the optimization of Raman excitation conditions for highly absorb-ing, nanoscale HE residues.

R e p R e s e n tat i v e p u b l i c at i o n s

Scaffidi, J., M.K. Gregas, B. Lauly, J.C. Carter, S.M. Angel, and T. Vo-Dinh, “Stand-off SERS and SERRS detection in the presence of ambient light,” Appl. Spectrosc., (2010): 64(5), 485–492.

Lawrence-Snyder, M., J.P. Scaffidi, W.F. Pearman, and S.M. Angel, “Depen-dence of Emission Intensity and Laser Inter-Pulse Delay on Solution Pressure in Dual-Pulse Laser-Induced Breakdown Spectroscopy of Bulk Aqueous Solu-tions,” Appl. Spectrosc., accepted pending approval of final revisions, Jan. 2010.

Vann, B.L., S.M. Angel, S.L. Morgan, J.E. Hendrix, and E.G. Bartick, “Anal-ysis of Titanium Dioxide in Synthetic Fibers using Raman Microspectros-copy,” Appl. Spectrosc., (2009); 63, 23–27.

Pearman, W.F., J.C. Carter, S.M.Angel, J.W-J. Chan, “Quantitative mea-surements of CO2 and CH4 using a multipass Raman capillary cell,” Appl. Opt., (2008); 47, 4627–4632.

Pearman, W.F., S.M. Angel, J.L. Ferry, and S. Hall, “Characterization of the Ag Mediated Surface-Enhanced Raman Spectroscopy of Saxitoxin,” Appl. Spectrosc., (2008); 62, 727–732.

Pearman, W.F., J.C. Carter, S.M. Angel, and J. W-J. Chan, “Multipass Cap-illary Cell for Enhanced Raman Measurements of Gases,” Appl. Spectrosc., (2008); 62, 285–289.

Michel, A.P.M., M. Lawrence-Snyder, S.M. Angel, and A.D. Chave, “Laser-induced breakdown spectroscopy of bulk aqueous solutions at oceanic pres-sures: evaluation of key measurement parameters,” Appl. Opt., (2007); 46, 2507–2515.

Pearman, W.F., M. Lawrence-Snyder, S.M. Angel, and A.W. Decho, “Sur-face-Enhanced Raman Spectroscopy for in Situ Measurements of Signaling Molecules (Autoinducers) Relevant to Bacteria Quorum Sensing,” Appl. Spec-trosc., (2007); 61, 1295–1300.

Lawrence-Snyder, M., J. Scaffidi, S.M. Angel, A.P.M. Michel, and A.D. Chave, “Sequential-Pulse Laser-Induced Breakdown Spectroscopy of High-Pressure Bulk Aqueous Solutions,” Appl. Spectrosc., (2007); 61, 171–176.

Lawrence-Snyder, M., J. Scaffidi, S.M. Angel, A.P.M. Michel, and A.D. Chave, “Laser-Induced Breakdown Spectroscopy of High-Pressure Bulk Aqueous Solutions,” Appl. Spectrosc., (2006); 60, 786–790.

Sharma, S.K., A.K. Misra, P.G. Lucey, S.M. Angel, and C.P. McKay, “Remote Pulsed Raman Spectroscopy of Inorganic and organic Materials to a Radial Distance of 100 Meters,” Appl. Spectrosc., (2006); 60, 871–876.

Scaffidi, J., W. Pearman, J.C. Carter, and S.M. Angel, “Observations in Col-linear Femtosecond–Nanosecond Dual-Pulse Laser-Induced Breakdown Spec-troscopy,” Appl. Spectrosc., (2006); 60, 65–71.

Scaffidi, J., S.M. Angel, and D.A. Cremers, “Emission Enhancement Mech-anisms in Dual-Pulse LIBS,” Anal. Chem. (2006); 78, 24–32.

Carter, J.C., J. Scaffidi, S. Burnett, B. Vasser, S.K. Sharma, and S. Michael Angel, “Stand-off Raman detection using dispersive and tunable filter based systems,” Spectrochim. Acta Part A, (2005); 61, 2288–2298.

Carter, J.C., S.M. Angel, M. Lawrence-Snyder, J. Scaffidi, R.E. Whipple, and J. Reynolds, “Standoff Detection of High Explosive Materials at 50 Meters in Ambient Light Conditions Using a Small Raman Instrument,” Appl. Spectrosc., (2005); 59, 769.

Michel, A.P.M., M.J. Lawrence-Snyder, S.M. Angel, and A.D. Chave, “Oce-anic applications of laser induced breakdown spectroscopy: laboratory valida-tion,” Dept. of Appl. Ocean Phys. & Eng., Massachusetts Inst. of Technol., Woods Hole, Mass., USA; This paper\ appears in: OCEANS 2005, Proceed-ings of MTS/IEEE, pp. 741–747, Vol. 1 (2005).

A n A ly t i c A l

s . m i c h A e l A n g e lF R e d M . W e I S S M A N C H A I R I N C H e M I C A l e C O l O G yangel@chem.sc.edu

B.S., 1979, North Carolina State Univer-sity; ph.d., 1984, North Carolina State Uni-versity; postdoctoral Fellow, 1985–1986, lawrence livermore National laboratory. Physics and Advanced Technologies Direc-torate Award, 2006; Georgia Southern State University, student seminar program featured research, 2006; editorial board member of International Journal of Spectroscopy; A-page advi-sory panel member for Analytical Chemistry; advisory board of Talanta; International Scien-tific Committee member NASlIBS, 2007; tour speaker for Society of Applied Spectroscopy (SAS), 2007; 2009 USC educational Founda-tion Research Award for Science, Mathemat-ics, and Engineering.

In LIBS, the sample is ablated and ionized using a pulsed laser. Analysis of the emission from the plasma provides information on the elemental composition of the sample. This technique is unique in that elemental composition can be determined remotely.

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o r g A n i c

B r i A n c . B e n i c e W i c Ze d U C AT I O N A l F O U N d AT I O N d I S T I N G U I S H e d p R O F e S S O R ;

C O e e C H A I R I N p O ly M e R N A N O C O M p O S I T e R e S e A R C Hbenice@mailbox.sc.edu

Research Areas: Polymer-organic chemistry, new monomer and polymer synthesis, polymer nano-composites, polymer membranes for fuel cells, electrically conducting polymers, liquid crystal-line polymers, controlled radical polymerization.

The underlying theme for all of the work in our group is our ability to synthesize polymers by new methods and with properties or combinations of properties not found in existing materials. We sim-ply enjoy making new materials. However, our work extends beyond the synthesis, and we character-ize the properties of these new materials and test them in potential applications to establish struc-ture-property relationships to further aid in the design of next generation polymers.

Polymer Nanocomposites: We are developing con-trolled radical polymerization techniques to design the interfacial properties of polymer nanocompos-ites. We have developed a toolbox of methods to control the chemistry at the surface of nanoparti-cles with great precision and use “click” chemistry techniques to introduce functionalities at the sur-face of nanoparticles which could not survive the polymerization conditions or may interfere with the polymerization. Block copolymerization is also used to establish multilayers at the nanoparticle surface. Our work relies on the use of the controlled radical polymerization technique, RAFT, or reversible addi-tion-fragmentation, chain transfer polymerization. The design of new RAFT agents, surface anchored RAFT agents, and new monomers have allowed us to prepare surface functionalized nanoparticles for many different applications.

Fuel Cell Membranes: We are investigating new poly-mers for high temperature fuel cell membranes. The polymer membrane is considered the “heart” of a polymer electrolyte membrane (PEM) fuel cell and represents a central challenge for the future of fuel cell devices. Polybenzimidazoles imbibed with phosphoric acid are being prepared and tested in fuel cells at temperatures up to 200˚C. Our work over the last several years has been focused on a new process that allows high phosphoric acid lev-els while still maintaining the mechanical strength for these highly loaded films. The conductivities and fuel cell performance have increased substan-tially and now exhibit values suitable for commer-cial applications.

We have also explored a great deal of new chem-istry associated with the basic synthetic methods and new compositions to further improve the basic conductivity of the polymer membrane. The syn-thesis of new compositions continues with the belief that the polymer plays an important role in the conductivity. An extensive fuel cell test labora-tory designed for high temperature membrane test-ing supports our work in this area. We have also extended this work to investigate electrochemical hydrogen pumping for hydrogen separation and purification applications.

R e p R e s e n tat i v e p u b l i c at i o n s

Dukes, D., Y. Li, S. Lewis, B. Benicewicz, L. Schadler, and S. Kumar. “Conformational Transitions of Spherical Polymer Brushes: Synthesis, Characterization and Theory.” Macromolecules (2010); 43, 1564–1570.

Bruckman, M.A., J. Liu, G. Koley, Y. Li, B. Benicewicz, Z. Niu, and Q. Wang. “Tobacco Mosaic Virus Based Electrochemical Sensor for Detection of Volatile Organic Compounds.” Journal of Materials Chemistry (2010); 20, 5715–5719.

Mader, J.A., and B.C. Benicewicz. “Sulfonated Polybenzimidazoles for High Temperature PEM Fuel Cells.” Macromolecules; (2010); 43, 6706–6715.

Akcora, P., S.K. Kumar, J. Moll, S. Lewis, L.S. Schadler, Y. Li, B.C. Benice-wicz, A. Sandy, S. Narayanan, J. Ilavsky, P. Thiyagarajan, R.H. Colby, and J.F. Douglas, “‘Gel-like’ Mechanical Reinforcement in Polymer Nanocom-posite Melts,” Macromolecules (2010); 43, 1003–1010.

Yu, S., and B.C. Benicewicz, “Synthesis and Characterization of Function-alized Polybenzimidazoles for High Temperature PEMFC’s,” Macromole-cules (2009); 42, 8640–8648.

Khan, J., S.E. Harton, P. Akcora, B.C. Benicewicz, and S.K. Kumar, “Poly-mer Crystallization in Nanocomposites: Spatial Reorganization of Nanopar-ticles,” Macromolecules (2009); 42, 5741–5744.

Qian, G., D.W. Smith Jr., and B.C. Benicewicz, “Synthesis and Character-ization of High Molecular Weight Perfluorocyclobutyl-Containing Polybenz-imidazoles (PFCB-PBI) for High Temperature Polymer Electrolyte Membrane Fuel Cells,” Polymer (2009); 50, 3911–3916.

Qian, G., and B.C. Benicewicz, “Synthesis and Characterization of High Molecular Weight Hexafluoroisopropylidene-containing Polybenzimidazole (6F-PBI) for High Temperature Polymer Electrolyte Membrane Fuel Cells,” J. Polym. Sci. Part A: Polym. Chem. (2009); 47, 4064–4073.

Yu, S., H. Zhang, L. Xiao, E.-W. Choe, B.C. Benicewicz, “Synthesis of Poly(2,2’-(p-phenylene) 5,5’-bibenzimidazole) (para-PBI) and Phosphoric Acid Doped Membranes for Fuel Cells,” Fuel Cells (2009); 9(4), 318–324.

Akcora, P., H. Liu, S.K. Kumar, J. Moll, Y. Li, B.C. Benicewicz, L.S. Schadler, D. Acehan, A.Z. Panagiotopoulos, V. Pryamitsyn, V. Ganesan, J. Ilavsky, P. Thiyagarajan, Colby, R.H., and J.F. Douglas, “Anisotropic Self-Assembly of Spherical Polymer-Grafted Nanoparticles,” Nature Mater (2009); 8, 354–359.

“High-Temperature Polybenzimidazole-Based Membranes,” D.C. Seel, B.C. Benicewicz, L. Xiao, and T.J. Schmidt, in Handbook of Fuel Cells: Advances in Electrocatalysis, Materials, Diagnostics and Durability, Vol. 5 & 6, W. Vielstich, H.A. Gasteiger, and H. Yokikawa (eds). John Wiley & Sons Ltd, Chichester, UK (2009); Chapter 19, pp. 300–312.

Li, Y., and B.C. Benicewicz, “Functionalization of Silica Nanoparticles via the Combination of Surface-initiated RAFT Polymerization and Click Reac-tions,” Macromolecules (2008); 41, 7986–7992.

B.S. 1976, Florida Institute of Technology; ph.d., 1980, University of Connecticut; Research Sci-entist, 1980–1982, Celanese Research Co.; Senior Scientist, 1982–1985, ethicon, Inc.; Staff Member, Section Leader, Deputy Group Leader, los Alamos National laboratory, 1985–1997; Professor and Director of the Center for Poly-mer Synthesis, Rensselaer Polytechnic Insti-tute, 1997–2008.

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P h y s i c A l

m A r k A . B e r gP R O F E S S O Rberg@chem.sc.edu

Research Areas: Ultrafast laser spectroscopy; dynamics of molecules in liquids, glasses, poly-mers, and other complex materials; development of new multiple-pulse spectroscopies.

Just as the static properties of macroscopic mate-rials are determined by structure on Angstrom to nanometer length scales, the macroscopic, dynamic properties are determined by motion on the fem-tosecond to nanosecond time scales. For exam-ple, single-collision times in solids and liquids are near 0.1 ps; sound waves transmit conformational changes across a 10 nm diameter protein in 10 ps; solar energy captured by a semiconductor nanopar-ticle persists no longer than a few 10’s of ns. If we want to understand the macroscopic behavior of materials in terms of molecular properties, exper-iments on these ultrafast time scales are required.

Although these times are natural for molecular pro-cesses, they can only be measured by using ultra-fast laser technology. In our laboratory, pulses with durations as short as 50 fs and with peak intensi-ties in the 10 gigawatt range are used to investigate these processes. These pulses are only 15 microns in physical length. They consist of 15–20 optical cycles if they are in the visible and only a few cycles if they are in the infrared. Using these pulses, we observe events as fast as the breaking of a chemical bond or of a single collision in solution.

In addition to ultrafast lasers, our experiments need new methods to measure molecular motion using only pulses of light. We are actively develop-ing complex sequences of pulses to measure new properties. These “multidimensional” spectrosco-pies exploit both the high-intensity electric fields in the laser pulses and the fact that materials retain memory of the phase of their excitation during these short times. We have recently demonstrated that a sequence of six pulses (called a MUPPETS experiment) can measure the electronic-relaxation rate of specific subpopulations within a heteroge-neous sample. A number of other new, but related, measurements have been predicted and are being brought into the laboratory to address problems of current interest.

Mesoscale Structure in Ionic Liquids. Materials con-sisting of organic cations and bulky anions remain liquid at room temperature, but have properties distinctly different from nonionic liquids. These unusual properties are being rapidly exploited in industrial applications. Computer simulations have suggested that structuring on the nanometer length scale may explain many of these properties. MUPPETS is one of the few methods available to directly measure the predicted heterogeneity. These experiments are being used to measure this struc-ture through its effect on solvent-sensitive reactions. Polarization MUPPETS will be used to measure molecular rotation and thereby probe the local vis-cosity of these regions.

Energy Pathways in Nanostructures. Semiconduct-ing nanostructures offer great promise for harvest-ing solar energy, but no two nanostructures are ever identical at the atomic level. Lattice defects, vari-ation in surface structure, and misplaced passivat-ing molecules are common and can greatly affect energy flow, but are difficult to detect in structural measurements. MUPPETS offers a means to mea-sure the different fates of energy in different parti-cles within a real sample.

Peptide Dynamics. In some circumstances, pro-teins do not have a well-defined structure: before folding, after denaturation, in “intrinsically disor-dered” proteins, and in short peptides. The speed of conformational changes makes it difficult to characterize either the range of conformations or the rate of interconversion between them. Ultra-fast multidimensional experiments coupled with FRET (fluorescence resonance energy transfer) is a new approach that will be used to make these measurements.

Our research draws on chemistry, laser physics, statistical mechanics, spectroscopy, and biology to answer broad issues in chemistry, physics, and mate-rials science. Students with a background in any of these fields can contribute to our efforts. Growth into unfamiliar areas is expected and is facilitated by interactions with students and postdocs from a variety of fields.

R e p R e s e n tat i v e p u b l i c at i o n s

Khurmi, C., and M.A. Berg. “Dispersed Kinetics without Rate Heterogene-ity in an Ionic Liquids Measured by Multiple Population-Period Transient Spectroscopy,” J. Phys. Chem. Lett. 1 (2010): 161.

Sen, S., D. Andreatta, S.Y. Ponomarev, D.L. Beveridge, and M.A. Berg. “Dynamics of Water and Ions Near DNA: Comparison of Simulation to Time-Resolved Stokes-Shift Experiments,” J. Am. Chem. Soc., 131 (2009): 1724.

Berg, M.A., R.S. Coleman, and C.J. Murphy. “Nanoscale Structure and Dynamics of DNA,” Phys. Chem. Chem. Phys. 10 (2008): 1229.

van Veldhoven, E., C. Khurmi, X. Zhang, and M.A. Berg. “Time-Resolved Optical Spectroscopy with Multiple Population Dimensions: A Gen-eral Method of Resolving Dynamic Heterogeneity,” Chem. Phys. Chem., 8 (2007): 1761.

Urbanek, D.C., and M.A. Berg. “Simultaneous Time and Frequency Detec-tion in Femtosecond Coherent Raman Spectroscopy. I. Theory and Model Calculations,” J. Chem. Phys., 127 (2007): 044306.

Nath, S., D.C. Urbanek, S.J. Kern, and M.A. Berg. “Simultaneous Time and Frequency Detection in Femtosecond Coherent Raman Spectroscopy. II. Appli-cation to Acetonitrile,” J. Chem. Phys., 127 (2007): 044307.

Liu, L.T., D. Yaron, and M.A. Berg. “Electron-Phonon Coupling in Phenyl-eneethynylene Oligomers: A Nonlinear One-Dimensional Configuration-Coordinate Model,” J. Phys. Chem. B 111 (2007): 5770.

Nath, S., D.C. Urbanek, S.J. Kern, and M.A. Berg. “High-Resolution Raman Spectra with Femtosecond Pulses: An Example of Combined Time- and Frequency-Domain Spectroscopy,” Phys. Rev. Lett., 97 (2006): 267401.

Andreatta, D., J.L. Pérez Lustres, S.A. Kovalenko, N.P. Ernsting, C.J. Mur-phy, R.S. Coleman, and M.A. Berg. “Power-Law Solvation Dynamics in DNA over Six Decades in Time,” J. Am. Chem. Soc., 127 (2005): 7270.

B.S., 1979, University of Minnesota; ph.d., 1985, University of California at Berkeley; postdoc-toral Fellow, 1985–1987, Stanford University.

Camille and Henry Dreyfus Distinguished young Faculty Award, 1987; National Science Foundation presidential young Investigator, 1990; Alfred p. Sloan Foundation Research Fellow, 1992; Fellow of the American Physical Society, 2000; USC educational Fund Research Award, 2007.

In a 2D experiment, a biexponential decay always pro-duces two peaks along the diagonal of a rate correlation spectrum. If the two rates are on the same molecule (left), cross peaks appear. If the rates belong to differ-ent molecules (right), they do not appear.

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D o n n A A . c h e nA S S O C I AT e p R O F e S S O R ; A d j U N C T A S S O C I AT e p R O F e S S O R I N C H e M I C A l e N G I N e e R I N Gchen@chem.sc.edu

P h y s i c A l

STM images of copper particles on a titania surface. All images are 100 nm x 100 nm.

Research Areas: Reactions at surfaces; scanning probe microscopy; chemical analysis and character-ization of surfaces; chemistry of metal nanoparticles.

My research focuses on understanding surface chemistry on the atomic and molecular levels. Spe-cifically, we are investigating surface reactions on metal, semiconductor, and oxide surfaces using in situ ultrahigh vacuum techniques and scanning probe microscopy.

One of our projects involves growing metal nanoparticles on oxide surfaces and studying the chemical reactivity of these nanoparticles as a func-tion of their size, shape, and interactions with the oxide substrate. The ultimate goals of this project are to improve the properties of commercial hetero-geneous catalysts, which typically consist of metal particles dispersed on an oxide substrate, and to

develop ideas for new catalysts. As an example, the figure below shows scanning tunneling micros-copy (STM) images of titania surfaces with cop-per nanoparticles. There is good reason to believe that quantum effects and other size-dependent phenomena can give rise to enhanced or modified reactivity for catalysts when their particle sizes can be controlled in the nanoscale range. The copper nanoparticles in the figure can be prepared with a relatively narrow size distribution, which provides us with the unique ability to study size-dependent effects in catalysis.

Ni, Pt, Rh, and Pt-Rh bimetallic particles have been prepared with varying sizes and narrow size distri-butions. Model catalytic reactions such as oxida-tion, desulfurization, and reduction of NO with CO have been studied on the metal nanoparticles since these reactions represent industrially impor-tant processes. The decomposition of dimethyl methyl phosphonate, which is used as a simulant for chemical warfare agents, is also being investi-gated on Ni and Cu nanoparticles.

Most of our work on this first project is performed under ultrahigh vacuum conditions (P<1x10-10

Torr) on single-crystal surfaces. This provides us with a well-controlled environment in which to study surfaces with known atomic structures. Scan-ning tunneling microscopy is used to characterize sizes and shapes of deposited metal nanoparticles on the atomic scale. X-ray photoelectron spectros-copy (XPS), low energy ion scattering (LEIS), low energy electron diffraction (LEED), temperature programmed desorption (TPD, a form of mass spectrometry), and other surface analysis tech-niques provide information on surface structure, atomic composition, chemical bonding, and reac-tion product identification.

In a second project, metal nanoparticles with con-trolled sizes, size distributions, and atomic com-

position (for bimetallic particles) are prepared in solution by using polyamidoamine dendrimers as templates. The dendrimer-encapsulated metal par-ticles are deposited on surfaces and characterized by atomic force microscopy and grazing angle infra-red spectroscopy. After thermal decomposition of the dendrimer, the surface chemistry of the result-ing supported metal nanoparticles is investigated in order to understand how to develop better catalytic materials based on nanoscale properties. This proj-ect involves extensive collaboration with the chem-ical engineering department at USC.

R e p R e s e n tat i v e p u b l i c at i o n s

D.A. Chen, J.S. Ratliff, X. Hu, W.O. Gordon, S.D. Senanayake, and D.R. Mullins, “Dimethyl Methylphosphonate Chemistry on Fully Oxidized and Partially Reduced Ceria Thin Films,” Surf. Sci., (2010): 604 (5–6), 574–587.

J.B. Park, S.F. Conner, and D.A. Chen. “Bimetallic Pt-Au Clusters on TiO2(110): Growth, Surface Composition and Metal-Support Interactions.” J. Phys. Chem. C, (2008): 112, 5490–5500.

O. Ozturk, J.B. Park, S. Ma, J. Ratliff, J. Zhou, D.R. Mullins, and D.A. Chen. “Probing the Interactions of Pt, Rh and Bimetallic Pt-Rh Clusters with the TiO2(110) Support.” Surf. Sci. (2007): 601, 3099–3113.

J.B. Park, J.S. Ratliff, S. Ma, and D.A. Chen. “Understanding the Reactivity of Oxide-supported Bimetallic Clusters: Reaction of NO with CO on TiO2(110)-supported Pt-Rh Clusters.” J. Phys. Chem. C, (2007): 111 (5), 2165–2176.

J.B. Park, J.S. Ratliff, S. Ma, and D.A. Chen. “In Situ Scanning Tunneling Microscopy Studies of Bimetallic Cluster Growth: Pt-Rh on TiO2(110).” Surf. Sci. (2006): 600, 2913–2923.

O. Ozturk, T.J. Black, K. Perrine, K. Pizzolato, C.T. Williams, F.W. Parsons, J.S. Ratliff, J. Gao, C.J. Murphy, H. Xie, H.J. Ploehn, and D.A. Chen. “Ther-mal Decomposition of Generation-4 Polyamidoamine Dendrimer Films: Decomposition Catalyzed by Dendrimer-Encapsulated Pt Particles.” Lang-muir, (2005): 21 (9), 3998–4006.

P.E. Colavita, P.G. Miney, L. Taylor, R. Priore, D.L. Pearson, J. Ratliff, O. Ozturk, D.A. Chen and M.L. Myrick. “Effects of Metal Coating on Self-assembled Monolayers on Gold. 2. Copper on an Oligo(phenylene-ethyn-ylene) Monolayer.” Langmuir 21, (2005): 12268–12277.

S. Ma, J. Zhou, Y.C. Kang, J.E. Reddic and D.A. Chen. “Dimethyl Meth-ylphosphonate Decomposition on Cu Surfaces: Supported Cu Nanoclusters and Films on TiO2(110).” Langmuir, (2004): 20 (2), 9686–9694.

K. Varazo, F.W. Parsons, S. Ma and D.A. Chen. “Methanol Chemistry on Cu and Oxygen-covered Cu Nanoclusters Supported on TiO2(110).” J. Phys. Chem. B (2004): 108(47), 18274–18283.

A. Illingworth, J. Zhou, O. Ozturk, and D.A. Chen. “Design of a Heat-ing-Cooling Stage for STM and TPD Experiments.” J. Vac. Sci. Technol. B (2004): 22(5), 2552–2554.

J. Zhou, S. Ma, Y.C. Kang and D.A. Chen. “Dimethyl Methylphospho-nate Decomposition on Titania-Supported Ni Clusters and Films: A Com-parison of Chemical Activity on Different Ni Surfaces.” J. Phys. Chem. B (2004): 108, 11633–11644.

J. Zhou, Y.C. Kang and D.A. Chen. “Adsorbate-induced Dissociation of Metal Clusters: TiO2(110)-supported Cu and Ni Clusters Exposed to Oxy-gen Gas.” Surf. Sci. (2004): 562(1-2), 113–127.

J. Zhou, Y.C. Kang, and D.A. Chen. “Oxygen-induced Dissociation of Cu Islands on TiO2(110).” J. Phys. Chem B (2003): 107(28), 6664–6667.

J. Zhou, Y.C. Kang and D.A. Chen. “Controlling Island Size Distributions: A Comparison of Nickel and Copper Growth on TiO2(110).” Surf. Sci. (2003): 537, L429–L434.

J. Zhou and D.A. Chen. “Controlling Size Distributions of Copper Islands Grown on TiO2(110)-(1x2).” Surf. Sci. (2003): 527, 183–187.

B.S., 1992, Rochester Institute of Technology; ph.d., 1997, Harvard University; postdoctoral Fellow 1997–1999, Sandia National laboratories.

Union Carbide Innovation Recognition Award, 1997; Army young Investigator Award, 2000; NSF CAReeR Award, 2002; young Scientist Governor’s Award for excellence in Science, 2008; Michael j. Mungo Undergradu-ate Teaching Award, 2010.

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J o h n h . D AW s o nC A R O l I N A d I S T I N G U I S H e d p R O F e S S O R ; C H A I R O F d e pA RT M e N Tdawson@chem.sc.edu

B i o c h e m i s t ry

Research Areas: Bio-inorganic, biophysical, and bio-organic chemistry; spectroscopy and mecha-nisms of action of dioxygen- and peroxide-activating heme iron enzymes and model systems; cytochrome P450; magnetic circular dichroism spectroscopy.

The mechanism of dioxygen activation for inser-tion into organic molecules is a problem of fun-

damental importance. The enzymes that catalyze these transformations often require metal ions for activity. Results obtained from the investigation of such metallo-enzymes, in addition to providing insight into their mechanism of action, are of obvi-ous relevance to the design of catalysts for nonen-zymatic oxidations. My research interests focus on the structure and function of dioxygen- and per-oxide-activating heme iron enzymes. Additional areas of interest include the role of metal ions in enzymatic catalysis and structure, structural and functional model systems, and the application of magnetic circular dichroism, X-ray absorption, and electron paramagnetic resonance spectroscopy to bioinorganic systems.

Two experimental approaches are being used: (a) spectroscopic studies to establish the structure of the metal binding site and (b) mechanistic investi-gations to define the molecular sequence of events involved in catalysis. All appropriate spectroscopic methods are being used to accomplish the first of these two goals. The mechanistic studies involve the use of cryoenzymology and rapid kinetic techniques such as stopped-flow rapid-scanning absorption spectroscopy and freeze-quenching, as well as the determination of important mechanistic parameters.

Cytochrome P-450 has been the focus of research in my lab for many years. This heme enzyme has unusual spectroscopic properties and catalytic reac-tivities relative to other heme enzymes. Its ability to oxygenate an extensive range of substrates has gen-erated considerable interest in its mode of action. In addition to spectroscopically examining the acces-sible stable states of this enzyme, emphasis is being placed on a detailed understanding of the substrate and ligand binding processes and on attempts to trap out the reactive intermediates responsible for oxygen insertion.

In collaboration with Professor Lukasz Lebioda, we are studying two fascinating heme-contain-ing peroxidases from marine sources. One haloge-nates aromatic substrates (phenols), and the other dehalogenates the resulting halophenol products. Both have unusual spectroscopic and mechanistic properties, relative to other peroxidases, that chal-lenge the conventional structure-function patterns of heme-containing peroxidases.

Magnetic circular dichroism (MCD) spectroscopy is a particularly powerful technique for studying heme systems because of its frequent ability to dis-

tinguish between porphyrin structures with dif-ferent axial ligands. To expand the utility of this technique, we are studying the spectroscopic prop-erties of porphyrin complexes of known structure and several heme proteins such as cystathionine beta synthase, nitric oxide synthase, guanylate cyclase, and heme oxygenase. We have both UV-visible and near-IR MCD spectrophotometers, the latter for studying low-energy structure-sensitive charge transfer transitions.

R e p R e s e n tat i v e p u b l i c at i o n s

Kinloch, R.D.; Sono, M.; Sudhamsu, J.; Crane, B.R.; Dawson, J.H. “Mag-netic Circular Dichroism Spectroscopic Characterization of the NOS-like Protein from Geobacillus stearothermophilus,” J. Inorg. Biochem. (2010): 104, 257–364.

Collins, D.P.; Spolitak, T.; Ballou, D.P.; Dawson, J.H. “The Generation and Characterization of the Compounds I and ES States of Cytochrome P450 Using Rapid Mixing Methods,” In Handbook of Porphyrin Science, Kadish, K.; Smith, K.; Guilard, R., Eds., Academic Press, New York (2010): Vol. 5, pp. 299–329.

Vetter, S.; Terentis, A.C.; Osborne, R.L.; Dawson, J.H.; Goodin, D.B. “Replace-ment of the Axial Histidine Heme Ligand with Cysteine in Nitrophorin I: Spectroscopic and Crystallographic Characterization.,” J. Biol. Inorg. Chem. (2009): 14, 179–191.

Osborne, R.L.; Coggins, M.K.; Raner, G.M.; Walla, M.; Dawson, J.H. “A. ornata Dehaloperoxidase Catalyzes Oxidative Halophenol Dehalogenation by a Mechanism Involving Two Consecutive One-Electron Steps: Charac-terization and Role of Compound II.,” Biochemistry (2009): 48, 4231–8.

Davydov, R.; Osborne, R.L.; Kim, S.H.; Dawson, J.H.; Hoffman, B.M. “EPR and ENDOR Studies of Cryoreduced Compounds II of Peroxidases and Myoglobin. Proton-Coupled Electron Transfer and Protonation Status of Ferryl Hemes.” Biochemistry (2008): 47, 5147–5155.

Spolitak, T.; Dawson, J.H.; Ballou, D.P. “Replacement of Tyrosine Resi-dues by Phenylalanine in Cytochrome P450cam Alters Formation of Cpd II-like Species in Reactions with Artificial Oxidants.” J. Biol. Inorg. Chem. (2008): 13, 599–611.

Osborne, R.L.; Coggins, M.K.; Terner, J.; Dawson, J.H. “Caldariomyces fumago Chloroperoxidase Catalyzes the Oxidative Dehalogenation of Chlo-rophenols by a Mechanism Involving Two One-Electron Steps.” J. Am. Chem. Soc. (2007): 129, 14838–9.

Osborne, R.L.; Coggins, M.K.; Walla, M.; Dawson, J.H. “Horse Heart Myoglobin Catalyzes the H2O2-Dependent Oxidative Dehalogenation of Chlorophenols to DNA-Binding Radicals and Quinones.” Biochemis-try (2007): 46, 9823–9.

Kim, S.H.; Perera, R.; Hager, L.P.; Dawson, J.H.; Hoffman, B.M. “Rapid-Freeze Quench ENDOR Study of Chloroperoxidase Compound I: The Site of the Radical.” J. Am. Chem. Soc. (2006): 128, 5598–5599.

Qin, J.; Perera, R.; Lovelace, L.L.; Dawson, J.H.; Lebioda, L. “The Struc-tures of Thiolate- and Carboxylate-Ligated Ferric H93G Myoglobin: Models for Cytochrome P450 and for Oxyanion-Bound Heme Proteins.” Biochem-istry (2006): 45, 3170–7.

Glascock, M.C.; Ballou, D.P; Dawson, J.H. “Direct Observation of a Novel Perturbed Oxyferrous Catalytic Intermediate During Reduced Putidaredoxin-Initiated Turnover of P45-CAM. Probing the Effector Role of Putidaredoxin in Catalysis.” J. Biol. Chem. (2005): 280, 42134–41.

Spolitak, T.; Dawson, J.H.; Ballou, D.P. “Reaction of Ferric P450-CAM with Peracids: Kinetic Characterization of Intermediates on the Reaction Pathway.” J. Biol. Chem. (2005) 280, 20300–9.

Davydov, R.; Perera, R.; Jin, J.; Yang, T.C., Bryson, T.A.; Sono, M.; Dawson, J.H. Hoffman, B.M. “Substrate Modulation of the Properties and Reactiv-ity of the Oxy-Ferrous and Hydroperoxoferric Intermediates of Cytochrome P450cam as Shown by Cryoreduction- EPR/ENDOR Spectroscopy.” J. Am. Chem. Soc. (2005): 127, 1403–1413.

A.B., 1972, Columbia University; ph.d., 1976, Stanford University; NIH postdoctoral Fellow, 1976–1978, California Institute of Technology.

Camille and Henry Dreyfus Teacher-Scholar Award, 1982–87; Alfred p. Sloan Foundation Research Fellow, 1983–1987; Research Career development Award, NIH, 1983–1988; Out-standing South Carolina Chemist Award, S.C. Section, American Chemical Society, 1988; Russell Research Award for Science, Univer-sity of South Carolina, 1988; Elected Fellow, American Association for the Advancement of Science, 1989; Basic Science Research Award, University of South Carolina School of Med-icine, 1993; Governor’s Award for excel-lence in Science discovery, 1997; Conference Chair, 10th International Conference on Cyto-chrome p450, San Francisco, 1997; Chair of the Bioinorganic Subdivision, Inorganic Division, American Chemical Society, 2000; Southern Chemist Award, Memphis Section, Ameri-can Chemical Society, 2003; Carolina Trustee Professorship, University of South Carolina, 2004; Chair, Metal Ions in Biology Gordon Research Conference, 2005; Charles H. Stone Award, Charlotte/Piedmont Section, American Chemical Society, 2006; International Scientific Committee, International Conference on Cyto-chrome p450, 1997-present; editorial Board, Chemtracts-Inorganic Chemistry, Springer-Verlag, Inc., 1992–present; Journal of Biological Chemistry, 2002–2007; editor-in-Chief, Journal of Inorganic Biochemistry, 1996–present; elected Fel-low, American Chemical Society, 2010.

16

Research Areas: Environmental chemistry; fate and transport of organic chemicals in the environment; water chemistry; photochemically driven oxidation; photocatalysis; trace organic analysis; combinato-rial chemistry; free radical chemistry.

My research is broadly centered on studying the fate of organic chemicals in the environment. This includes man-made chemicals like pollutants, phar-maceuticals, and pesticides and also naturally occur-ring chemicals like biotoxins, signaling molecules, and various plant products. My group applies advanced analytical techniques to learn how these chemicals are transformed in or removed from the environment.

Analytical approaches: Environmental analyses need to be fast, sensitive, and selective. We use whatever analytical tools we need to, but most often work with gas or liquid chromatographs with mass spec-trometric or spectroscopic detectors. We also use absorbance or fluorescence spectroscopy (steady state and time resolved), various electrochemical techniques, nuclear magnetic resonance spectros-copy, infrared spectroscopy, and transmission elec-tron microscopy.

Experimental approaches: Environmental chemists spend time in the field making measurements and in the laboratory testing explanations for their field-work. My group has done fieldwork measuring the fate and distribution of organic chemicals, nanopar-ticles, transition metals, and oxidants like hydro-gen peroxide or the hydroxyl radical. We quantify the relationships between those analytes in the lab-oratory with sophisticated environmental model-ing techniques. We use robotic systems to generate solutions modeling hundreds of different environ-mental conditions simultaneously, a process called combinatorial environmental chemistry. These solu-tions are spiked with a variety of probe molecules and contaminants and then subjected to weather-ing processes in the laboratory. This allows us to rapidly interrogate environmental systems for their ability to promote photodegradation, free radical oxidation, complexation of transition metals, etc. Coupling this approach with field monitoring is one of the surest ways to make sound predictions about what will happen to pollutants as they are processed by environmental systems.

R e p R e s e n tat i v e p u b l i c at i o n s

Burns, J.M.; P.S. Craig; T.J. Shaw; J.L. Ferry. “Multivariate Examina-tion of Fe(II)/Fe(III) Cycling and Consequent Hydroxyl Radical Genera-tion.” Environmental Science & Technology, (2010); http://pubs.acs.org/doi/pdf/10.1021/es903519m.

Ferry, J.L.; P.S. Craig; C. Hexel; P. Sisco; R. Frey; P.L. Pennington; M.H. Ful-ton; I.G. Scott; A.W. Decho; S. Kashiwada; C.J. Murphy; T.J. Shaw. “Trans-fer of gold nanoparticles from the water column to the estuarine food web.” Nature Nanotechnology, (2009): 4(7), 441–444.

Cui, Y.; R.L. Frey; J.L. Ferry; P.L. Ferguson. “Identification of hydroxyl radi-cal oxidation products of N-hexanoyl-homoserine lactone by reversed-phase high-performance liquid chromatography coupled with electrospray ioniza-tion tandem mass spectrometry.” Rapid Communications in Mass Spectrome-try, (2009): 23(8), 1212–1220.

Burns, J.M.; S. Hall; J.L. Ferry. “The adsorption of saxitoxin to clays and sed-iments in fresh and saline waters.” Water Research, (2009): 43(7), 1899–1904.

Craig, P.S.; T.J. Shaw; P.L. Miller; P.J. Pellechia; J.L. Ferry. “Use of Multi-parametric Techniques to Probe the Effects of Naturally Occurring Ligands on the Oxidation of Fe(II).” Environmental Science & Technology, (2009): 43 (2), 337–342.

Decho, A.W.; P.T. Visscher; J.L. Ferry; T. Kawaguchi; L. He; K.M. Prze-kop; S.R. Norman; P.R. Reid, P.R. “Autoinducers extracted from microbial mats reveal a surprising diversity of N-acylhomoserine lactones (AHL) and abundance changes that may relate to diel pH.” Environmental Microbiol-ogy, (2009): 11(2), 409-420.

Alkilany, A.M.; R.L. Frey; J.L. Ferry; C.J. Murphy. “Gold Nanorods as Nanoadmicelles: 1-Naphthol Partitioning into a Nanorod-Bound Surfac-tant Bilayer.” Langmuir, (2008): 24(18), 10235–10239.

Pearman, W.F.; S.M. Angel; J.L. Ferry; S. Hall. “Characterization of the Ag mediated surface-enhanced Raman spectroscopy of saxitoxin.” Applied Spec-troscopy, (2008): 62(7), 727–732.

Wyatt, M.D., and J.L. Ferry. “Nanomaterials-Toxicity, Health and Envi-ronmental Issues” Challa S.S.R. Kumar, Ed. Small. (2007): Vol. 3, 1272.

Grassian, V.H.; G. Meyer; H. Abruna; G.W. Coates; L.E. Achenie; T. Alli-son; B. Brunschwig; J. Ferry; M. Garcia-Garibay; J. Gardea-Torresday; C.P. Grey; J. Hutchison; C.-J. Li; C. Liotta; A. Ragauskas; S. Minteer; K. Muel-ler; J. Roberts; O. Sadik; R. Schmehl; W. Schneider; A. Selloni; P. Stair; J. Stewart; D. Thorn; J. Tyson; B. Voelker; J.M. White; and F. Wood-Black. “Chemistry for a sustainable future.” Environmental Science & Technology, (2007): 41(14),4840–4846.

Ford, Q.L.; J.M. Burns; J.L. Ferry. “Aqueous in situ derivatization of carboxylic acids by an ionic carbodiimide and 2,2,2-trifluoroethylamine for electron-cap-ture detection.” Journal of Chromatography A, (2007): 1145(1–2), 241–245.

Burns, J.M.; T.B. Schock; M.H. Hsia; P.D.R. Moeller; J.L. Ferry. “Photo-stability of kainic acid in seawater.” Journal of Agricultural and Food Chemis-try, (2007): 55(24), 9951–9955.

J o h n l . f e r ryA S S O C I AT E P R O F E S S O Rferry@mail.chem.sc.edu

A n A ly t i c A l

B.S., 1990, University of Illinois-Urbana; M.S., 1993, University of North Carolina-Chapel Hill; ph.d., 1996, University of North Caro-lina-Chapel Hill; postdoctoral Fellow, 1996–1998; University of Texas-Austin.

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P h y s i c A l

Research Areas: Theoretical and computational chemistry including quantum effects in dynamics of nuclei, development of approximate quantum potential method applicable to large molecu-lar systems and studies of reactivity of hyperther-mal oxygen.

Quantum effects in dynamics of nuclei: Quantum-mechanical effects in molecular dynamics are essen-tial for accurate description and understanding of many chemical processes, such as those in surface reactions, in photochemistry, in interactions of molecules with electric field, and in chemistry of polymers, clusters, and liquids. QM effects are the most pronounced in processes involving atomic and molecular hydrogen including reactions in enzymes, other biomolecular environments, and nanomate-rials. For example, the isotope effects in water are manifested in such basic properties as melting point, which is 3.82ºC for D2O, and the temperature of maximum density in liquid state, which is 4ºC for H2O and 11.2ºC for D2O. The exact methods of

solving the time-dependent Schrodinger equation based on the grid or basis function representation are unfeasible for systems beyond 10–12 degrees of freedom because of the exponential scaling of numerical efforts with the system size. In contrast, methods of molecular dynamics based on classical trajectories are routinely applied to high-dimen-sional systems of hundreds of atoms, but they have two fundamental limitations: (1) the Born-Oppen-heimer separation of motion of electrons and nuclei resulting in a single electronic surface dynamics and (2) the classical motion of nuclei. Both issues can be resolved by doing dynamics simulation with quantum trajectories. Our theoretical work is guided by the ultimate goal—to study dynam-ics of complex molecular systems using an accurate and efficient method which incorporates the quan-tum effects and is compatible with classical molec-ular dynamics. Possible applications include proton transfer processes in enzymes and other biomolec-ular environments and incoherent electron trans-port in open quantum systems, such as molecular electronic devices.

Quantum or Bohmian trajectories: The time-depen-dent Schrodinger equation can be recast in terms of the wave function amplitude and phase associ-ated with the trajectories evolving in time according to Hamilton’s equations of motion. All quantum effects are expressed through the action of quan-tum potential dependent on the amplitude and its derivatives, acting on a trajectory in addition to the external “classical’’ potential. For general problems, the exact determination of the quantum potential is at least as difficult as the solution of the standard Schrodinger equation, but the quantum trajectory formulation provides a convenient starting point for approximation of the “quantum’’ quantities, which are small in the semiclassical limit of heavy particles such as nuclei. We develop global approximations to the quantum potential, which capture domi-nant quantum effects, such as zero-point energy, tunneling, and wavepacket bifurcation, in a com-putationally efficient manner (currently tested for up to 40 degrees of freedom). Longtime (picosec-onds) zero-point energy description is of special importance in condensed phase (system interacting with the environment). Current work extends the quantum trajectory formalism to evolution under the Boltzmann operator, which enables direct com-putation of thermal reaction rate constants from trajectory dynamics.

Reactivity of hyperthermal oxygen: Reactions of oxy-gen colliding with various gas phase molecules and surfaces at energies of several eV are studied using quasi-classical and quantum trajectories in conjunc-tion with experiments. Conceptual issues of interest are effects of intersystem crossing and zero-point energy redistribution on reactivity.

R e p R e s e n tat i v e p u b l i c at i o n s

S. Garashchuk. “Calculation of reaction rate constants using approximate evolution of quantum trajectories in imaginary and real time.” Chem. Phys. Lett. (2010): 491, 96–101.

T. K. Minton, A. Brunsvold, J. Zhang, H.P. Upadhyaya, J.P. Camden, S. Garashchuk, and G.C. Schatz. “Crossed-beams and theoretical stud-ies of hyperthermal reactions of O(3P) with HCl.” J. Chem. Phys. (2010): A 114, 4905–4916.

S. Garashchuk. “Quantum trajectory dynamics in imaginary time with the momentum-dependent quantum potential.” J. Chem. Phys. (2010): 132, 014112.

S. Garashchuk and V.A. Rassolov. “Stable long-time semiclassical descrip-tion of zero-point energy in high-dimensional molecular systems.” J. Chem. Phys. (2008): 129, 024109.

S. Garashchuk, V.A. Rassolov, and G.C. Schatz. “Semiclassical nonadiabatic dynamics based on quantum trajectories for the O(3P, 1D)+H2 system.” J. Chem. Phys. 124 (2006): 244307.

S. Garashchuk and V.A. Rassolov. “Energy conserving approximations to the quantum potential: Dynamics with linearized quantum force.” J. Chem. Phys. (2004):120, 1181.

S. Garashchuk and V.A. Rassolov. “Semiclassical dynamics with quantum trajectories: Formulation and comparison with the semiclassical initial value representation propagator.” J. Chem. Phys. 118 (2003): 2482.

D.J. Tannor and S. Garashchuk. “Semiclassical calculation of chemical reaction dynamics via wavepacket correlation functions.” Annu. Rev. Phys. Chem. 51 (2000): 553.

S. Garashchuk, F. Grossmann, and D. Tannor. “Semiclassical approach to the hydrogen-exchange reaction—Reactive and transition-state dynamics.” J. Chem. Soc. Faraday Trans. 93 (1997): 781.

s o P h yA g A r A s h c h U kA S S I S TA N T p R O F e S S O Rgarashchuk@chem.sc.edu

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M.S., Physics, 1992, Moscow Institute of Phys-ics and Technology, Ph.D., 1999, University of Notre dame postdoctoral Fellow, 1999–2001, University of Chicago.

IBM-lowdin Fellowship, 2004, Sanibel sym-posium.

Figure 1

Figure 2

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A n A ly t i c A l

Research Areas: Analytical atomic spectroscopy; plasma spectroscopy; laser atomization; chemical instrumentation; automated and interactive com-puter control over analytical experiments; environ-mental analytical chemistry; analytical chemistry of radioactive wastes.

Research in modern analytical chemistry is research in understanding measurements, their accuracy, their precision, and their sources of errors. The analytical chemist oversees the entire process that transforms physical and chemical information, like concentration, into a form meaningful to scien-tists—a number. The goal of the analytical chemist is to produce the “best,” or optimum, measurement. But in order to optimize the measurement, the

sources of errors and imprecision of each step in the measurement process must be known. We are cur-rently studying microwave induced plasmas, induc-tively coupled plasmas, and laser induced plasmas to learn the fundamental plasma processes and to use them as excitation sources in atomic spectroscopy.

The Laser Induced Breakdown Spectroscopy (LIBS). LIBS uses a tightly focused laser beam to vaporize a sample and form a plasma. This relatively new method has many advantages since it can use gas, liquid, or solid samples and is amenable to remote analysis via fiber-optic link. For LIBS to realize its full potential, the events leading to the generation of the optical signal must be studied and under-stood. One of the most important questions fac-ing the users of this (and of any) analytical tool is whether the sample matrix influences the analytical results. If the analysis is matrix independent, then

2.0 percent lead in paint produces the same signal as 2.0 percent lead in steel. Although the matrix effect could possibly be studied empirically, funda-mental studies of the laser induced breakdown spec-

troscopy provide a much more organized basis to answer this and many other questions. Such work is in progress in our laboratory.

R e p R e s e n tat i v e p u b l i c at i o n s

Dockery, C.R., M.J. Blew, and S.R. Goode. “Visualizing the solute vaporiza-tion interference in flame atomic absorption spectroscopy.” Journal of Chem-ical Education (2008): 85(6), 854–858.

Dockery, C.R., J.E. Pender, and S.R. Goode. “Speciation of Chromium via Laser-Induced Breakdown Spectroscopy of Ion Exchange Polymer Mem-branes.” Applied Spectrosc., (2005): 59(2), 252–257.

Metz, L.A., N.K. Meruva, S.L. Morgan, and S.R. Goode. “UV Laser Pyrol-ysis Fast Gas Chromatography/Time-of-Flight Mass Spectrometry for Rapid Characterization of Synthetic Polymers: Optimization of Instrumental Param-eters.” J. Anal. Appl. Pyrolysis (2004): 71, 313–325.

Metz, L.A., N.K. Meruva, S.L. Morgan, and S.R. Goode. “UV laser pyrolysis fast gas chromatography/time-of-flight mass spectrometry for rapid character-ization of synthetic polymers: optimization of instrumental parameters.” Jour-nal of Analytical and Applied Pyrolysis 71 (1), (2004): 327–341.

Dockery, C.R., and S.R. Goode. “Laser-induced breakdown spectroscopy for the detection of gunshot residues on the hands of a shooter: applicability and analysis of error.” Appl. Optics. (2003): 42(30), 6099–6106.

Goode, S.R., and L.A. Metz. “Emission Spectroscopy in the Undergraduate Laboratory.” J. Chem. Educ. 80 (12), (2003): 1455–1459.

Scaffidi, J., J. Pender, B. Pearman, S.R. Goode, B.W. Colston Jr., J.C. Carter, and S.M. Angel. “Dual-pulse LIBS using combinations of femtosecond and Nanosecond laser pulses.” Applied Optics 42 (30), (2003): 6099–6106.

Schmidt, N.E., and S.R. Goode. “Analysis of aqueous solutions by LIBS of Ion Exchange Membranes.” Appl Spectrosc. (2002): 55, 370–74.

Eland, K.L., D.N. Stratis, D.M. Gold, S.R. Goode, and S.M. Angel. “Energy Dependence of Emission Intensity and Temperature in a LIBS Plasma using Femtosecond Excitation.” Appl. Spectrosc. (2001): 55, 286–291.

Eland, K.L., D.N. Stratis, T. Lai, M.A. Berg, S.R. Goode and S.M. Angel. “Some Comparisons of LIBS Measurements Using Nanosecond and Pico-second Laser Pulses.” Appl. Spectrosc. (2001): 55, 279–285.

Goode, S.R. “Influence of the Isotopic Composition of Standards on the Accuracy of Atomic spectrometry.” Appl. Spectrosc. (2001): 55, 1225–1228.

Goode, S.R., S.L. Morgan, R. Hoskins, and A. Oxsher. “Identifying alloys by laser-induced breakdown spectroscopy with a time-resolved high resolu-tion echelle spectrometer.” J. Anal. At. Spectrom. (2000): 15, 1133–1138.

Figure 3. Identification of alloys by principal component analysis of their LIBS spectra

s c ot t r . g o o D eP R O F E S S O Rgoode@sc.edu

B.S., 1969, University of Illinois - Urbana; Ph.D., 1974, Michigan State University.

Distinguished Professor, South Carolina Hon-ors College, University of South Carolina, 1986; Amoco Foundation Outstanding Teach-ing Award, University of South Carolina, 1991; Michael J. Mungo Award for Excellence in Undergraduate Teaching, University of South Carolina, 1998; College of Science and Mathe-matics Undergraduate Student Advisor of the year Award, University of South Carolina, 1998; Ada B. Thomas Outstanding Faculty Advisor Award, 2000; S.C. Section ACS distinguished Service Award, 2009.

Figure 2. Typical LIBS spectrum

Figure 1. Block diagram of lIBS experiment

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Research Areas: The Greytak lab explores physical and materials chemistry at the liquid-solid inter-faces of semiconductors.

A strong inspiration for this work is the opportu-nity to impact fields including energy conversion, energy storage, and bioimaging with current inter-est in understanding how the properties of semi-conductor nanostructures (colloidal nanocrystals, catalytically synthesized nanowires, and heterostruc-tures) can be modified by controlling the chemis-try at their surfaces.

There are two general themes that guide our choice of problems. One is electronic and con-cerns the motion of charge within nanoscale sys-tems and across interfaces and how we can learn to stimulate and detect such charge transfer pro-cesses from afar. The second is structural and is an attempt to develop synthetic strategies and imag-ing techniques that can allow us to draw analogies between forms of the same material with different dimensionalities. These themes will be explored in several project areas.

Ligand-mediated chemistry at nanowire and nanocrys-tal surfaces: Semiconductor nanocrystals (NCs, also known as quantum dots) are readily prepared by wet chemistry techniques, and a (usually organic) ligand coating passivates their surfaces and pro-vides colloidal stability. One-dimensional semi-conductor nanowires (NWs) can be synthesized by using a catalyst nanoparticle to direct growth in only one crystal direction—and can be synthe-sized “dry” using vapor-phase precursors. Both NCs

and NWs are of interest for solar energy capture in photovoltaic or photocatalytic systems as they can absorb sunlight at energies above their bandgaps, can be deposited on diverse and inexpensive sub-strates, and exhibit large junction areas that could increase the rate at which absorbed light is cap-tured as separated charges.

Nanowires have several potential strengths, includ-ing efficient charge transport in the axial direction and a solvent-free synthesis that can be run at high temperature to minimize formation of crystal defects that could act as recombination centers. However, when compared to NCs, relatively less attention has been paid to specific chemistries at their surfaces.

This project aims to develop ligand-mediated, solu-tion-phase approaches to growing conformal layers on NWs prepared by high-temperature vapor-source growth. The ultimate goal is to form semiconduc-tor and/or dielectric shells that enable the NWs to function as light-absorbing components of photo-voltaic and photocatalytic cells.

Electronic properties of nanowire semiconductor-liquid junctions and role of interfacial layers: The basic electronic structure of semiconductor NWs and NCs is set by the nature of the semiconduc-tor material and the shape of the nanostructures. However, the surface interfaces of these materials are critically important to determining the rate at which excited states decay and at which charge is transported.

Nanowires can be a good system for studying the electronic effects of surface modification as they are easily contacted with microfabricated electrodes and have high surface areas; moreover, they are a system of interest for solar energy conversion via charge transfer across their surfaces, including direct solar fuel synthesis by coupling NWs to catalysts capable of performing energy-storing chemical reactions.

This project aims to measure and visualize charge transport and charge transfer in NWs with chemi-cally modified surfaces. The microfabrication pro-cesses used to contact NWs also lend themselves to the study of charge transport in catalytic films directly via multipoint probe techniques.

Colloidal nanocrystals with heterogeneous solution interfaces as biological probes: Because NWs are easily immobilized, can be suspended over vacuum in the electron microscope, and are invariant in the axial direction, they can serve as a convenient “studio”

to study the structure of surface-bound layers in ways that would be difficult to implement on zero-dimensional nanoparticles or on planar substrates.

We will use semiconductor nanowires to assess ligand conformation, binding kinetics, and phase segregation of mixtures of dissimilar ligands at nanostructured chalcogenide semiconductor sur-faces. We will seek to apply this knowledge in the design of fluorescent nanocrystal sensors targeted to the lipid bilayer.

Skills and techniques: The focus of the lab is on mea-surement and imaging, but we will bring together a variety of synthetic techniques to achieve the neces-sary control of structure and electronic properties.

Students and postdocs with a variety of academic backgrounds including physical, inorganic, and organic chemistry; condensed matter physics; mate-rials science; and electrical engineering will be able to make strong contributions to the group’s research. Group members can expect to master techniques including chemical vapor deposition, synthetic inorganic and organic (for ligand design) chemis-try, scanning and transmission electron microscopy, microfabrication, and photoluminescence imaging and spectroscopy.

R e p R e s e n tat i v e p u b l i c at i o n s

W. Liu, A.B. Greytak, J. Lee, C.R. Wong, J. Park, L.F. Marshall, W. Jiang, P.N. Curtin, A.Y. Ting, D.G. Nocera, D. Fukumura, R.K. Jain, and M.G. Bawendi. “Compact biocompatible quantum dots via RAFT-mediated syn-thesis of imidazole-based random copolymer ligand.” J. Am. Chem. Soc. (2010): 132, 472.

E.J. McLaurin, A.B. Greytak, M.G. Bawendi, and D.G. Nocera. “Two-Pho-ton Absorbing Nanocrystal Sensors for Ratiometric Detection of Oxygen.” J. Am. Chem. Soc. (2009): 131, 12994.

W. Liu, M. Howarth, A.B. Greytak, Y. Zheng, D.G. Nocera, A.Y. Ting, and M.G. Bawendi. “Compact biocompatible quantum dots functionalized for cellular imaging.” J. Am. Chem. Soc. (2008): 130, 1274.

A.B. Greytak, C.J. Barrelet, Y. Li, and C.M. Lieber. “Semiconductor nanow-ire laser and nanowire waveguide electro-optic modulators.” Applied Physics Letters, (2005): 87, 151103.

O. Hayden, A.B. Greytak, and D.C. Bell. “Core-Shell Nanowire Light-Emit-ting Diodes.” Advanced Materials, (2005): 17, 701.

C.J. Barrelet, A.B. Greytak, and C.M. Lieber. “Nanowire photonic circuit elements.” Nano Letters (2004): 4, 1981.

A.B. Greytak, L.J. Lauhon, M.S. Gudiksen, and C.M. Lieber. “Growth and transport properties of complementary germanium nanowire field effect tran-sistors.” Applied Physics Letters (2004): 84, 4176.

P h y s i c A l

A n D r e W B . g r e y tA kA S S I S TA N T p R O F e S S O Rgreytak@chem.sc.edu

B.S., 2000, Massachusetts Institute of Tech-nology; ph.d., 2006, Harvard University; post-doctoral, 2006–2010, Massachusetts Institute of Technology.

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W. s t e P h e n k i s t l e rP R O F E S S O Rkistler@chem.sc.edu

B i o c h e m i s t ry

Research Areas: Molecular biology; regulation of gene expression and function of chromosomal pro-teins; current emphasis is on the use of recombi-nant DNA technology to characterize genes that have roles in the male reproductive tract; under-standing the transcriptional regulation of the gene for the testis-specific linker histone, H1t, and one of its transcriptional regulators, Rfx2.

Chromosomal proteins impart both structure and regulation to DNA sequences. Characterization of specific chromosomal proteins will lead to better understanding of both chromatin structure and regulation of gene expression. The process of sper-matogenesis involves a complex program of ordered gene expression as well as a series of nuclear events that are unique to male gamete differentiation. For example, meiosis describes the process by which homologous chromosomes pair, undergo genetic

recombination, and finally separate to yield hap-loid cells. During this period several testis-specific histone variants appear. Histones are small pro-teins that are responsible for packaging DNA into chromosomes. H1t is one of the novel variants made during meiosis, and we have isolated and sequenced the H1t gene. Later during spermato-genesis, a complete reorganization of the nucleus occurs. Histones of all kinds are largely eliminated. For a brief period the so-called nuclear transition proteins appear. They are then replaced by the prot-amines, which are very small, basic proteins that organize DNA in the nucleus of the sperm cell. We have also isolated genes for one of the transition proteins (TP1) as well as the major rat protamine.

We are interested in the factors that cause these genes to be expressed in an ordered way during spermatogenesis and also in the ways these novel proteins interact with DNA. Recent work has iden-tified transcription factor RFX2 as a good can-didate to regulate expression of H1t as well as a number of other genes expressed during the mei-otic phase of spermatogenesis. RFX2 is expressed almost uniquely in testis germ cells beginning dur-ing meiotic prophase. In an attempt to trace regu-lation of spermatogenic gene expression backward, we recently showed that transcription factor A-MYB is likely to regulate Rfx2 expression. We now hope to identify the full complement of germline targets for these two transcription factors by the ChIP-Seq technique. This involves immunoprecipitation of chromatin sites bound by the factor followed by next-generation sequence analysis of the recovered DNA fragments. We also plan to create a mouse with a targeted Rfx2 deletion to establish its criti-cal role in spermatogenesis.

R e p R e s e n tat i v e p u b l i c at i o n s

Horvath, G.C., M.K. Kistler, and W.S. Kistler. “RFX2 is a Candidate Down-stream Amplifier of A-MYB Regulation in Mouse Spermatogenesis.” BMC Develop. Biol. 9, (2009): 63.

Kistler, W.S., G.C. Horvath, A. Dasgupta, M.K. Kistler. “Differential Expression of Rfx1-4 during Mouse Spermatogenesis.” Gene Exp. Pat-terns 9, (2009): 515.

Ma, W., G.C. Horvath, M.K. Kistler, and W.S. Kistler. “Expression patterns of SP1 and SP3 during mouse spermatogenesis: SP1 down-regulation corre-lates with two successive promoter changes and translationally compromised transcripts.” Biol. Reprod. 79, (2008): 289.

Ma, W., G.C. Horvath, and M.K. Kistler. “Alternative promoter use dur-ing mouse spermatogenesis leads to marked down-regulation of transcrip-tion factor Sp1.” FASEB J. 21, (2007): A1034.

Horvath, G.C., W.S. Kistler, and M.K. Kistler. “RFX2 is a potential tran-scriptional regulatory factor for histone H1t and other genes expressed dur-ing the meiotic phase of spermatogenesis.” Biol. Reprod. 71, (2004): 1551.

Horvath, G.C., A. Dasgupta, M.K. Kistler, and W.S. Kistler. “The Rat Histone H1d Gene Has Intragenic Activating Sequences That Are Absent from the Testis-Specific Variant H1t.” Biochim. Biophys. Acta. 1625, (2003): 165–172.

Horvath, G.C., S.E. Clare, M.K. Kistler, and W.S. Kistler. “Characterization of the H1t Promoter: Role Of Conserved H1 AC And TG Elements And Dominance Of The Cap-Proximal Silencer.” Biol. Reprod. 65, (2001): 1074.

Fantz, D.A., W.R. Hatfield, G. Horvath, M.K. Kistler, and W.S. Kistler. “Mice With A Targeted Disruption Of The H1t Gene Are Fertile And Undergo Normal Changes In Structural Chromosomal Proteins During Spermato-genesis.” Biol. Reprod. 64, (2001): 425.

A.B., 1964, princeton University; ph.d., 1970, Harvard University; Postdoctoral Fellow, 1971–1975, University of Chicago.

Basic Science Research Award, University of South Carolina School of Medicine, 1989.

Two-dimensional pAGe shows that knockout mouse lacks linker histone variant H1t. Immunofluorescent stain shows that transcription

factor B-MyB is found only in early germ cells while A-MyB appears in the same cells that express his-tone H1t. Green: immuno stain; Red: dNA.

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Research Areas: Molecular recognition, supramo-lecular chemistry, sensors, materials, bio-organic, physical organic.

The overriding goal in our lab is to understand and predictably control how molecules interact in order to develop new self-assembled materials for real world applications. For example, these assem-blies can serve as diagnostics for cancer and food spoilage, as nano-porous materials for gas storage

and separation, as novel conjugated polymers for use in OLEDs and PVs, and as new age plastics.

Students are involved in the design, synthesis, and analysis phases for each project. Computational methods are often used to aid in molecular design. Organic synthesis provides the foundation to build-in the interactions that control the assem-bly process and ultimately define the materials’ properties. Finally, analytical methods (e.g. optical spectroscopy, mechanical, electronic) are used to assess the assembly performance. Ultimately we enjoy projects where an end use beyond the lab is imaginable (often resulting in patents). With this in mind, the research experience gained in the group is often coupled to a biomedical or engi-neering component. In our efforts we work with three general types of compounds: boronates, conjugated polymers, and peptides.

Boronates: Novel self-assembling boronate-linked materials have been generated as linear polymers, conjugated materials, and nanoporous covalent organic frameworks (COFs). Given that this interaction is covalent yet reversible, these assem-blies form with high fidelity. Boronate ester formation maintains all of the desired attributes of self-assembling materials, including ease of syn-thesis and dynamic self-repair, while at the same time offering stable, covalently linked materials by a route oftentimes more facile and with higher efficiency than conventional polymer synthesis. Boronate-linked specialty plastics exhibit self-repair capabilities and environmental responsive-ness. Conjugated poly(boronate)s serve as novel photonic materials and sensitive sensors. Porous COFs and coordination polymers find utility in separations, sequestration, storage, sensing, and catalysis. We continue to investigate the mechani-cal, optical, and adsorption properties of these unique materials.

Conjugated Polymers: Using conjugated polymers that interact with small molecules and proteins, we have created cross-reactive “aggregative” sen-sors whose response is defined by the size, shape, and valency of the analyte. For example, a colori-metric sensing approach has been developed that can produce a response visible to the naked eye to determine the freshness of foods as a function of spoilage. A simple, point-of-use dipstick has been developed to assess food quality in restaurants and at home. Advanced analysis can be used to

deconvolute complex samples and simplify the device read-out. Studies to detect analytes such as proteins and small molecule biomarkers produce diagnostics for diseases such as cancer and HIV. This concept also investigates how small molecule additives can tune the electronic properties of the polymer-additive assemblies, for use in photonic applications.

New synthetic protocols, based on post-polym-erization modifications, are developed to modu-larly incorporate diverse functionality. This design allows for the rapid generation of new com-pounds and screening of properties to identify the most interesting candidates for new photonic and sensory materials.

Peptides: Synthetic lectins (SLs) are created to bind glycans and glycoproteins associated with numer-ous disease states. Specifically, SLs have identified aberrant glycosylation patterns associated with colorectal and other cancer types. These unique compounds have been used as in vitro diagnostics and hold great potential as in vivo imaging agents and therapeutics.

R e p R e s e n tat i v e p u b l i c at i o n sMaynor, M.S.; Deason, T.K.; Nelson, T.L.; Lavigne, J.J. “Multidimensional Response Analysis Towards the Detection and Identification of Soft Divalent Metal Ions.” Supramolecular Chem. (2009): 21, 310–315.

Tilford, R.W.; Mugavero, S.J.; Pellechia, P.J.; Lavigne, J.J. “Tailoring Micro-porosity in Covalent Organic Frameworks (COFs).” Adv. Mater. (2008): 20, 2741–2746.

Zuo, Y.; Broughton, D.L.; Bicker, K.L.; Thompson, P.R.; Lavigne, J.J. “Pep-tide Borono-Lectins (PBLs): A New Tool for Glycomics and Cancer Diag-nostics.” ChemBioChem (2007): 8, 2048–2051.

Nelson, T.L.; Tran, I.; Ingallinera, T.G.; Maynor, M.S.; Lavigne, J.J. “Multi-Layered Analyses Using Directed Partitioning to Identify and Discriminate between Biogenic Amines.” Analyst (2007): 132, 1024–1030.

Maynor, M.S.; Nelson, T.L.; O’Sullivan, C.; Lavigne, J.J. “A Food Fresh-ness Sensor using the Multi-State Response from Analyte Induced Aggrega-tion of a Cross-Reactive Poly(thiophene).” Org. Lett. (2007): 9, 3217–3220.

Rambo, B.M.; Lavigne, J.J. “Defining Self-Assembling Linear Oligo (diox-aborole)s.” Chem. Mater. (2007): 19, 3732–3739.

Niu, W.; Lavigne, J.J. “Self-Assembling Poly(Dioxaborole)s as Blue-Emissive Materials.” J. Am. Chem. Soc. (2006): 128; 16466–16467.

Tilford, R.W.; Gemmill, W.R.; zur Loye, H.-C.; Lavigne, J.J. Facile Synthesis of a Highly Crystalline, Covalently Linked Porous Boronate Network.” Chem. Mater. (2006): 18, 5296–5301.

Nelson, T.L.; O’Sullivan, C.; Greene, N.T.; Maynor, M.S.; Lavigne, J.J. “Cross-Reactive Conjugated Polymers: Analyte-Specific Aggregative Response for Structurally Similar Diamines.” J. Am. Chem. Soc. (2006): 128, 5640–5641.

Niu, W.; O’Sullivan, C.; Rambo, B.M. Smith, M.D.; Lavigne, J.J. “Self-Repairing Polymers: Poly(dioxaborolane)s Containing Trigonal Planar Boron.” Chem. Commun. (2005): 4342–4344.

J o h n J . l Av i g n eA S S O C I AT E P R O F E S S O Rlavigne@chem.sc.edu

o r g A n i c

B.S., 1993, St. lawrence University; M.ed., 1997, St. lawrence University; ph.d., 2000, University of Texas at Austin.

Honors/Awards: Michael J. Mungo Under-graduate Teaching Award, 2009; distinguished Undergraduate Research Mentor Award, 2007; Golden Key Faculty Award for Creative Integration of Research and Teaching, 2007; Research Corporation Research Innovation Award, 2004–2009.

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B i o c h e m i s t ry

l U k A s Z l e B i o D AG U y F. l I p S C O M B p R O F e S S O R O F B I O C H e M I S T Ry

lebioda@chem.sc.edu

Research Areas: Structural biochemistry; ratio-nal drug design based on enzyme structures and mechanisms; protein engineering and thermosta-bility; molecular evolution.

My laboratory is involved in studies of the struc-ture-function relationship of enzymes either related to cancer chemotherapy, the process of fertilization, or potential environmental applications.

The crystal structure of the complex of human thymidylate synthase (TS) with a substrate, dUMP, and a drug, Tomudex, determined at USC, is shown here (see figure). Inhibitors of TS are used in cancer chemotherapy. However, cancer cells develop resistance to the existing drugs typically by increasing the TS levels by a factor between 4 and 10. One of the mechanisms proposed to explain this phenomenon is increased stability to intracellular degradation upon forma-tion of complexes with presently used drugs. We are developing a new class of allosteric TS inhibitors that should not generate this problem. In our approach we stabilize an unusual confor-mation specific to human TS that leads to an inactive conformation rather than following the old approach of developing inhibitors targeting the active site. Moreover, inhibitors developed by

us show positive cooperativity with the classical active site directed inhibitors augmenting their anticancer properties.

My group, in collaboration with Dr. John Dawson, is studying the structure-function rela-tionship in enzymes catalyzing dehalogenation and halogenation of halocarbons. The most advanced are investigations of the structure and activity of dehalogenase from the marine poly-chaete organism Amphitrite ornata (DHP). This enzyme utilizes the oxidative potential of hydro-gen peroxide to dehalogenate chlorophenols (and also fluorophenols, bromophenols, and iodophe-nols) and is an order of magnitude faster than any other known dehalogenase despite its miniscule size, 16 kD per subunit. Contamination of waste water from paper mills and other industrial operations with chlorophenols is a serious envi-ronmental problem. In order to develop industrial biocatalysts with dehalogenase activity, DHP has been immobilized with retention of its cata-lytic activity. The enzyme, however, is not stable enough for large-scale applications. We are study-ing its structure and activity to engineer changes in the molecule that will lead to an increase in the enzyme’s stability. Such changes could include the introduction of cysteine bridges, elimination of solvent cavities, and reduction of the peptides chain flexibility by increasing the contents of proline residues and reducing the contents of glycine residues. The DHP ability to defluorinate halophenols is unique; we are not aware of any other enzyme that can catalyze the breakage of the

carbon-fluorine bond. We would like to utilize the enzymatic capability and work on engineering such modifications to the active site of DHP that will switch the affinity from the natural substrates, halophenols, to haloaromatics and even freons. The modified enzyme should find applications in the destruction of these pollutants responsible for the creation of the ozone holes.

R e p R e s e n tat i v e p u b l i c at i o n s

X. Huang, L.M. Gibson, B.J. Bell, L.L. Lovelace, M.M.O. Peña, F.G. Berger, S.H. Berger, and L. Lebioda. “Replacement of Val3 in Human Thymidylate Synthase Affects Its Kinetic Properties and Intracellular Stability.” Biochemistry (2010): 49, 2475–2482.

J. Jones, C.P. Causey, L.L. Lovelace, B. Knuckley, H. Flick, L. Lebioda, and P.R. Thompson. “Characterization and Inactivation of an Agmatine Deiminase from Helicobacter pylori.” Bioorg. Chem. (2010): 38, 62–73.

L.L. Lovelace, S.R. Johnson, L.M. Gibson, B.J. Bell, S.H. Berger, and L. Lebioda. “Variants of Human Thymidylate Synthase with Loop 181-197 Stabilized in the Inactive Conformation.” Protein Sci. (2009): 18, 1628–1636.

L.M. Gibson, N.N. Dingra, C.E. Outten, and L. Lebioda. “Structure of the thioredoxin-like domain of yeast glutaredoxin 3.” Acta Crystallogr. D. (2008): 64, 927–932.

H. Zheng, M. Chruszcz, P. Lasota, L. Lebioda, and W. Minor. “Data mining of metal ion environments present in protein structures.” J. Inorg. Biochem. (2008): 102, 1765–1776.

D.J. Slade, L.L. Lovelace, M. Chruszcz, W. Minor, L. Lebioda, and J.M. Sodetz. “Crystal Structure of the MACPF Domain of Human Complement Protein C8α in Complex with the C8γ Subunit.” J. Mol. Biol. (2008): 379, 331–342.

L.M. Gibson, L.L. Lovelace, and L. Lebioda. “The R163K Mutant of Human Thymidylate Synthase Is Stabilized in an Active Conformation: Asymmetry and Reactivity of Cys195.” Biochemistry (2008): 47, 4636–4643.

L.L. Lovelace, B. Chiswell, D.J. Slade, J.M. Sodetz, and L. Lebioda. “Crystal Structure of Complement Protein C8γ in Complex with a Peptide contain-ing the C8γ Binding Site on C8α: Implications for C8γ Ligand Binding.” Mol. Immunol. (2008): 45, 750–756.

B.S., 1965; ph.d., 1972; d.Sc., 1979, jagiellonian University (poland); postdoctoral Fellow, 1979–1982, Michigan State University.

Foreign Member of the Polish Academy of Arts and Sciences; Educational Foundation Research Award for Science, Mathematics, and Engi-neering, University of South Carolina, 1998; South Carolina Chemist of the year Award of the S.C. Division of the American Chemi-cal Society, 2009.

The structure of human thymidylate synthase in complex with the substrate dUMP and inhibitor/drug Tomudex.

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s t e P h e n l . m o r g A nP R O F E S S O Rmorgan@chem.sc.edu

A n A ly t i c A l

Research Interests: Analytical chemistry. Foren-sic and environmental analysis using chromatogra-phy and mass spectrometry; trace evidence analysis of textile fibers and polymers; rapid spectroscopic visualization of biological stains; analytical pyrol-ysis; chemometrics.

I have wide ranging research interests in analytical chemistry and applied statistics, especially in ana-lytical method development using experimental design, optimization, and pattern recognition. Our research has targeted diverse areas including analytical separations (GC, LC, and CE), mass spectrometry, analytical pyrolysis, and spectros-copy (UV/visible, fluorescence, ATR-IR, diffuse reflectance IR, and Raman). Recent research has focused on improvements in forensic fiber analy-sis, remote detection of biological stains at crime scenes using DRIFTS, and sample preparation methods coupled to GC/MS and LC/MS for pesticides, food adulterants, and drugs of abuse (with Dr. Brewer).

Dyes Extracted from Trace Evidence Fibers: We are developing and validating forensic analytical methods using microextraction, followed by sepa-rations and mass spectrometry, for trace analysis of fiber dyes. Figure 1 shows reconstructed ion electropherograms compared to standards for three dyes extracted from a 2 mm acrylic fiber, with detection limits in the picogram range.

Determining the number and relative amounts of dyes present, and characterizing those dyes at the molecular level by MS, offers an entirely new level of forensic trace fiber discrimination.

Chemometrics: We are using multivariate statis-tics to facilitate visualization of differences and hypothesis testing for decisions based on forensic analytical data. Figure 2 shows linear discriminant analysis for 10 replicate UV/vis spectra from 7 different fibers. Except for fibers 4 and 5, which have similar dye formulations, patterns of all other groups of fibers are discriminated. Spectra from two fibers not dyed with a blue dye (6 and 7) are at the bottom of the plot. The three groups of spectra from fibers dyed with the red 1 dye are on the left side of the plot, and those dyed with the red 2 dye are on the right side of the plot. Identi-fying unique features (chromatographic peaks or spectral wavelengths) that distinguish one pattern from another is essential for understanding the chemical basis for differences at a fundamental level.

Forensic Imaging with DRIFTS: In collaboration with the Myrick group, we have developed remote imaging techniques for the visualization of bio-logical stains at crime scenes. Detection is based

on processed reflectance measurements of char-acteristic absorption bands in mid-infrared range reflected from surface stains that contain proteins. Figure 3 shows diffuse reflectance spectra for neat and blood-coated acrylic fabric. Spectral differ-ences are seen in regions where IR absorbances due to blood proteins are found (amide I, II, and III peaks at 1200–1650 cm-1, amide A and B at 2800–3500 cm-1). Detection limits are estimated in the range of 200× diluted blood.

R e p R e s e n tat i v e p u b l i c at i o n s

H. Brooke, M.R. Baranowski, J.N. McCutcheon, S.L. Morgan, M.L. Myrick. “Multi-mode Imaging in the Thermal Infrared for Chemical Contrast Enhancement Part 3: Visualizing Blood on Fabrics,” Analytical Chemistry (2010): 2010, publication date (Web): September 23, 2010; DOI: 10.1021/ac101107v.

H. Guan, W.E. Brewer, S.T. Garris, S.L. Morgan. “Disposable pipette extrac-tion for enrichment of pesticides from fruits and vegetables and direct analy-sis by GC/MS.” J. Chromatogr. A (2010): 1217, 1867–1874.

B.L. Vann, S.M. Angel, S.L. Morgan, J.E. Hendrix, E.G. Bartick. “Analy-sis of titanium dioxide in synthetic fibers using Raman microspectroscopy.” Applied Spectroscopy (2009): 63(4), 407–411.

S.T. Ellison, A.P. Gies, D.M. Hercules, and S.L. Morgan. “MALDI-TOF/TOF CID study of polysulfone fragmentation reactions.” Macromolecules (2009): 42 (8), 3005–3013.

S.T. Ellison, A.P. Gies, D.M. Hercules, and S.L. Morgan. “Py-GC/MS and MALDI-TOF/TOF CID study of polyphenylsulfone fragmentation reac-tions.” Macromolecules (2009): 42 (15), 5526–5533.

S.T. Ellison, W.E. Brewer, S.L. Morgan. “Comprehensive analysis of drugs of abuse in urine using disposable pipette extraction.” J. Anal. Toxicol. (2009): 33 (7), 356–365.

A.R. Stefan, C.R. Dockery, A.A. Nieuwland, S.N. Roberson, B.M. Baguley, J.E. Hendrix, S.L. Morgan. “Forensic analysis of anthraquinone, azo, and metal complex acid dyes from nylon fibers by micro-extraction and capillary electrophoresis.” Anal. Bioanal. Chem. (2009): 394, 2077–2085.

C.R. Dockery, A.R. Stefan, A.A. Nieuwland, S.N. Roberson, B.M. Baguley, J.E. Hendrix, S.L. Morgan. “Automated extraction of direct, reactive, and vat dyes from cellulosic fibers for forensic analysis by capillary electrophore-sis.” Anal. Bioanal. Chem. (2009): 394, 2095–2103.

A.R. Stefan, C.R. Dockery, B.M. Baguley, B.C. Vann, A.A. Nieuwland, J.E. Hendrix, S.L. Morgan. “Microextraction, capillary electrophoresis, and mass spectrometry for forensic analysis of azo and methine basic dyes from acrylic fibers.” Anal. Bioanal. Chem. (2009): 394, 2087–2094.

B.S., 1971, duke University; M.S., 1974, emory University; ph.d., 1975, emory University; postdoctoral Fellow, 1975–1976, University of Houston.

Distinguished Undergraduate Research Mentor Award, University of South Carolina, May 2007; Sigma Xi distinguished lecturer, 2008–2010.

Figure1. Reconstructed ion electropherograms for dyes extracted from a 2 mm acrylic fiber.

Figure 2. ldA of UV/visible spectra from 7 dyed nylon fibers.

Figure 3. Replicate DRIFTS spectra of neat acrylic fabric (blue) and blood-coated acrylic fabric (red).

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Research Areas: The following sections describe two projects we are currently pursuing.

Spectroscopy of Phytoplankton: Phytoplankton use photosynthesis to produce fixed carbon and are thus key players in pelagic food webs. Many phytoplank-ton species also form harmful algal blooms (HABs) and can release toxins into the environment that create health problems or kill fish, marine mam-mals, and humans.

The traditional method for identifying phytoplank-ton species is light microscopy by a human expert. Fluorescence spectroscopy, using excitation and/or emission spectra, provides a noninvasive, non-destructive alternative approach to pigment-based identification, and phytoplankton can be examined intact. The research groups of Prof. Timothy Shaw and Prof. Tammi Richardson (biological sciences) have been working with us to address this problem. As a first step, we have constructed an instrument capable of capturing full-spectrum fluorescence excitation data from single phytoplankton cells.

Using this instrument, we determined that the flu-orescence excitation spectra of plankton can then be used to identify the class of plankton to which they belong, at least for the limited numbers of species we have been able to study so far. In some cases, aspects of the environment can be detected by changes in the fluorescence of particular species.

The ultimate goal of this project is to use the infor-mation from this first instrument to design another that can be field-deployed. The operation of the sec-ond-generation system will be based on a method we developed called multivariate optical comput-ing, and it permits us to essentially record a bar-code identifying phytoplankton based on their fluorescence spectra.

Forensic Infrared Imaging: With support from the National Institute of Justice, we are working in col-laboration with the Morgan research group, the S.C. State Law Enforcement Division, and SPEX Forensic Division of Horiba Jobin Yvon Inc. to develop improved methods for the visualization of biological fluids at crime scenes. Using a sili-con microbolometer camera of the type normally used for detecting blackbody emission from warm objects, we developed hardware and software tools that make it possible to visualize dilute stains on a variety of fabrics.

In addition, we are pioneering methods for com-puter-designed instruments that are optimized to increase selectivity in imaging, so that blood and other biological fluids can be discriminated from other coatings. This method is based on spectral correlation and represents the simplest approach to building an IR camera to aid crime scene investiga-tors, and it is a significant departure from previous work on alternate light source systems as often seen on forensic science television programs.

Figure 1 shows an example image taken with one of our cameras illustrating the ability to visualize even diluted stains. In it, data from a camera is used to record AC images that reveal true reflectance. This alone provides excellent contrast based on chemical differences in a scene. The use of chem-ical filters then enables us to distinguish and type different stains.

R e p R e s e n tat i v e p u b l i c at i o n s

At this writing we have a number of manuscripts in this area that are submitted for publication, and interested students should contact us for an up-to-date list.

L.S. Hill, T.L. Richardson, L.T.M. Profeta, T.J. Shaw, C.J. Hintz, B.S. Twin-ing, E. Lawrenz, and M.L. Myrick. “Construction, Figures of Merit and Test-ing of a Single-Cell Fluorescence Excitation Spectroscopy System.” Rev. Sci. Instrum. 81 (2010): article 013103 (13 pp.).

H. Brooke, B.V. Bronk, J. McCutcheon, S. Morgan, and M.L. Myrick. “A Study of Electric Field Standing Waves on Reflection Micro-spectroscopy of Polystyrene Particles.” Appl. Spectrosc. 63 (2009): 1293–302.

M.L. Myrick, A.E. Greer, A.A. Nieuwland, R.J. Priore, J. Scaffidi, D. Andre-atta, and P. Colavita. “Birge-Sponer Estimation of the C-H bond dissociation energy in Chloroform using Infrared, Near-Infrared, and Visible Absorp-tion Spectroscopy—An experiment in Physical Chemistry.” J. Chem. Educ. 85 (2008): 1276–78.

H. Brooke, D.L. Perkins, B. Setlow, P. Setlow, B.V. Bronk, and M.L. Myrick. “Sampling and Quantitative Analysis of Clean B. subtilis Spores at Sub-Monolayer Coverage by Reflectance Fourier Transform Infrared Microscopy Using Gold-Coated Filter Substrates.” Appl. Spectrosc. 62 (2008), 881–8.

L.T.M. Profeta and M.L. Myrick. “Spectral resolution in multivariate optical computing.” Spectrochim. Acta A Mol. Biomol. Spectrosc. 67 (2007): 483–502.

M.N. Simcock and M.L. Myrick. “Precision in imaging multivariate optical computing.” Applied Optics 46 (2007): 1066–1080.

X. Li, H. Gao, W.A. Scrivens, D. Fei, X. Xu, M. A. Sutton, A.P. Reynolds, and M.L. Myrick. “Reinforcing mechanisms of single-walled carbon nanotube-rein-forced polymer composites.” J. Nanosci. Nanotechnol. 7 (2007): 2309–2317.

W.A. Scrivens, Y. Luo, M.A. Sutton, S.A. Collette, M.L. Myrick, P. Miney, P.E. Colavita, A.P. Reynolds, and X. Li. “Development of Patterns for Digi-tal Image Correlation Measurements at Reduced Length Scales.” Experimen-tal Mechanics. 47 (2007): 63–77.

M.N. Simcock and M.L. Myrick. “Tuning D* with modified thermal detec-tors.” Appl. Spectrosc. 60 (2006): 1469–1476.

M.L. Myrick, A.E. Greer, A. Nieuwland, R.J. Priore, J. Scaffidi, D. Andre-atta, and P. Colavita. “Fine-structure measurements of oxygen a band absor-bance for estimating the thermodynamic average temperature of the earth’s atmosphere - An experiment in physical and environmental chemistry.” J. Chem. Educ. 83 (2006): 263–264.

J.C. Carter, R.M. Alvis, S.B. Brown, K.C. Langry, T.S. Wilson, M.T. McBride, M.L. Myrick, W.R. Cox, M.E. Grove, and B.W. Colston. “Fabricating optical fiber imaging sensors using inkjet printing technology: A pH sensor proof-of-concept.” Biosensors and Bioelectronics. 21 (2006): 1359–1364.

P.E. Colavita, P.G. Miney, L. Taylor, R. Priore, D.L. Pearson, J. Ratliff, S.G. Ma, O. Ozturk, D.A. Chen, and M.L. Myrick. “Effects of metal coating on self-assembled monolayers on gold. 2. Copper on an oligo(phenylene-ethy-nylene) monolayer.” Langmuir 21 (2005): 12268–12277.

P.E. Colavita, P. Miney, L. Taylor, M. Doescher, A. Molliet, J. Reddic, J. Zhou, D. Pearson, D. Chen, M.L. Myrick. “Copper coated self-assembled monolayers: alkanethiols and prospective molecular wires.” In Topics in Flu-orescence Spectroscopy Volume 8, J. Lakowicz and C. Geddes, eds., Plenum Press: N.Y. (2005): pp. 275–303.

X. Li, H. Gao, W. Scrivens, D. Fei, V. Thakur, M. Sutton, A. Reynolds, and M. Myrick. “Structural and mechanical characterization of nanoclay-rein-forced agarose nanocomposites.” Nanotechnology. 16 (2005): 2020–2029.

m i c h A e l l . m y r i c kP R O F E S S O Rmyrick@sc.edu

P h y s i c A l / A n A ly t i c A l

B.S., 1985, North Carolina State University; ph.d., 1988, New Mexico State University.

Army young Investigator Award, 1992; Out-standing Honors College Professor in the Sci-ences, University of South Carolina, 1994; Imag ing Solution of the year Award, Advanced Imag-ing Magazine, 1999.

AC thermal infrared (8–12 µm wavelength) image of a polyester fabric with bloodstains. Stains are neat (I), 10X diluted (X), 25X diluted (V), 50X diluted (l), and 100X diluted (C). The bright object on the lower right is a diffuse reflectance standard. Light vertical and hori-zontal lines in the image are folds in the fabric.

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B i o c h e m i s t ry

Research Areas: Bioinorganic chemistry; protein biochemistry; characterization of cytosolic and mitochondrial redox homeostasis factors; gluta-thione metabolism; structure-function studies of iron homeostasis proteins in prokaryotic and eukaryotic cells.

Our group is using in vitro and in vivo techniques to identify and characterize mitochondrial and cyto-solic factors that regulate iron homeostasis and redox balance in the cell. Saccharomyces cerevisiae, or bak-ers’ yeast, is our model system of choice since this simple eukaryote is easy to maintain and geneti-cally manipulate in the lab, yet expresses many of the same redox and metal homeostasis systems as mammalian cells. A variety of biochemical, genetic, and molecular and cell biology techniques are used in our studies, including recombinant protein purification and characterization, enzyme activity assays, growth assays, gene deletion experiments, site-directed mutagenesis, subcellular fractionation, immunodetection, metal analysis, biophysical char-acterization of metalloproteins, and fluorescence microscopy. Our research focus is divided into two main areas as described below.

Subcellular Thiol Redox Control Mechanisms. The goal of this project is to characterize the cellular and molecular mechanisms for maintaining thiol redox homeostasis in the cytosol, mitochondrial matrix, and mitochondrial intermembrane space (IMS). Intracellular thiol-disulfide balance is crit-ical for the activity of proteins with functionally

important cysteine residues. The tripeptide gluta-thione (GSH) helps maintain thiol-disulfide bal-ance by catalyzing disulfide exchange reactions and protecting cysteines residues from oxidation by reactive oxygen species (ROS). Mitochondrial GSH metabolism is a key component of cellular thiol redox homeostasis since this organelle is the main source and target of ROS produced from aer-obic metabolism. Consequently, disruption of mito-chondrial thiol-disulfide balance has been linked to cancer, neurodegenerative diseases, and aging. To better characterize redox control pathways in mito-chondria, we have targeted green fluorescent protein (GFP)-based redox sensors to the IMS and matrix of yeast mitochondria to allow localized thiol redox monitoring (Fig. 1). These sensors equilibrate with the local glutathione (GSH:GSSG) pool and reg-ister thiol redox changes via disulfide bond forma-tion. This approach allows us to separately monitor the redox state of the matrix and the IMS, provid-ing a more detailed picture of redox processes in these two compartments. Our long-term goal is to characterize the subcellular impact of environmen-tal and genetic factors on thiol redox homeostasis to more fully understand their effects on human health and disease.

Monothiol Glutaredoxins and BolA Proteins in Iron Homeostasis. Though iron is a cofactor for many essential proteins, an excess of this redox-active metal ion is toxic to cells. To maintain optimal intracellu-lar iron levels, iron transport and storage is tightly regulated in all eukaryotic cells ranging from yeast to humans. Monothiol glutaredoxins (Grxs) and BolA-like proteins have recently emerged as novel players in iron homeostasis; however, the molecu-lar interactions and specific roles of these proteins are unclear. We are employing complementary bio-physical and molecular genetic methods to char-acterize the structural and functional interactions between these two highly conserved protein families and provide mechanistic insight into their regula-tory roles in iron metabolism. In yeast, transcrip-tion of iron uptake and storage genes is regulated by the transcription factor Aft1 and its paralogue

Aft2. Nucleocytoplasmic shuttling of Aft1 (and presumably Aft2) is dependent upon a signaling pathway that includes the cytosolic monothiol glu-taredoxins (Grx3 and Grx4) and the BolA-like pro-tein Fra2. We have shown that Fra2 and Grx3/4 form an unusual [2Fe-2S]2+-bridged heterodimer with Fe ligands provided by the active site cysteine of Grx3/4, glutathione, and a single histidine res-idue (Fig. 2). Overall our results suggest that the ability of the Fra2-Grx3/4 complex to assemble a [2Fe-2S] cluster may act as a signal to control the iron regulon in response to cellular iron status in yeast. Given the high similarity between yeast and human homologues of numerous components in this Fe signaling pathway, this information will be instrumental for identifying new therapeutic tar-gets for the prevention and treatment of disorders of iron metabolism.

R e p R e s e n tat i v e p u b l i c at i o n s

Li, H., D.T. Mapolelo, N.N. Dingra, S.G. Naik, N.S. Lees, B.M. Hoff-man, P.J. Riggs-Gelasco, B.H. Huynh, M.K. Johnson, and C.E. Outten. “The yeast iron regulatory proteins Grx3/4 and Fra2 form heterodimeric complexes containing a [2Fe-2S] cluster with cysteinyl and histidyl ligation.” Biochemistry. 48 (2009): 9569–81.

Leitch, J.M., L.T. Jensen, S.D. Bouldin, C.E. Outten, P.J. Hart, and V.C. Culotta. “Activation of Cu/Zn superoxide dismutase in the absence of oxy-gen and the copper chaperone CCS.” J. Biol. Chem. 284 (2009): 21863–71.

Hu, J., L. Dong, and C.E. Outten. “The redox environment in the mito-chondrial intermembrane space is maintained separately from the cytosol and matrix.” J. Biol. Chem. 283 (2008): 29126–34. (Highlighted in Chem. Res. Toxicol., Dec. 2008.)

Gibson, L.M., N.N. Dingra , C.E. Outten, and L. Lebioda. “Structure of the thioredoxin-like domain of yeast glutaredoxin 3.” Acta Crystallogr. D Biol. Crystallogr. 64 (2008): 927–32.

Kumanovics, A., Chen, O., Li, L., Bagely, D., Adkins, E., Lin, H., Dingra, N.N., Outten, C.E., Keller, G., Winge, D., Ward, D. and Kaplan, J. “Identification of FRA1 and FRA2 as genes involved in regulating the yeast iron regulon in response to decreased mitochondrial iron-sulfur cluster syn-thesis.” J. Biol. Chem. 283 (2008): 10276–86.

Outten, C.E., and V.C. Culotta. “Alternative start sites in the Saccharomy-ces cerevisiae GLR1 gene are responsible for mitochondrial and cytosolic isoforms of glutathione reductase.” J. Biol. Chem. 279 (2004): 7785–91.

Outten, C.E., and V.C. Culotta. “A novel NADH kinase is the mito-chondrial source of NADPH in Saccharomyces cerevisiae.” EMBO J., 22 (2003): 2015–24.

c A ry n e . o U t t e nA S S I S TA N T p R O F e S S O Rcaryn.outten@chem.sc.edu

Figure 1. Fluorescence microscopy images of yeast cells expressing cytosol, matrix, or IMS redox sensors

Figure 2. Proposed Fe-S complexes formed by Grx3/4 and Fra2

B.S., 1995, College of William and Mary; ph.d., 2001, Northwestern University; postdoctoral Fellow, 2001–2005, johns Hopkins University.

NIeHS Transition to Independent positions (K22) Award, 2005–08.

26

B i o c h e m i s t ry

Research Areas: Microbial metal metabolism, bio-inorganic chemistry, microbial physiology, and microbial genetics; biochemical mechanisms of Fe-S cluster assembly; characterization of transition metal acquisition, trafficking, and storage systems during environmental stress; metal homeostasis during bio-film formation in micro-organisms.

Metal Trafficking and Metal Cofactor Assembly Under Stress Conditions: My broad research goal is to under-stand how homeostasis of essential transition met-als is maintained in response to environmental

stresses. Due to their unique chemical properties, transition metals such as copper, iron, and zinc are critical cofactors in the active sites of enzymes and as structural components in proteins. However, many of these essential metals are toxic when pres-ent in excess, indicating a requirement for the cell to maintain a fairly narrow intracellular concentra-tion of each metal. In addition, metal metabolism may be altered by environmental stress through multiple mechanisms. Cells can adjust transport and storage of the metal in response to the stress, either through increased uptake, efflux, or expres-

sion of metal storage proteins. The metal or metal cofactor may be directly modified, for instance by oxidation or reduction, leading to a subsequent change in reactivity, ligand affinity, or bioavail-ability. Conversely, the proteins or other biomole-cules that interact with the metal or metal cofactor may themselves be altered by the stress, causing a change in metal metabolism such as release of metal from an active site. Defining the biochemi-cal strategies used by organisms to maintain metal homeostasis under stress will provide insight into critical areas ranging from bacterial pathogenesis to human disease.

The suf pathway and Fe-S cluster assembly under stress: Fe-S clusters, which contain inorganic sul-fur and iron, play key roles in electron transport as active site cofactors in TCA cycle enzymes and as exquisite sensors of oxygen and oxygen radicals in stress-responsive transcription factors. However, Fe-S clusters are perturbed by multiple stress con-ditions. During oxidative stress, superoxide anion (O2•

-) can damage 4Fe-4S clusters, leading to clus-ter degradation and release of iron. Therefore, Fe-S clusters are assembled in vivo via intricate biosyn-thetic pathways. The Fe-S cluster assembly path-way encoded by the sufABCDSE operon is required to assemble Fe-S clusters during iron starvation or oxidative stress, conditions known to disrupt Fe-S clusters in vivo. To determine the biochemi-cal mechanisms used by the suf pathway to achieve this feat, we have purified all six of the suf-encoded proteins. We have found that SufB, SufC, and SufD co-purify as a stable complex. This three-protein complex interacts with the SufE protein to dramat-ically enhance sulfur donation by the SufS cysteine desulfurase enzyme. SufE acts as a sulfur transfer partner and, together with the SufBCD complex, comprises a novel sulfur transfer pathway for Fe-S cluster assembly under stress conditions. Further genetic, regulatory, and biochemical analysis will elucidate how the suf gene products are adapted to acquire iron and sulfur for construction of Fe-S clusters during iron starvation and oxidative stress.

Metal homeostasis in biofilms: One nearly universal strategy used by microbes to respond to stress is for-mation of a complex, three-dimensional structure known as a biofilm. Biofilms occur among micro-organisms growing in natural environments and often include multiple species. It is well established that biofilms are highly resistant to environmental stresses, including heavy metal toxicity and oxida-

tive stress. However, the genetic and biochemical mechanisms of biofilm resistance are only partially defined. Understanding metal homeostasis during biofilm formation is critical for understanding bio-film stress resistance and will provide insight into multiple microbial processes. For instance, mixed species biofilms growing on metal surfaces, such as household plumbing or ship hulls, are known to stimulate biocorrosion. In addition, microbial pathogens that form biofilms during infection also encounter metal starvation as they interact with mammalian host cells. Biofilm-specific metal homeostasis systems might be optimized for the microaerobic or nutrient-depleted environments that exist within the biofilm. We have recently uncovered a regulatory pathway that integrates cel-lular Fe-S cluster metabolism and iron homeostasis with the developmental decision to enter the bio-film mode of growth in Escherichia coli. We are continuing to use genetic, biochemical, and cell biology approaches to identify and characterize such systems in order to understand their impor-tance for biofilm physiology.

R e p R e s e n tat i v e p u b l i c at i o n s

Chahal, H.K., Dai, Y., Saini, A., Ayala-Castro, C., and Outten, F.W. “The SufBCD Fe-S scaffold complex interacts with SufA for Fe-S cluster trans-fer.” Biochemistry. (2009): 48(44): 10644–10653.

Gupta, V., Sendra, M., Naik, S.G., Chahal, H.K., Huynh, B.H., Outten, F.W., Fontecave M, and S. Ollagnier de Choudens. “Native Escherichia coli SufA, coexpressed with SufBCDSE, purifies as a [2Fe-2S] protein and acts as an Fe-S transporter to Fe-S target enzymes.” J. Am. Chem. Soc. (2009): 131(17) 6149–6153.

Wada, K., Sumi, N., Nagai. R., Iwasaki, K., Sato, T., Suzuki, K., Hasegawa, Y., Kitaoka, S., Minami, Y., Outten, F.W., Takahashi, Y., and Fukuyama, K. “Molecular dynamism of Fe-S cluster biosynthesis implicated by the struc-ture of the SufC2-SufD2 complex.” J. Mol. Biol. (2009): 387(1): 245–258.

Wu, Y., and, Outten, F.W. “IscR controls iron-dependent biofilm forma-tion in Escherichia coli by regulating type I fimbria expression.” J. Bacteriol. (2009): 191(4): 1248–1257.

Layer, G., Gaddam, S.A., Ayala-Castro, C.N., Ollagnier-de Choudens, S., Las-coux, D., Fontecave M., Outten F.W. “SufE transfers sulfur from SufS to SufB for iron-sulfur cluster assembly.” J. Biol. Chem. (2007): 282(18): 13342–13350.

f. WAy n e o U t t e nA S S I S TA N T p R O F e S S O Rwayne.outten@chem.sc.edu

B.S., 1995, College of William and Mary; ph.d., 2001, Northwestern University; postdoctoral Fellow, 2001 –2005, National Institutes of Health.

Cottrell Research Scholar, 2008–2010.

27

P h y s i c A l

v i tA ly r A s s o l ov A S S O C I AT E P R O F E S S O Rrassolov@mail.chem.sc.edu

Research Areas: Quantum chemistry; hyperfine interactions; use of linear operators to describe elec-tron correlation effects in molecules.

Currently my work focuses on three topics.

Geminal Theory. Modern electronic structure meth-ods can be divided into two groups: simple single-reference methods (Hartree-Fock, Coupled Cluster, Kohn-Sham Density Functional Theory) and “cus-tom-made” multireference methods (MCSCF, CASPT2). Single-reference methods work well for equilibrium ground states of not very reac-tive species, and multireference methods are often computationally expensive and are hard for non-theorists to use. We are developing a new, well-defined method based on geminal representation of the wave function. Its full name is Antisymme-trized Product of Singlet type Strongly orthogo-nal Geminals (APSSG), and SSG is the shorter acronym. The SSG method is the only practical model that is both variational and size consistent. Its computational cost is only modestly higher than the versatile Hartree-Fock. The target applications of SSG are chemistry of transition metal elements and potential energy surfaces (reaction barriers, bond energies).

Semiclassical Dynamics Based on Quantum Trajecto-ries. It is well known to theorists that most chemi-cal reactions require quantum description of nuclei due to the effects of tunneling, zero point energy, and non-adiabatic phenomena. It is appealing to describe quantum effects using semiclassical meth-ods. The problem is that modern semiclassical meth-ods are often more expensive than full quantum treatment, and their error is difficult to assess. My group develops a method based on Bohmian tra-jectories that is very inexpensive at the semiclassi-cal limit, favorably compares to other semiclassical methods (such as Herman-Kluk), and is systemat-ically improvable.

Correlation Operator Approach. Exact theoretical description of chemical systems is impossible beyond the smallest model systems (this is a so-called NP-hard problem in the computational complexity ter-minology). The widely popular Density Functional Theory attempts to bypass this problem by mod-eling chemical systems aiming for adequate accu-racy. The underlying theoretical machinery of this modeling mainly comes from solid-state physics. We work on using instead the traditional tools of quantum chemistry, such as linear operators. We seek a universal two-electron operator that can describe electron correlation effects in single deter-minant wave functions, with sufficient accuracy.

R e p R e s e n tat i v e p u b l i c at i o n s

Cassam-Chenai, P., Rassolov, V.A.. “2010 The electronic mean field config-uration interaction method: III - the p-orthogonality constraint.” Chemical Physics Letters, 487(1–3), 147–152.

Rassolov, V.A. “Semiclassical electron correlation operator.” Journal of Chem-ical Physics, (2009): 131(20), 204102.

Rassolov, V.A., Garashchuk, S. “Computational complexity in quantum chem-istry.” Chemical Physics Letters, (2008): 464 (4–6), 024109.

Rassolov, V.A., Xu, F. “Geminal model chemistry III: Partial spin restriction.” Journal of Chemical Physics, 126 (23), (2007): 234112.

Rassolov, V.A., Xu, F. “Geminal model chemistry. IV. Variational and size con-sistent pure spin states.” Journal of Chemical Physics, 127 (4), (2007): 044104.

Garashchuk, S., Rassolov, V.A. “Semiclassical nonadiabatic dynamics of NaFH with quantum trajectories.” Chemical Physics Letters, 446 (4–6), (2007): 395–400.

M.S., Physics, 1992, Moscow Institute of Phys-ics and Technology; M.S., Chemistry, 1992, Uni-versity of Notre dame; ph.d., Chemistry, 1996, University of Notre dame.

Invited professor, University of Nice,France, 2009.

28

Research Areas: Inorganic chemistry. Synthesis of third generation poly(pyrazolyl)methane and poly(pyrazolyl)borate ligands and ligands contain-ing aromatic groups that form strong π-π stack-ing interactions; preparation of metal complexes of these ligands that have unusual magnetic and structural properties.

Our group is the leader worldwide in the devel-opment of the chemistry of tris(pyrazolyl)methane ligands. These ligands, the neutral analogs of the extensively investigated, isoelectronic tris(pyrazolyl)borate ligands, were not studied extensively prior to our work because they were difficult to prepare. We have now dramatically improved these prepa-rations, making the whole family of HC(3-Rpz)3 (pz = pyrazolyl ring; R = Ph, Pri, But) ligands and HC(3,5-Me2pz)3 readily available for the first time. We have functionalized these new ligands to prepare a number of new polytopic ligands (those with multiple poly[pyrazolyl]methane units in a single molecule), a development that represents

the first major effort to prepare “third generation” poly(pyrazolyl)methane ligands. Third generation ligands are specifically functionalized at the non-coordinating, “back” position, distal from the metal environment, for the purpose of appending new/desired functionality into the systems under study while not impacting the direct environment about the metal.

We have developed unusual chemistry of many dif-ferent metal systems with these ligands. A particu-larly exciting example is the reaction of M(BF4)2 compounds with Lm resulting in fluoride abstrac-tion leading to the complexes [M2(μ-F)(μ-Lm)2](BF4)3 (see below for M=Fe structure) in which a single fluoride ligand and two Lm molecules bridge the two metal centers. The M=Fe complex shows weakly antiferomagnetic behavior.

In a separate project we have used tris(pyrazolyl)methane ligands to prepare new iron(II) complexes that show very unusual spin properties. The com-plex {[HC(3,5-Me2pz)3]2Fe}(BF4)2 is fully high spin from 350 K to 206 K, then undergoes an abrupt spin change to a mixture of high and low spin forms, an unprecedented result. It also under-goes a solid-state phase change at 206 K, a change we have observed for other analogous complexes of first row metals, showing that the phase change drives the spin-state change. In recent work we are studying the effects of controlling spin-crossover effects by manipulating the supramolecular struc-tures of the compounds. We have synthesized a new family of “third generation” poly(pyrazolyl)borate ligands. Using these ligands, we have been able to show that subtle changes in either molecu-lar or supramolecular structure can greatly influence the spin-crossover behavior of iron(II) complexes. The figure shows the three-dimensional structure of one polymorph of Fe[(p-IC6H4)B(3-Mepz)3]2 where the highly organized structure prevents the molecule from undergoing spin crossover at low temperature.

Incorporating the 1,8-naphthalimide group into bis(pyrazolyl)-methane ligands allows the association of their metal complexes into directionally ordered

dimers by strong π-π stacking interactions in both solution and solid-state, as pictured. The incorpo-ration of this π-bonding group into acetate ligands leads to the formation of paddlewheel metalladi-mers with very unusual supramolecular structures held together by non-covalent forces, as pictured.

R e p R e s e n tat i v e p u b l i c at i o n s

Reger, D.L.; Foley, E.A.; Smith, M.D. “Synthesis of a tritopic, third-gener-ation bis(1-pyrazolyl)methane ligand and its silver(I) complex: Unexpected structure with high coordination numbers.” Inorg. Chem. Commun. (2010): 13, 568–572.

Reger, D.L.; Foley, E.A.; and Smith, M.D. “Structural Impact of Multitopic Third Generation Bis(1-pyrazolyl)methane Ligands: Double, Mononuclear Metallacyclic Silver(I) Complexes.” Inorg. Chem. (2010): 49, 234–242.

Reger, D.L.; Sirianni, E; Horger, J.J.; Smith, M.D.; and Semeniuc, R.F.; “Supramolecular Architectures of Metal Complexes Controlled by a Strong π-π Stacking, 1,8-Naphthalimide Functionalized Third Generation Tris(pyrazolyl)methane Ligand.” Cryst. Growth & Design, (2010): 10, 386–393.

Reger, D.L.; Horger, J.J.; Smith, M.D.; and Long, J.L. “Homochiral, Helical Metal Organic Framework Structures Organized by Strong Non-Covalent π-π Stacking Interactions.” Chem. Comm. (2009): 6219–6221.

Reger, D.L.; Foley, E.A.; Watson, R.P.; Pellechia, P.J.; Smith, M.D.; Long, G.J.; and Grandjean, F. “Monofluoride Bridged, Binuclear Metallacycles of First Row Transition Metals Supported by Third Generation Bis(1-pyrazo-lyl)methane Ligands: Unusual Magnetic Properties.” Inorg. Chem. (2009): 48, 10658–10669.

Reger, D.L.; Debreczeni, A.; Reinecke, B.; Rassolov, V.; Smith, M.D.; and Semeniuc, R.F. “Highly organized structures and unusual magnetic proper-ties of copper(II) paddlewheel dimers containing the π –π stacking, 1,8-naph-thalimide synthon,.” Inorg. Chem. (2009): 48, 8911–8924.

Reger, D.L.; Elgin, J.D.; Smith, M.D.; Grandjean, F.; and Long, G.J. “Struc-tural, Magnetic, and Mössbauer Spectral Study of the Electronic Spin-State Transition in {Fe[HC(3-Mepz)2(5-Mepz)]2}(BF4)2,” Inorg. Chem. (2009): 48, 9393–9401.

D A n i e l l e W i s r e g e rC A R O l I N A d I S T I N G U I S H e d p R O F e S S O Rreger@chem.sc.edu

i n o r g A n i c

B.S., 1967, dickinson College; ph.d., 1972, Massachusetts Institute of Technology; Vis-iting Fellow, Australian National University, 1985, 1994.

Educational Foundation Research Award for Science, Mathematics, and Engineering, Uni-versity of South Carolina, 1995; Michael J. Mungo Award for Excellence In Undergrad-uate Teaching, University of South Carolina, 1995; Amoco Foundation Outstanding Teach-ing Award, University of South Carolina, 1996; Carolina Trustee professorship, 2000, Michael J. Mungo Award for Excellence In Graduate Teaching, 2003; South Carolina Governor’s Award for Excellence in Scientific Research, 2007; University of South Carolina educa-tional Foundation Outstanding Service Award, 2008; American Chemical Society Outstand-ing South Carolina Chemist of the year, 2008.

29

AnAlyticAl/environmentAl

t i m ot h y J . s h AW P R O F E S S O Rshaw@chem.sc.edu

Research Areas: Trace element geochemistry; envi-ronmental analytical chemistry; techniques devel-opment for trace elements of both anthropogenic and natural origin in the environment; geochem-ical cycling of trace elements in the environment.

My work is focused on identifying factors that con-trol the exchange of trace elements between the dis-solved and particulate phases in both the marine and fresh water systems. The goal is to identify the processes that control cycling of trace elements and trace contaminants in the environment. Toward this end, my group routinely measures trace elements and tracers in groundwater, seawater, sediments, and icebergs. In order to make these measurements, we also develop analytical techniques for trace element analysis in aqueous, colloidal, and solid phases and design and build sampling equipment. We main-tain and operate an Elemental Mass Spectrometry Facility, a clean room facility, and a separate radio-chemical analysis laboratory. Our facility includes two High Resolution Inductively Coupled Plasma Mass Spectrometers (HR-ICP-MS), multple coin-cidence counters for analysis of 223Ra and and 224Ra as well as 227Ac isotopes, and a low level Beta counter for 234Th analysis.

My group is in the midst of a program to examine the impact of groundwater mixing and exchange at the terrestrial/ocean interface. We have been funded by the NSF to quantify the formation of “superoxidants” at the groundwater/seawater inter-face as a function of the oxidation of Fe(II). This work is part of a combined set of laboratory/field experiments with Dr. John Ferry’s research group.

We are also funded by the NSF to evaluate the role of free drifting icebergs as a micronutrient source in the Southern Ocean. This work is part of a large collaborative program with Dr. Ken Smith at the Monterey Bay Aquarium Research Institute (MBARI). The project involves the measurement of tracers of terrestrial material flux to the Southern Ocean and requires the development of specialized sampling equipment and new analytical methods.

We are currently active in the development of new analytical techniques to measure uranium and tho-rium daughters and rare earth elements associated with environmental samples. Potential applications include: study of the burial histories of refractory elements in coastal and deep-ocean sediments, mea-surement of toxic trace elements in environmental samples, and measurement of trace element accu-mulation and transport in the coastal environment. The NSF has funded us to measure trace element distribution coefficients in benthic foraminifera. We currently have the only facility capable of complet-ing this project. This work will help verify recon-structions of paleo climate records in the world’s oceans. Future work in this area will include the examination of contaminant body burdens in shal-low water foraminifera species to reconstruct pollu-tion histories in nearshore environments.

R e p R e s e n tat i v e p u b l i c at i o n s

J.M. Burns, P.S. Craig, T.J. Shaw, and J.L. Ferry. “Multivariate examination of Fe(II)/Fe(III) cycling and consequent hydroxyl radical yield.” Environmen-tal Science & Technology. In press 2010.

L.S. Hill, T.L. Richardson, L.T.M. Profeta, T.J. Shaw, C.J. Hintz, B.S. Twin-ing, E. Lawrenz, and M.L. Myrick. “Construction, figures of merit, and testing of a single-cell fluorescence excitation spectroscopy system.” Rev. Sci. Instrum. (2010): 81.

W.S. Moore, M. Beck, T. Reidel, M.R. van der Loeff, O. Dellwig, T.J. Shaw, and H.J. Brumsack. “Fluxes of pore waters which transport met-als and nutrients to the German Wadden Sea.” Geochim. Cosmochim. Acta. (2009): 73(13), A900.

J.L. Ferry, P.S. Craig, C.R. Hexel, P. Sisco R. Frey, P. Pennington, M. Fulton, G. Scott, A. Decho, S. Kashiwada, C.J. Murphy, and T.J. Shaw. “Transfer of Gold Nanoparticles from the Water Column to the Estuarine Food Web.” Nature:Nano (2009): (4), 441–444.

A.M. Alkilany, P.K. Nagaria, C.R. Hexel, T.J. Shaw, C.J. Murphy, and M.D. Wyatt. “Cellular Uptake and Cytotoxicity of Gold Nanorods: Molecular Origin of Cytotoxicity and Surface.” Effects Small. (2009): 5(6), 701–708.

P.S. Craig, T.J. Shaw, P.L. Miller, P.J. Pellechia, and J.L. Ferry. “Use of Multipa-rametric Techniques To Quantify the Effects of Naturally Occurring Ligands on the Kinetics of Fe(II) Oxidation.” Env. Sci. Tech. (2009): 43(2), 337–342.

W.S. Moore and T.J. Shaw. “Fluxes and behavior of radium isotopes, bar-ium, and uranium in Southeastern US rivers and estuaries.” Marine Chem-istry. 108 (2008): 236–254.

K.L. Smith, B.H. Robison, J.J. Helly, R.S. Kaufmann, H.A. Ruhl, T.J. Shaw, B.S. Twining, and M. Vernet. “Free-Drifting Icebergs: Hot Spots of Chemical and Biological Enrichment in the Weddell Sea.” Science. 317 (2007): 478–482.

D.C. McCorkle, J.M. Bernhard, C.J. Hintz, J.K. Blanks, G.T. Chandler, and T.J. Shaw. “The Carbon and Oxygen Stable Isotopic Composition of Cultured Benthic Foraminifera.” Geological Society of London, in press.

C.J. Hintz, T.J. Shaw, G.T. Chandler, J.M. Bernhard, D.C. McCorkle, and J.K. Blanks. “Trace/minor Element:Calcium Ratios in Cultured Benthic For-aminifera, Part I: Interspecies Differences.” Geochimica et Cosmochimica Acta. 70(8) (2006): 1952–1963.

C.J. Hintz, T.J. Shaw, G.T. Chandler, J.M. Bernhard, D.C. McCorkle, and J.K. Blanks. “Trace/minor Element:Calcium Ratios in Cultured Benthic For-aminifera, Part II: Ontogenetic Variation.” Geochimica et Cosmochimica Acta. 70(8) (2006): 1964–1976.

C. J. Hintz, G.T. Chandler, J.M. Bernhard, D.C. McCorkle, S. Havach, J.K. Blanks, and T.J. Shaw*. “A physicochemically-constrained seawater culturing system for production of viable, calcite-producing, paleoceano-graphically-important benthic foraminifera Limnol.” Oceanogr. Methods. 2 (2004): 160–170.

T.J. Shaw. “Biogeochemical processes in coastal aquifers and permeable sed-iments.” Aqua. Geochem. 9 (2003): 165–169.

T. Duncan and T.J. Shaw. “The mobility of rare earth elements and redox sensitive metals in the groundwater/seawater mixing zone of a shallow coastal aquifer.” Aqua. Geochem. 9 (2003): 233–255.

T.J. Shaw, T. Duncan, and B. Schnetger. “A Preconcentration/Matrix Reduc-tion Method for the Analysis of Rare Earth Elements in Seawater and Ground-waters by ID-ICP-MS.” Anal. Chem. 75 (2003): 3396–3403.

T.J. Shaw and W.S. Moore. “Analysis of 227 Ac in seawater by delayed coin-cidence counting.” Mar. Chem. 78 (2002): 197–203.

S.M. Havach, G.T. Chandler, A. Wilson-Finelli, and T.J. Shaw. “Experi-mental determination of trace element distribution coefficients in cultured benthic foraminifera.” Geochim. Chosmochim. Acta. 65 (2001): 1277–1283.

H.A. Alegria, T.F. Bidleman, and T.J. Shaw. “Organochlorine Pesticides in Ambient Air in Belize, Central America.” Environ. Sci. Tech. 34(10) (2000): 1953–1958.

H.A. Alegria, J.P. d’Autel, and T.J. Shaw. “Offshore Transport of Pesticides in the South Atlantic Bight: Preliminary Estimates of Transport Budgets.” Marine Pollution Bulletin. 40 (2000): 1186–1200.

B.S., 1981, California State Polytechnic Uni-versity Pomona; Ph.D., 1988, University of California, San Diego, Scripps Institute of Oceanography; postdoctoral Fellow, Woods Hole - MIT.

Fellowship at the Hanse Institute for Advanced Study, Wissenschaftskolleg, Germany, 1999; Visiting professor, University of Oldenburg, 2002; Fellowship to the Hanse Institute for Advanced Study in Delmenhorst Germany for 2010–2011.

(photo: dr. Shaw on the icebreaker LM Gould in an Antarctic ice field)

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Research Areas: Organic, polymer, materials, supramolecular, and physical organic chemistries.

Introduction: We are interested in understanding and controlling the three-dimensional shape and conformation of molecules and polymers. Con-trol over shape on the molecular level provides a new and efficient route to manipulating chemi-cal properties such as dipole moment, refractive index, viscosity, chirality, and melting point. We are particularly interested in using this approach to develop new molecular recognition platforms and to study weak noncovalent forces.

Molecularly Imprinted Polymers: The molecular imprinting approach is a synthetically efficient route to cross-linked polymers with tailorable rec-

ognition properties (Figure 1). The polymers are formed in a one-step process in the presence of a template molecule. Removal of the template from the rigid polymer matrix creates molecular-sized cavities with shape and functional group comple-mentarity to the template. Imprinted polymers have been used in a wide range of applications requiring molecular recognition such as sensing, chromatography, solid-phase extraction, and even catalysis. One difficulty has been the low fidelity of the imprinting process. Imprinted polymers con-tain sites of widely varying affinity and selectivity. We have developed tools to characterize this bind-ing site heterogeneity and also new strategies for making more homogeneous polymers. One method is site-selective chemical modification, where we selectively chemically modify and suppress the low-affinity sites. A second method is to develop tem-plate-activated monomers that will only form sites in the presence of the template.

Molecules and polymers with molecular memory: We have developed a new class of molecules and poly-mers in which the molecular-level conformations can be “written,” “saved,” and “erased” (Figure 2). These dynamic properties are due to the presence of Caryl-Nimide single bonds with high rotational barriers. Thus at rt, they are structurally rigid. On

heating, the material becomes malleable and flex-ible due to bond rotation and can be shaped by their environment. On cooling, these new shapes are preserved as the framework becomes rigid again. These compounds have applications as molecular memory devices, reprogrammable separation mate-rials, and sensors.

Measuring noncovalent arene-arene interactions: A unique application of our shape-switchable materials is the development of a molecular balance to mea-sure weak noncovalent interactions (Figure 3). The molecule adopts distinct folded and unfolded con-formations due to restricted rotation about a Caryl-Nimide single bond. By measuring the change in the folded/unfolded ratio, we can accurately mea-sure the intramolecular interactions in the folded conformer. We have used this approach to study face-to-face pi-stacking, edge-to-face pi-stacking, and CH-pi interactions.

R e p R e s e n tat i v e p u b l i c at i o n s

Rasberry, R.D.; X. Wu; B.N. Bullock; M.D. Smith; and K.D. Shimizu. “A small molecule diacid with long-term chiral memory.” Org. Lett., (2009): 11, 2599–2602.

Zhang, Y.; J.M. Lavin; and K.D. Shimizu. “Solvent Programmable Polymers Based on Restricted Rotation.” J. Am. Chem. Soc., (2009): 131, 12062–12063.

Carroll, W.R.; P. Pellechia; and K.D. Shimizu. “A Rigid Molecular Balance for Measuring Face-to-Face Arene−Arene Interactions.” Org. Lett., (2008): 10, 3547–3550.

Chong, Y.S.; W.R. Carroll; W.G. Burns; M.D. Smith; and K.D. Shimizu. “A High-Barrier Molecular Balance for Studying Face-to-Face Arene-Arene Interac-tions in the Solid State and in Solution.” Chem-Eur. J., (2009): 15, 9117–9126.

Rasberry, R.D.; M.D. Smith; K.D. Shimizu. “Origins of selectivity in a colo-rimetric charge-transfer sensor for diols.” Org. Lett., (2008): 10, 2889–2892.

Wu, X.Y.; W.R. Carroll; and K.D. Shimizu. “Stochastic lattice model Sim-ulations of molecularly imprinted polymers.” Chem. Mater., (2008): 20, 4335–4346.

k e n D. s h i m i Z U P R O F E S S O Rshimizu@chem.sc.edu

B.A., 1990, phi Beta Kappa, Cornell University; Ph.D., 1995, Massachusetts Institute of Tech-nology; NIH postdoctoral Fellow, 1995–1997, Boston College.

Mungo Undergraduate Teaching Award, 2008; Editorial Advisory for the Journal of Molecular Recognition, 2008; japan Society for the promo-tion of Science Postdoctoral Fellowship Pro-gram, 2004; Mortar Board Teaching Award, 2001; Research Corporation Award, 1994.

Figure 2

Figure 1

Figure 3

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Research Areas: Organic, supramolecular chemis-try, nanomaterials, bioorganic, organic photochem-istry, and crystal engineering.

Research Summary: Organic chemists use C-C bond forming strategies to elaborate molecules generat-ing myriad compounds. Nature uses amides and phosphoamides to organize huge arrays of nano-materials. We are interested in developing predict-able supramolecular chemistry using non-covalent urea-urea interactions to build an array of structures and materials with a diverse array of applications.

Self-assembled bis-urea macrocycles: The study of enzymes has demonstrated that reactions carried out in confined environments proceed with extraordi-nary efficiency and selectivity. However, the devel-opment of synthetic reaction environments has been very challenging. We have identified bis-urea mac-rocyclic building blocks that predictably assemble to form porous crystalline materials (Figure 1). It is constructed from molecular units (bis-urea macro-cycles) that are readily synthesized from rigid spac-ers and protected ureas. The donut-shaped building

blocks reliably assemble into columns that pack together to form porous crystals. The dimensions of the homogeneous channels are controlled by the size of the macrocyclic units, which allows for pre-cise and rational control over cavity dimensions, shape, and functionality. The goal of our research is to understand and apply this supramolecular assembly strategy to generate homogeneous micro-porous materials for use as confined environments for a wide range of chemical reactions.

Nanoreactors: Phenylether 1 self-assembles into columnar structures via urea-urea hydrogen bonds and aryl-stacking interactions to form crystals, which display permanent porosity. These crystals reversibly bound guests that matched the size and shape of the channel. Host 1 crystals facilitated [2+2]-pho-tocycloadditions of enones with high conversion and selectivity. Benzophenone 2 replaces the ether oxygen of host 1 with a carbonyl group, effectively placing a known triplet photosensitizer within the host framework. New host 2 is similar in dimen-sions to host 1 and absorbs similar guests with nearly the same host:guest ratios. Although simi-lar in size, the two hosts promote markedly differ-ent photochemical reactivity for absorbed guests. Host 1 enables the facile [2+2]-cycloaddition to yield exo head-to-tail photodimers in high selectiv-ity and conversion. In contrast, host 2 facilitated the triplet sensitized cis-trans photoisomerization of trans-b-methylstyrene. We are currently explor-ing other reactions within these hosts as well as within other hosts that contain interior functional groups for catalysis.

Effects of molecular confinement on physical proper-ties: The three-dimensional structure and orien-tation of molecules is known to influence their physical properties including their conductivity and optical properties. We are currently investi-gating the feasibility of loading or synthesizing conjugated polymers within our columnar nano-tubes. We will study the effect of this encapsula-tion on their stability and on their absorptive and emissive properties.

R e p R e s e n tat i v e p u b l i c at i o n s

Xu, Y.; Smith, M.D.; Geer, M.F.; Pellechia, P.J.; Brown, J.C.; Wibowo, A.C.; Shimizu, L.S. “Thermal reaction of a columnar assembled diacetylene mac-rocycle.” J. Am. Chem. Soc. (2010): 132, 5334–5335.

Tian, L.; Wang, C.; Dawn, S.; Smith, M.D.; Krause, J.A.; Shimizu, L.S. “Macrocycles with switchable exo/endo metal binding sites.” J. Am. Chem. Soc. (2009): 131, 17620–17629.

Yang, J.; Dewal, M.B.; Sobransingh, D.; Xu, Y.; Smith, M.D.; Shimizu, L.S. “An examination of the structural features that favor the columnar self-assem-bly of bis-urea macrocycles.” J. Org. Chem. (2009): 74, 102–110.

Xu, Y.; Smith, M.D.; Krause, J.; Shimizu, L.S. “Control of the intramolec-ular [2+2] photocycloaddition of a bis-stilbene macrocycle.” J. Org. Chem. (2009): 74, 4874–4877.

Yang, J.; Dewal, M.B.; Profeta, S.; Li, Y.; Smith, M.D.; Shimizu, L.S. “Ori-gins of selectivity for the [2+2] cycloaddition of a,b-unsaturated ketones within a porous self-assembled organic framework.” J. Am. Chem. Soc. (2008): 130, 612–621.

Sobransingh, D.; Dewal, M.B.; Hiller, J.; Smith, M.D.; Shimizu, L.S. “Inclu-sion of electrochemically active guests by novel oxacalixarene hosts.” New J. Chem. (2008): 32, 24–27.

Dewal, M.B.; Xu, Y.; Yang, J.; Mohammed, F.; Smith, M.D.; Shimizu, L.S. “Manipulating the cavity of a porous material changes the photoreactivity of included guests.” Chem. Commun. (2008): 3909–3911.

Shimizu, L.S. “Perspectives in main-chain hydrogen bonded supramolecu-lar polymers.” Polym. Int. (2007): 56, 444–452.

Yang, J.; Dewal, M.B.; Shimizu, L.S. “Self-assembling bis-urea macrocycles used as an organic zeolite for a highly stereoselective photodimerization of 2-cyclohexenone.” J. Am. Chem. Soc. (2006): 128, 8122–8123.

Dewal, M.B.; Lufaso, M.W.; Hughes, A.D.; Samuel, S.A.; Pellechia, P.; Shimizu, L.S. “Absorption properties of a porous organic crystalline apohost formed by a self-assembled bis-urea macrocycle.” Chem. Mater. (2006): 18, 4855–4864.

Shimizu, L.S.; Smith, M.D.; Hughes, A.D.; Samuel, S.; Ciurtin-Smith, D. “Assembled tubular structures from bis-urea macrocycles.” Supramolecular Chem. (2005): 17, 27–30.

Ricks, H.L.; Shimizu, L.S.; Smith, M.D.; Bunz, U.H.F.; Shimizu, K.D. “An N,N’-diaryl urea based conjugated polymer model system.” Tetrahedron Lett. (2004): 45, 16, 3229–3232.

Shimizu, L.S.; Hughes, A.D.; Smith, M.D.; Davis, M.J.; Zhang, P.; zur Loye, H.-C.; Shimizu, K.D. “Self-assembled nanotubes that reversibly bind acetic acid guests.” J. Am. Chem. Soc. (2003): 125, 14972–3.

Shimizu, L.S.; Smith, M.D.; Hughes, A.D.; Shimizu, K.D. “Self-assem-bly of a bis-urea macrocycle into a columnar nanotube.” Chem. Commun. (2001): 1592–1593.

l i n D A s . s h i m i Z U A S S I S TA N T p R O F e S S O Rshimizul@chem.sc.edu

B.A., 1990 Wellesley College; ph.d. 1997, Mas-sachusetts Institute of Technology; NIH post-doctoral Fellow, 1997–1998, Massachusetts Institute of Technology; Research Assistant Pro-fessor, University of South Carolina.

Figure 1. Macrocycles 1 and 2 assembled into columns to form porous hosts.

Figure 3. Host 2 also forms porous crystals that facili-tated the photoisomerization of b-trans-methylstyrene to the less stable cis-isomer.

Figure 2. Host 1 reversibly adsorbed a variety of guests including alpha, beta-unsaturated ketones. Irradiation of 2-cyclohexenone in this confined environment selectively yielded the head-to-tail photodimer in high conversion.

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J A m e s m . s o D e t ZC A R O l I N A d I S T I N G U I S H e d p R O F e S S O R ; d I R e C TO R O F M e d I C A l B I O C H e M I S T Rysodetz@mail.chem.sc.edu

Research Areas: Biochemistry; protein chemis-try, protein engineering, and molecular biology; structure-function studies of proteins and enzymes of blood with emphasis on the human comple-ment system.

Our laboratory is studying the structure and func-tion of a group of blood proteins which are com-ponents of the human “complement system.” The complement system is composed of about 35 dif-ferent proteins, enzymes, and regulatory molecules that interact to provide host defense against bacteria and other pathogenic organisms. One product of these interactions is C5b-9, a large protein complex composed of complement proteins C5b, C6, C7, C8 and C9. The C5b-9 complex is also referred to as the “membrane attack complex” (MAC) of complement because it forms a transmembrane pore on target cells. Formation of this pore dis-rupts membrane organization and contributes to bacterial cell killing. Assembly of the MAC is of biochemical interest because it occurs by a sequen-tial, nonenzymatic mechanism and involves major

hydrophilic to amphiphilic transitions by the con-stituent proteins. The binding interactions involved are complex and determined by distinct structural features on each protein. One goal of our lab is to identify these features.

Current efforts are focused on the physical and structural characterization of human C8 and anal-ysis of its interaction with the other MAC compo-nents. Human C8 is an unusual protein composed of three nonidentical subunits referred to as α, b and γ. Through cDNA cloning and sequencing, we determined the complete amino acid sequence of C8 and gained valuable insight into how this protein functions. Specific roles for α and b have been iden-tified and it appears that each subunit contains sev-eral different binding sites. We also determined that α, b and γ are encoded in different genes. Genomic structures of α and b indicate these proteins share a close ancestral relationship to each other and to C6, C7 and C9. By contrast, γ is a member of the “lipocalin” family of proteins, and its role in the complement system is unknown.

Our study of human C8 utilizes the methods of modern biotechnology. All three subunits have been cloned and expressed as recombinant proteins in insect and mammalian cells. Truncated forms of α and b as well as full-length γ have also been pro-duced in E. coli and used to investigate the location and properties of key binding sites. Several regions have been identified as being important in inter-actions with other components of the MAC, and with membrane proteins that regulate MAC activ-ity. We also determined the X-ray crystal structure of the γ subunit and more recently the structure of a functionally important fragment of human α. The structures suggest that human MAC proteins use a mechanism of pore formation that is similar to one used by bacterial pore-forming proteins, i.e. the cytolysins. By further exploring these and other structure-function relationships within the MAC proteins we hope to gain a better understanding of MAC formation and function. Such information will be useful for developing inhibitors of the MAC and for engineering MAC analogues that could destroy undesirable cells, e.g. tumor cells.

R e p R e s e n tat i v e p u b l i c at i o n s :Slade, D.J., Lovelace, L.L., Chruszcz, M., Minor, W., Lebioda, L. and Sodetz, J.M. “Crystal Structure of the MACPF Domain of Human Com-plement Protein C8α in Complex with the C8γ Subunit.” J. Mol. Biol. 379 (2008): 331–342.

Lovelace, L.L., Chiswell, B., Slade, D.J., Sodetz, J.M. and Lebioda, L. “Crys-tal Structure of Complement Protein C8γ in Complex with a Peptide Con-taining the C8γ Binding Site on C8α: Implications for C8γ Ligand Binding.” Mol. Immunol. 45 (2008): 750–756.

Chiswell, B., Lovelace, L.L., Brannen, C., Ortlund, E.A., Lebioda, L. and Sodetz, J.M. “Structural Features of the Ligand Binding Site on Human Complement Protein C8γ: A Member of the Lipocalin Family.” Biochim. Biophys. Acta 1774 (2007): 637–644.

Brannen, C.L., and Sodetz, J.M. “Incorporation of Human Complement C8 into the Membrane Attack Complex is Mediated by a Binding Site Located within the C8b MACPF Domain.” Mol. Immunol. 44 (2007): 960–965.

Chiswell, B., Slade, D.J. and Sodetz, J.M. “Binding of the Lipocalin C8γto Human Complement Protein C8α is Mediated by Loops Located at the Entrance to the C8γ Ligand Binding Site.” Biochim. Biophys. Acta 1764 (2006): 1518-1524.

Slade, D.J., Chiswell, B., Sodetz, J.M. “Functional Studies of the MACPF Domain of Human Complement Protein C8α Reveal Sites for Simulta-neous Binding of C8b, C8γ and C9.” Biochemistry 45 (2006): 5290–5296.

Dijk, W.V., DoCarmo, S., Rassart, E., Dahlback, B. and Sodetz, J.M. “The Plasma Lipocalins α1-acid glycoprotein, Apolipoprotein D, Apolipoprotein M and Complement Protein C8γ.” In Lipocalins, Åkerström, B., Borregaard, N., Flower, D. and Salier, J-P, Eds., Landes Bioscience/Eurekah, Georgetown, Texas (2006): 140–166.

Lebioda, L. and Sodetz, J.M. “Human Complement Protein C8.” In Struc-tural Biology of the Complement System. Morikis, D. and Lambris, J.D. Eds., CRC Press, London (2005): 233–250.

Scibek, J.J., Plumb, M.E., and Sodetz, J.M. “Binding of Human Comple-ment C8 to C9: Role of the N-Terminal Modules in the C8α Subunit, Bio-chemistry 41 (2002): 14546–14551.

Parker C.L. and Sodetz, J.M. “Role of the Human C8 Subunits in Comple-ment-Mediated Bacterial Killing: Evidence that C8γ is Not Essential.” Mol. Immunol. 39 (2002): 453–458.

Musingarimi, P. and Sodetz, J.M. “Interaction between the C8α-γ and C8b Subunits of Human Complement C8: Role of the C8b N-Terminal Throm-bospondin Type 1 Module and Membrane Attack Complex/Perforin Domain” Biochemistry 41 (2002): 11255–11260.

Ortlund, E., Parker, C.L., Schreck, S.F., Ginell, S., Minor, W., Sodetz, J.M. and Lebioda, L. “Crystal Structure of Human Complement Protein C8γ at 1.2Å Resolution Reveals a Lipocalin Fold and a Distinct Ligand Binding Site.” Biochemistry 41 (2002): 7030–7037.

Plumb, M.E. and Sodetz, J.M. “An Indel Within the C8α Subunit of Human Complement C8 Mediates Intracellular Binding of C8γ and Formation of C8α-γ.” Biochemistry 39 (2000): 13078–13083.

Schreck, S.F., Parker, C.P., Plumb, M.E. and Sodetz, J.M. “Human Com-plement Protein C8γ.” In BBA-Protein Structure and Molecular Enzymol-ogy (Special Issue on ‘Lipocalins’), Salier, J-P, Akerstrom, B. and Flower, D., eds. Biochim. Biophys. Acta. 1482 (2000): 199–208.

Plumb, M.E., Scibek, J.J., Barber, T.D., Dunlap, R.J., Platteborze, P.L. and Sodetz, J.M. “Chimeric and Truncated Forms of Human Complement Pro-tein C8α Reveal Binding Sites for C8b and C8γ within the Membrane Attack Complex/Perforin Region.” Biochemistry 38 (1999): 8478–8484.

Plumb, M.E. and Sodetz, J. M. “Proteins of the Membrane Attack Complex.” in The Human Complement System in Health and Disease, J.E. Volanakis and M.M. Frank, eds. Marcel Dekker, New York (1998): 119–148.

B i o c h e m i s t ry

B.A., 1970, Knox College; ph.d., 1975, Univer-sity of Notre dame; NIH postdoctoral Fellow, 1975–1977, duke University Medical Center.

Established Investigator Award, American Heart Association, 1982–1987; Basic Science Research Award, University of South Carolina School of Medicine, 1990; Russell Research Award for Sci-ence, Mathematics, and engineering, 2000; Car-olina Trustee professor Award, 2007.

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c h U A n B i n g tA n gA S S I S TA N T p R O F e S S O Rtang.c@chem.sc.edu

Research Areas: Organic polymer synthesis, con-trolled/living radical polymerization, renewable polymers from biomass, organometallic polymers, macromolecular self-assembly, polymer nanotech-nology, clean energy.

Our research combines synthesis of innovative poly-meric materials, including both novel monomers and polymers, and macromolecular self-assem-bly, particularly focusing on the control at the nanoscale. By controlling functionality at the side chains or main chains, we want to deliver polymers with unprecedented properties with the aid of self-assembly. Each of our projects starts with funda-mental understanding of scientific problems and breakthrough.

Renewable Polymers from Biomass: Synthesis of renewable polymeric materials from natural

resources has becoming a rapidly growing area as these materials could potentially replace or partially replace environmentally and energy unfavorable plastics derived from petroleum chemicals. How-ever, applications of renewable polymers are signifi-cantly behind petroleum-derived polymers, partially because of limitations in the monomer resources and therefore derived polymers. We have devel-oped a variety of renewable monomers and poly-mers using gum rosin as a natural resource. Our goal is to revolutionize traditional renewable poly-mers and develop a new class of green polymers such as thermoplastic elastomers, degradable poly-mers, and natural fiber reinforced nanocomposites.

Metallocene Polymers: Metallocene containing poly-mers have attracted significant attentions since they have great potentials in catalytic, optical, magnetic, and biological applications as well as uses for semi-conductors, lithographic resists, and ceramic pre-cursors due to the specific and unique geometries and their properties of metallocenes. Compared to ferrocene and ferrocene polymers, cobaltocene has received far less attention, partly because of greater difficulty in preparing substituted derivatives. We have developed a strategy to prepare substituted cobaltocenium derivatives. We aim to develop a synthetic toolbox toward well-defined cobalto-cenium polymers: (1) side-chain polymers, (2) main-chain polymers, and (3) end-functionalized polymers. The goal is to explore a broad range of spectra of novel cobaltocenium polymers and to lay out synthetic foundation of this type of poly-mers for many potential applications.

Macromolecular Self Assembly in Thin Films and Solution: One of the major motivations to syn-thesize well-defined polymers is to make them self-assemble and lead to unusual but desirable functions. The self-assembly of block copolymers in thin films has drawn much attention due to its potential applications in microelectronic devices, data storage system, membranes, etc. In thin films, 2D confinement and surface/substrate interactions are additional key parameters that affect ordering behavior. By developing new strategies, we aim to combine long-range ordering and novel functions. The use of amphiphilic block copolymers as a tem-plate to form discrete nanostructures has numer-ous applications such as drug delivery, templates toward ordered metallic, magnetic, and inorganic nanoobjects. Characterization is carried out with the aid of state-of-the-art scanning force micros-copy for localized surface information and synchro-tron grazing incidence x-ray scattering technique for probing macroscopic structures.

R e p R e s e n tat i v e p u b l i c at i o n s

Ren C.; Hardy, C.G.; Tang, C. “Synthesis and solution self assembly of side-chain cobalticinium-containing block copolymers.” Journal of American Chem-ical Society, (2010): 132, 8874–8875.

Zheng, Y.; Yao, K.; Lee, J.S.; Chandler, D.; Wang, J.; Wang, C.; Chu, F.; Tang, C. “Well-defined polymers derived from gum rosin.” Macromolecules, (2010): 43, 5922–5924.

Tang, C.; Sivanandan, K.; Stahl, B.C.; Fredrickson, G.H.; Kramer, E.J.; Hawker, C.J. “Multiple nanoscale templates by orthogonal degradation of a supramolecular block copolymer lithographic system.” ACS Nano, (2010): 4, 285–291.

Tang, C.; Lennon, E.M.; Fredrickson, G.H.; Kramer, E.J.; Hawker, C.J. “Evolution of block copolymer lithography to highly ordered square arrays.” Science, (2008): 322, 429–432.

Tang, C.; Bang, J.; Stein, G.; Fredrickson, G.H.; Hawker, C.J.; Kramer, E.J. “Square packing and structural arrangement of ABC triblock copolymer spheres in thin films.” Macromolecules, (2008): 41, 4328–4339.

Tang, C.; Bombalski, L.; Kruk, M.; Jaroniec, M.; Matyjaszewski, K.; Kow-alewski, K. “Nanoporous carbon films from ‘hairy’ polyacrylonitrile-grafted colloidal silica nanoparticles.” Advanced Materials, (2008): 20, 1516–1522.

Tang, C.; Tracz, A.; Kruk, M.; Zhang, R.; Smiligies, D.; Matyjaszewski, K.; Kowalewski, T. “Long-range ordered thin films of block copolymers pre-pared by zone-casting and thermal conversion into ordered nanostructured carbon.” Journal of American Chemical Society, (2005): 127, 6918–6919.

Tang, C.; Qi, K.; Wooley, K.; Matyjaszewski, K.; Kowalewski, T. “Well-defined carbon nanoparticles prepared from water soluble shell cross-linked micelles containing polyacrylonitrile cores.” Angewandte Chemie International Edition, (2004): 43, 2783–2787.

B.S., 1997, Nanjing University; ph.d., 2006, Carnegie Mellon University; Postdoctoral Fellow, 2006–2009, University of California at Santa Barbara.

Singapore National Research Foundation Research Fellow, 2009; Chinese Academy of Forestry Oversea professor, 2010–2012.

Figure 2. Self-assembled nanotubes from cobaltocenium block copolymers

Figure 1. Renewable functional polymers and nanocomposites

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t h o m A s vo g te d U C AT I O N A l F O U N d AT I O N d I S T I N G U I S H e d p R O F e S S O R O F C H e M I S T Ry ;d I R e C TO R O F T H e U S C N A N O C e N T e Rtvogt@mailbox.sc.edu

i n o r g A n i c

Research Areas: Crystallography; general struc-tural chemistry; chemical synthesis, structures, and properties of metal oxides; electron, x-ray, and neu-tron diffraction techniques and instrumentation (i.e high pressure x-ray diffraction, high-temperature electron microscopy)

Research Project 1: The Design of Novel Photocatalysts

Both solar energy conversion and photo-catalytic waste remediation are based on the excitation of electron-hole pairs and the subsequent promotion of electrons into the conduction band enabling the reduction of an acceptor, while the holes left behind in the valence band will oxidize a donor. The energy required for this process is equal to or greater than the band gap of the semiconductor. In many cases cocatalysts such as Pt or NiO are added to further facilitate the redox process after the electron-hole formation. The peak power of the sun is in the yel-low region near 2.5 eV. The photo-catalytic activity of various calcium bismuth oxides (Ca6O6O15, Ca4Bi6O13, CaBi6O10) are being investigated by monitoring the decomposition of methlyene blue

(MB) under visible light. Cheap and easy to pre-pare Ca-Bi-oxides are promising photo-catalysts operating in visible light. The long-term stabil-ity and activity as well as antibacterial and antimi-crobial properties are currently being investigated.

Research Project 2: New Phosphors for Up- and Down-Conversion of Light

Luminescenece, the absorption of energy with subsequent emission of light and, more specifi-cally, fluorescence, the absorption of energy with subsequent emission of light in the visible spec-trum, are the basis of a broad range of everyday applications such as lighting and x-ray detectors for medical and technical applications. Lumines-cent materials, also called phosphors, consist of a host lattice in which activator ions are doped into in small concentrations, typically less than a mole percent. The activator ions have energy levels that can be populated by direct excitation or indirectly by energy transfer and are responsible for the lumi-nescence. We have discovered a new family of lumi-nescent materials and are currently exploring its use in white light LED applications as well as upcon-version applications such as biomedical imaging. This work involves solid-state synthesis, structural characterization using x-ray powder diffraction, and extensive characterization of the optical properties.

Research Project 3: Imaging at the Nanoscale.

High-Angle-Annular-Dark-Field/Scanning Trans-mission Electron Microscopy (HAADF/STEM) is a technique uniquely suited for detailed studies of the structure and composition of complex oxides. The HAADF detector collects electrons that inter-act inelastically with the potentials of the atoms in the specimen and therefore resembles the better known Z2 (Z is atomic number) Rutherford scat-tering. One class of important catalysts consists of bronzes based on pentagonal {Mo6O21} building units; these include Mo5O14 and Mo17O47. In the last 20 years, new materials doped with a vari-ety of substitution elements, but built upon the same structural building units, have been made and evaluated for their catalytic properties. Appli-

cations include the selective oxidation of light par-affins and olefins, as well as the partial oxidation of methanol.

We engage in HAADF-STEM investigations of various complex oxide phases and have shown that we can, for example, distinguish metal-containing sites within these structurally and compositionally complex-oxides through Z2-contrast analysis. We compare our experiments to image simulations that are done in collaboration with the Interdisciplinary Mathematics Institute here at USC. Collaboration with Douglas Blom (University of South Carolina) and Douglas Buttrey (University of Delaware).

R e p R e s e n tat i v e p u b l i c at i o n s

Pyrz, W.D., D.A. Blom. T. Vogt, D.J. Buttrey. “Direct Imaging of the MoVTeNbO M1 Phase using a Cs-corrected High-resolution Scanning Transmission Electron Microscope (STEM).” Angewandte Chemie Int. Ed., (2008): 47, 2788–2791.

Pyrz, W.D., D.A. Blom, D.J. Buttrey, T. Vogt. “High-Angle Annular Dark field Scanning Transmission Electron Microscopy (HAADf-STEM) Inves-tigations of Bimetallic nickel-Bismuth Nanomaterials Created by Electron Induced Electron Beam Induced Fragmentation (EBIF).” J. Phys. Chem C (2010): 114, 2538–2543.

Pyrz, W.D., D.A. Blom, M. Sadakane, K. Kodato, W. Ueda, T. Vogt, and D.J. Buttrey. “Atomic-Level Imaging of Mo-V-O Complex Oxide Phase Intergrowth, Grain Boundaries, and Defects using HAADF-STEM.” Pro-ceedings of the National Academy of Sciences, (2010): 107 (14) 6152–6157.

Pyrz, W.D., D.A. Blom, M. Sadakane, K. Kodato, W. Ueda, T. Vogt, and D.A. Buttrey. “Atomic-Scale Investigation of Two-Component MoVO Complex Oxide Catalysts Using Aberration-Corrected High-Angle Annu-lar Dark-Field Imaging.” Chemistry of Materials, (2010): 22 (6), 2033–2040.

Park, S., T. Vogt. “Near UV Excited Line and Broad Band Photoluminescence of an Anion-Ordered Oxyfluoride.” J. Am. Chem. Soc., (2010): 132, 4516.

Park, S., T. Vogt. “Luminescent Phosphors based on Rare earth Substituted Oxyfluorides in the A(1)3-xA(2)xMO4F Family with A(1)/A(2) = Sr, Ca, Ba and M =Al, Ga.” Journal of Luminescence, (2009): 129, 952–957.

Diplom, 1985, University of Töbingen, Germany; ph.d., 1987, University of Töbingen, Germany

Scientist, 1988–1992, Institute laue-lan-gevin, Grenoble, France; physicist, 1992–2000, Brookhaven National laboratory (BNl); Group leader powder diffraction, 2000 –2003, BNl; Head of Materials Synthesis & Characterization Group, 2003 –2005, BNl; fellow of the American physical Society, 2006; fellow of the American Association for the Advancement of Science, 2008; International Visiting Research Fellow-ship at the University of Sydney, Australia, 2009; adjunct faculty at the African University of Sci-ence and Technology in Abuja, Nigeria, 2009.

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P h s y i c A l

Research Areas: Biophysical chemistry; single-molecule spectroscopies and microscopies; single-molecule manipulation; nanostructure fabrication; nanoscale self-assembly; nanophotonics; single-particle spectroscopies; plasmon-enhanced spec-troscopies.

The central theme of our research is to use physi-cal chemistry approaches to tackle challenging problems in molecular biology and materials science. We perform cutting-edge research at the interface of physical chemistry, molecular biology, and materials science with a major focus on using single-molecule or single-particle spectroscopy/microscopy approaches to gain deep insight into complicated biomolecular processes and novel nanophotonic material systems.

Probing nanoscale DNA bending by single-molecule spectroscopies. Double-stranded DNA (dsDNA) has long been considered as a relatively stiff poly-mer with a bending-persistence length of about 50 nm in buffered salt solutions. Although sharp bending of a dsDNA segment over nanometer length scale requires large force and energy-cost, a large number of important biological pro-cesses, such as genomic packaging and transcrip-tional regulation, involve DNA bending over length scales as short as a few nanometers. Such nanoscale DNA bending can occur spontaneously with the help of DNA-bending proteins upon the formation of the nucleoprotein complexes. Here we use single-molecule spectroscopies to study protein-induced nanoscale DNA bending. These studies will be of paramount importance to the

development of molecular-level understanding on how the local bending of DNA over nanome-ter length scale controls and regulates a series of important biological processes.

Probing DNA condensation using Single-molecule Hydrodynamic Flow-stretching Assays. The exis-tence of distinct states of DNA condensation is vital to the functions of the cells. The highly condensed DNA conformations lead to the effi-cient compaction of the DNA genomes. Equally important are some transient, less condensed conformations of DNA required during much of the cell life cycle to allow proteins to access the genomic DNA for a multitude of biological tasks, such as gene regulation and transcription. We are interested in DNA condensation induced by proteins over a much longer length scale than the nanoscale DNA bending. We perform single-molecule measurements using hydrodynamic flow-stretching assays based on single-particle manipulation and tracking in microfluid flow cells. The goal of this set of projects is to develop a molecular-level understanding on the relation-ship between localized DNA bending and global DNA condensation. We expect to establish the correlation of molecular conformation and con-formational dynamics with the biological func-tions.

Single-nanoparticle plasmonics. Metallic nano-structures have emerged as an important class of subwavelength components with interesting optical properties essentially arising from the col-lective oscillation of free electrons of the metals known as plasmons. Many interesting phenom-ena associated with plasmonic excitations have

been observed and investigated, such as sub-wavelength wave-guiding, super lensing effects, and surface-enhanced molecular spectroscopies. A key feature of these metallic nanostructures is that their far-field and near-field optical proper-ties are geometrically tunable, which enables widespread applications. Our interests in nano-plasmonics broadly span several important aspects in this field, including but not limited to nano-structure fabrication, nanoscale self-assembly, mechanisms of nanostructure formation, and plasmon-enhanced molecular spectroscopies. The goals of our research are to develop quantitative understanding on the geometry-property rela-tionship of complex plasmonic nanostructures at single-nanoparticle level and to explore the possibility of using a single plasmonic nanopar-ticle with optimized properties as ultrasensitive molecular sensors based on plasmon-enhanced spectroscopies.

R e p R e s e n tat i v e p u b l i c at i o n s

Wang, H.; Yeh, Y.S.; Barbara, P.F. “HIV-1 Nucleocapsid Protein Bends Double-Stranded Nucleic Acids.” Journal of the American Chemical Society, (2009): 131 (42), 15534–15543.

Wang, H.; Brandl, D.W.; Nordlander, P.; Halas, N.J. “Plasmonic nano-structures: Artificial molecules.” Accounts of Chemical Research, (2007): 40 (1), 53–62.

Wang, H.; Kundu, J.; Halas, N.J. “Plasmonic nanoshell arrays combine sur-face-enhanced vibrational spectroscopies on a single substrate.” Angewandte Chemie-International Edition, (2007): 46 (47), 9040–9044.

Wang, H.; Wu, Y.P.; Lassiter, B.; Nehl, C.L.; Hafner, J.H.; Nordlander, P.; Halas, N.J. “Symmetry breaking in individual plasmonic nanoparticles.” Proceedings of the National Academy of Sciences of U.S.A. 2006, 103 (29), 10856–10860.

Wang, H.; Brandl, D.W.; Le, F.; Nordlander, P.; Halas, N.J. “Nanorice: A hybrid plasmonic nanostructure.” Nano Letters, (2006): 6 (4), 827–832.

Wang, H.; Levin, C.S.; Halas, N.J. “Nanosphere arrays with controlled sub-10-nm gaps as surface-enhanced Raman spectroscopy substrates.” Journal of the American Chemical Society, (2005): 127 (43), 14992–14993.

h U i WA n gA S S I S TA N T p R O F e S S O Rwang.hui@chem.sc.edu

B.S., 2001, Nanjing University; ph.d., 2007, Rice University; postdoctoral fellow, 2007–2010, Uni-versity of Texas at Austin.

(left panel) probing conformational dynamics of dNA-NC complexes by Single-Molecule Förster Resonance Energy Transfer (SM-FRET); (right panel) complex plasmonic nanostructures with unique tunable optical proper-ties that are exploitable for ultrasensitive molecular sensing applications

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Research Areas: Organic synthesis, bioconjugation chemistry, biomaterials chemistry, and soft materials.

Introduction: The central concept of our research is how to marry organic chemistry with the logic of biology in order to develop new materials and solve the problems in chemistry and biology. Synthetic chemistry and molecular biology will be employed as the major tools to pursue our research. Students will work in a highly interdisciplinary research team and will have the opportunity to learn a variety of techniques, such as organic synthesis, combina-torial chemistry, molecular biology, and modern instrumental analysis. Some of the areas that we are interested in are as follows:

Bionanoparticles as molecular scaffolds: Bionanopar-ticles (BNPs), including viruses, ferritins, and self-assembled protein cages, can be considered building blocks, scaffolds, and nanoreactors for chemical operations and materials development. Many BNPs are structurally well characterized at near atomic resolution and can be safely handled and easily obtained in large quantities. BNPs can be treated as “molecules” by synthetic chemists. Each BNP has

unique physical, chemical, and biological properties. Despite viruses’ greater structural and functional complexities in comparison to other biomolecules such as nucleic acids and proteins, the shell pro-teins of BNPs are well-arrayed as helical or spher-ical morphology. These features make BNPs very attractive polyvalent platforms for developing new chemistry and materials (Figure). We will exploit non-enveloped icosahedral or helical viruses and ferritins as scaffolds in chemical reactions. Upon chemical or genetic modification, various func-tionalities (i.e. sensing moieties, enzyme mimetic sites, energy harvesting molecules, cell targeting and permeating groups, in vivo imaging reagents, and DNA binding groups, etc.) will be engineered on the exterior or the interior surface, to create novel functional nanoparticles. In addition, the viral shell proteins (capsids) constrain a special microenviron-ment that will be employed as a “nano-vessel” for chemical reactions.

Developing new biomaterials on the basis of self-assembly. Quantitative understanding of the chem-ical, physical, dynamic, and mechanical aspects of nanoparticle-based self-assembly to form hierarchi-cally ordered structures at the nanometer scale is the basis of novel optical, acoustic, electronic, and magnetic materials and devices. A fundamental dis-advantage in the use of synthetic nanoparticles for such studies is the inherent polydispersity of the par-ticle size and non-uniformity of their surface prop-erties. In addition, the chemistries associated with particle fabrication are difficult, and the degree of functionality of the particles is always uncertain. In contrast, BNPs are monodisperse in size and can be functionalized in a robust, well-defined man-ner under the control of malleable genetic infor-mation. These properties, unique to BNP’s, make them uniquely suited for studies of self-assembly

that will have broad applications. Our major efforts will focus on two aspects: interfacial assembly of BNPs between immiscible fluids (Figure) and hier-archical self-assembly of BNPs with diblocks copo-lymers. By the chemical and genetic modification on the basis of the structure information, we hope to program the viral particle to form controllable one-, two-, or three-dimensional arrays.

Fluorogenic reactions for bioconjugation and bioim-aging: We have developed a series of fluorogenic CuAAC reactions. In addition to being used in the combinatorial synthesis of fluorescent dyes, the most important application of these reactions is the bioconjugation and bioimaging within the intra-cellular environment. Incorporation of exogenous natural or unnatural tags into proteins or glycans by cellular biosynthetic pathways is an emerging strategy for investigating their cellular activities. Since those processes involve multistep enzymatic transformations that prohibit the incorporation of large signaling moieties, chemoselective reactions are often employed for post-labeling. In this case, a bioorthogonal fluorogenic reaction is invaluable, in which unreacted reagents show no fluorescent background and the purification process can be cir-cumvented. One of the 3-azidocoumarins devel-oped in our group had been successfully utilized for in vivo protein labeling studies.

R e p R e s e n tat i v e p u b l i c at i o n s

Le Droumaguet, C.; Wang, C.; Wang, Q. “Fluorogenic Click Reaction.” Chem. Soc. Rev. (2010): 39, 1233–1239 (cover paper).

Kaur, G.; Valarmathi, M.T.; Potts, J.D.; Jabbari, E.; Sabo-Attwood, T.; Wang, Q. “Regulation of osteogenic differentiation of rat bone marrow stromal cells on 2D nanorod substrates.” Biomaterials, (2010): 31, 1732–1741.

Lin, Y.; Balizan, E.; Lee, L.A.; Niu, Z.; Wang, Q. “Self-assembly of rod-like bionanoparticles in capillary tube.” Angew. Chem. Int. Ed. (2010): 49, 868–872 (frontispiece cover story).

Li, T.; Niu, Z.; Emrick, T.; Russell, T.P.; Wang, Q. “Raspberry-like Core-Shell Nanocomposite from Hierarchical Assembly of Virus and Polymer.” Small, (2008): 4, 1624–1629.

Kaur, G.; Valarmathi, M.T.; Potts, J.D.; Wang, Q. “Plant virus as polyvalent substrate to promote the osteoblastic differentiation of rat bone marrow stro-mal cells.” Biomaterials, (2008): 29, 4074–4081.

Barnhill, H.N.; Claudel-Gillet, S.; Ziessel, R.; Charbonnière, L.; Wang, Q.; “A Prototype Protein Assembly as Scaffold for Time-Resolved Fluoroimmuno Assays.” J. Am. Chem. Soc. (2007): 129, 7799–7806.

q i A n WA n gA S S O C I AT e p R O F e S S O R , R O B e RT l . S U M WA lT p R O F e S S O R O F C H e M I S T Rywang@chem.sc.edu

o r g A n i c

B.A., 1992, Tsinghua University, China; Ph.D., 1997, Tsinghua University, China; postdoctoral Fellow, 1997–1999, University of lausanne; Skaggs postdoctoral Fellow, 1999–2001, and Senior Research Associate, 2003, The Scripps Research Institute.

National Science Foundation CAReeR Award, 2008; Alfred p. Sloan Foundation Research Fellow, 2008; Camille dreyfus Teacher-Scholar Award, 2008; CApA distinguished junior Fac-ulty Award, 2008; South Carolina Governor’s young Scientist Award, 2009.

Controlling cell growing in capillary by viral assemblies

Flourogenic reactions

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Research Areas: Synthetic methodology; organo-catalysis; physical organic; bio-organic.

My research interests lie within the area of synthetic organic methodology. We are focused on devel-oping facile methods for the formation of chiral compounds directly as well as identifying ways to efficiently resolve and isolate medicinally impor-tant enantiopure intermediates. Most recently we have been focused on kinetic resolutions toward accomplishing this goal.

Optically active intermediates are of increasing importance in the pharmaceutical and agrochem-ical industries as the number of active chiral com-pounds in their pipelines grow. Chiral alcohols and amines are of particular importance in the develop-ment of many products for these industries. While there are ways to form these compounds asymmet-rically, industry has still found kinetic resolution to be a very efficient and economical way to deal with their asymmetric formation. A kinetic reso-lution is a separation of enantiomers by selectively reacting one enantiomer over the other in an asym-metric reaction. While there are reactions to asym-metrically form both alcohols and amines, there are issues with substrate variability in methodology.

One of the advantages of a kinetic resolution over an asymmetric reaction is that the ee of the starting material is continuously increasing as the reaction progresses (see Figure 1). This allows for the recov-

ery of highly enriched material, even when the res-olution only has moderate selectivity.

We are developing new strategies for the separa-tion of these compounds as well as employing new techniques toward this goal. Our approach toward this has included employing a silyl group to asym-metrically derivatize one enantiomer over another. We have employed this in a one-step and a two-step process while also exploring the mechanism of these reactions. We have also developed an enanti-oselective polishing process that couples moderately selective reactions with moderately selective kinetic resolutions to obtain highly enriched compounds in higher yield and enantiomeric excess than could have been obtained with the individual processes. Ultimately, we are finding new and novel ways to obtain highly enantiomerically enriched materials.

R e p R e s e n tat i v e p u b l i c at i o n s

Klauck, M; Patel, S.G.; Wiskur, S.L. “Highly Enriched Compounds via a Tandem Asymmetric Reaction and Kinetic Resolution Polishing Sequence.” (2010): in preparation.

Sheppard, C.I.; Taylor, J.; Wiskur, S.L. “A Silylation Based Kinetic Resolution of Monofunctional Secondary Alcohols.” (2010): in preparation.

Patel, S.G.; Wiskur, S.L. “Mechanistic Investigations of the Mukaiyama Aldol Reaction as a Two Part Enantioselective Reaction.” Tetrahedron Lett. (2009): 50, 1164–1166.

Wiskur, S.L.; Fu, G.C. “Catalytic Asymmetric Synthesis of Esters from Ketenes.” J. Am. Chem. Soc. (2005): 127, 6176–6177.

Wiskur, S.L.; Korte, A.; Fu, G.C. “Cross-Couplings of Alkyl Electrophiles Under ‘Ligandless’ Conditions: Negishi Reactions of Organozirconium Reagents.” J. Am. Chem. Soc. (2004): 126, 82–83.

Wiskur, S.L.; Lavigne, J.J.; Metzger, A.; Tobey, S.; Lynch, V.; Anslyn, E.V. “Thermodynamic Analysis of Receptors Based on Guanidinium/Boronic Acid Groups for the Complexation of Carboxylates, α-Hydroxycarboxylates, and Diols: Driving Force for Binding and Cooperativity.” Chem. Eur. J. (2004): 10, 3792–3804.

Wiskur, S.L.; Floriano, P.N.; Anslyn, E.V.; McDevitt, J.T. “A Multicomponent Sensing Ensemble in Solution: Differentiation between Structurally Similar Analytes.” Angew. Chem. Int. Ed. (2003): 42, 2070–2072.

Wiskur, S.L.; Ait-Haddou, H.; Lavigne, J.J.; Anslyn, E.V. “Teaching Old Indicators New Tricks.” Acc.Chem. Res. (2001): 34, 963–972.

Wiskur, S.L.; Anslyn, E.V. “Using a Synthetic Receptor to Create an Optical-Sensing Ensemble for a Class of Analytes: A Colorimetric Assay for the Aging of Scotch.” J. Am. Chem. Soc. (2001): 123, 10109–10110.

s h e ry l W i s k U rA S S I S TA N T p R O F e S S O Rwiskur@chem.sc.edu

B.S., 1997, Arizona State University; ph.d., 2003, University of Texas–Austin; postdoctoral Associate, Massachusetts Institute of Technol-ogy, 2003–2005..

o r g A n i c

Figure 2. Our enantioselective polishing sequence showing an asymmetric reduction and kinetic resolution paired to obtain high ee’s and high yields.

Figure 1. Generic kinetic resolution scheme highlighting the principle of selectivity arises by the enantiomers have different rates in the reaction and that the ee of the starting material increases as the reaction progresses.

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Research Areas: Molecular and inorganic bio-chemistry; biochemistry of biological mineraliza-tion; characterization of cellular events leading to mineralization of growth plate cartilage; charac-terization of matrix vesicles (MVs), key initiators of mineralization; characterization of the inor-ganic phosphate (Pi) ion-transporter; mechanism of action of Fusarochromanone (FC101), a potent inhibitor of both angiogenesis and proliferation of numerous cancer cell lines.

Calcification of developing bones is complex involv-ing the deposition of calcium-phosphate (apatite) mineral into the extracellular matrix of growth plate cartilage. Membrane-enclosed extracellular matrix vesicles (MVs) initiate this process. Our past work aimed at elucidating the mechanism by

which MVs form and then catalyze the creation of biological apatite. From research at USC we dis-covered a key set of acidic phospholipid-depen-dent CaTT2+ -binding proteins, the annexins, which act as Ca2+ -ion channel proteins in MV membranes. Current studies also aim at character-ization of the Pi-transporter in MVs and chondro-cytes (cells involved in longitudinal bone growth). From these cells, we have cloned and sequenced a new Pi-transporter, showing it to have special pH and cation dependency, as well as locus of expres-sion. Studies are also in progress to produce large unilamellar vesicles from known constituents, mod-eling their physico-chemical properties to match those of native MVs. These studies will enable us to establish the essential machinery used by MVs to initiate endochondral mineralization.

An important spin-off of this work has been the dis-covery that a fungal metabolite, Fusarochromanone (FC101), known to cause avian tibial dyschondro-plasia, is an inhibitor not only of angiogenesis, but also of the proliferation of many human cancer cell lines. FC101 has highly selective action, inhibiting growth of many melanoma cell lines with IC50 s in the 0.5 nM range, as well as various lung can-cer and colon cancer cells in the 10–50 nM range. FC101 has low toxicity toward normal nonprolif-erating cells, but does inhibit proliferation of the vascular endothelial cells involved in angiogenesis, with an IC50 of ~50 nM. FC101 has little effect on the proliferation of chondrocytes from several species (IC50 ~3,000 nM). The drug was found to inhibit well over half of the 60 human cancer cell lines used in the screening assay of the National Cancer Institute Drug Development Program.

R e p R e s e n tat i v e p u b l i c at i o n s

Wu, L.N.Y., Genge, B.R., and Wuthier, R.E. “Differential effects of zinc and magnesium ions on mineralization activity of phosphatidylserine calcium phos-phate complexes.” J. Inorg. Biochem. (2009): 103, 948–962.

Furmanski, B.D., Dréau, D., Wuthier, R.E., and Fuseler, J.W. “Differential uptake and selective permeability of fusarochromanone (FC101), a novel membrane-permeable anticancer naturally fluorescent compound in tumor and normal cells.” Microsc. Microanal. (2009): 15, 545–557.

Dréau, D., Foster, M., Hogg, M., Nunes, P., and Wuthier, R.E. “Inhibitory effects of Fusarochromanone on melanoma growth.” Anti-Cancer Drugs 18 (2007): 897–904.

Genge, B.R., Wu, L.N.Y., and Wuthier, R.E. “Kinetic analysis of mineral formation during in vitro modeling of matrix vesicle mineralization: Effect of annexin a5, phosphatidylserine, and type II collagen.” Analyt. Biochem. (2007): 367 (2), 159–166.

Genge, B.R., Wu, L.N.Y., and Wuthier, R.E. “In vitro modeling of matrix vesicle nucleation: Synergistic stimulation of mineral formation by annexin A5 and phosphatidylserine.” J. Biol. Chem. (2007): 282 (36), 26035–26045.

Wu, L.N.Y., Genge, B.R., and Wuthier, R.E. “Analysis and molecular mod-eling of the formation, structure and activity of the phosphatidylserine-cal-cium-phosphate complex associated with biomineralization.” J. Biol. Chem. (2008): 283 (7), 3827–3838.

Genge, B.R., Wu, L.N.Y., and Wuthier, R.E. “Mineralization of biomimetic models of the matrix vesicle nucleation core: Effect of lipid composition and modulation by cartilage collagens.” J. Biol. Chem. (2008): 283 (15), 9737–9748.

r oy e . W U t h i e rG U y F. l I p S C O M B S R . d I S T I N G U I S H e d C H A I R e M e R I T U Swuthier@chem.sc.edu

B i o c h e m i s t ry

Physicochemical characterization of the nucle-ational complex of matrix vesicles

A. Solid-state 31p-NMR spectrum of a synthetic phosphatidyl-serine (PS):Ca2+:Pi complex modeled to that present in the nucleational core of matrix vesicles. The marked increase in intensity of the spinning sidebands in the 31p-NMR spectrum induced by 1H-cross polarization reveals the presence of a pro-tonated phosphate group. The NMR spectrum of this complex is unique and unlike that of any known crystalline phosphate group. Fourier-transform infrared (FT-IR) spectra of the com-plex (not shown) indicate that the phosphate environment is extremely similar to that in crystalline calcium phosphate min-erals, even though X-ray and electron diffraction reveal that the complex is not a classically crystalline compound.

B. Putative structure of the PS:Ca2+:Pi complex. Direct chem-ical analyses, radial distribution function (RDF), extended X-ray absorption fine structure (EXAFS), and Cd2+-substituted ana-logues of the complex indicate a stoichiometry of PS:Ca2+:Pi (1:1:1) in which Ca2+ is coordinated with two oxygens and one nitrogen of the polar head group of PS, as well as to HPO4

2-. Two water molecules (not shown) are coordinated in axial positions above and below the Ca2+. In this complex, Ca2+ is coordinated to the amino-N of the serine forming 2 glycinate ring systems analogous to the 4 present in EDTA, a strong chelator of Ca2+. This metastable complex is an intermediate in the progression from solution to non-crystalline-solid to crystalline state. The short range order of the complex is like that of crystalline min-erals, but there is no long-range order. This PS:Ca2+:Pi complex is a key component of the nucleation core of the matrix vesicles that induce mineral formation during bone growth.

A

B

B.S., 1954, University of Wyoming; M.S., 1958, University of Wisconsin; ph.d., 1960, Univer-sity of Wisconsin; postdoctoral Research Fel-low, 1961, Postdoctoral Research Associate, 1962–1964, Harvard University.

Research Career development Award, Natl. Inst. of Health, 1964–1971; Basic Research Award in Biological Mineralization, International Association for Dental Research, 1982; Basic Science Research Award, University of South Carolina School of Medicine, 1983, 1997; Rus-sell Research Award for Science, Mathematics, and Engineering, University of South Carolina, 1993; Editorial Board, Bone, 1983–1994; edito-rial Board, Bone and Mineral, 1989–1993; edito-rial Board, Bone and Calcified Tissue International, 1991–1993; Governor’s Award for excellence in Science Discovery, South Carolina Academy of Science, 1999; U.S. patent No. 5,932,611, “Use of FC101 as an Angiogenesis Inhibitor for the Treatment of Cancer,” 1999; U.S. patent No. 6,225,340, “Angiogenesis Inhibitor for the Treat-ment of endothelial Cell proliferation,” 2001; Editorial Board, Annexins, 2004.

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Research Areas: Inorganic materials chemistry; syn-thesis of novel solid-state materials and character-ization of their physical properties; investigation of cooperative structure-property relationships; crystal growth of low-dimensional oxides and investigation of their electronic and magnetic properties; synthe-sis of organic/inorganic framework materials; syn-thesis of polymer nanocomposites.

Our research interests lie in the area of solid-state chemistry. The unifying theme in the research is the synthesis of novel solid-state materials and the correlation of structure with observed properties.

One research area that we focus on is the develop-ment of high-temperature solution crystal growth techniques that enable us to prepare single crystals of novel complex oxides. We have built upon our

success in the adaptation and exploration of crystal growth methods and synthesized well over 100 new compositions in the past two years. A current focus is to develop the methodology to grow larger than millimeter-sized crystals for single crystal neutron dif-fraction experiments at the Spallation Neutron Source at Oak Ridge National Laboratory. Another effort is to combine rare earth elements with early transi-tion elements, such as titanium, niobium, or tan-talum, to prepare new oxide compositions in novel structure types that are highly luminescent. We have also pioneered a new research direction, the growth of complex uranium-containing oxide crystals for fundamental and practical reasons. The synthesis of both small, high-quality crystals for structure analy-ses and large, high-quality crystals for use in oriented magnetic measurements and single crystal neutron diffraction experiments are ongoing.

A second area we are interested in is the directed supramolecular assembly of organic and inorganic modules into functional solids with pores of defined size, shape, chemical environment, and function, such as fluorescence. We are working to synthesize three types of materials: (1) those that exhibit selec-tive absorption of small molecules, (2) those that exhibit optical properties, such as fluorescence for potential applications in sensors and light emitting diodes (LEDs), and (3) those that exhibit long-range magnetic ordering. The proposed syntheses can lead to an understanding of structure-composition rela-tionships for such materials and, ultimately, may enable the prediction of the topology and/or the periodicity of crystalline lattices constructed from the molecular structures of the participating small building blocks; in other words, true crystal engi-neering at the nanoscale.

A third research area is the preparation of polymer nanocomposite materials. Specifically, we are focused on the synthesis of layered oxides, including clays and phosphonates, for their incorporation into various

polymer systems. We have developed approaches for preparing nanocomposite materials with extremely high weight loadings of the layered nanomaterials. To understand the effect of the layered materials on the overall performance of the nanocomposite, such as gas-barrier enhancement or increased phys-ical strength, we are employing diverse nano-sheets and are extensively characterizing the physical attri-butes of these composite systems.

The underlying theme in all areas under investiga-tion is the desire to understand how structure and composition affect properties, which will ultimately allow us to synthesize compounds with specific struc-tures and, consequently, specific properties.

R e p R e s e n tat i v e p u b l i c at i o n s

Roof, I.P., Smith, M.D., zur Loye, H.-C., “Hydroxide Flux Growth of K2UO4 and Na4UO5.” J. Cryst. Growth, (2010): 312, 1240–1243.

Roof, I.P., Smith, M.D., zur Loye, H.-C. “Crystal Growth of a New Series of Layered Tantalates LnKNaTaO5 (Ln = La, Pr, Nd, Sm, Gd).” Solid State Sci., (2010): 12, 759–764.

Mugavero III, S.J., Gemmill, W.R., Roof, I.P., zur Loye, H.-C. “Materials Discovery by Crystal Growth: Lanthanide Metal Containing Oxides of the Platinum Group Metals (Ru, Os, Ir, Rh, Pd, Pt) from Molten Alkali Metal Hydroxides.” J. Solid State Chem., (2009): 182, 1950–1963.

Jagau, T.-C., Roof, I.P., Smith, M.D., zur Loye, H.-C. “Crystal Growth, Structural Properties, and Photophysical Characterization of Ln4Na2K2M2O13 (M = Nb, Ta; Ln = Nd, Sm, Eu, Gd).” Inorg. Chem., (2009): 48, 8220–8226.

Roof, I.P., Jagau, T.-C, Zeier, W.G., Smith, M.D., zur Loye, H.-C. “Crystal Growth of a New Series of Complex Niobates, LnKNaNbO5 (Ln = La, Pr, Nd, Sm, Eu, Gd and Tb): Structural Properties and Photoluminescence.” Chem. Mater., (2009): 21, 1955–1961.

Barber, P., Houghton, H., Balasubramanian, S., Anguchamy, Y.K., Ploehn, H.J., zur Loye, H.-C. “New Layered Mixed-Valent Metal Phosphonates for High Dielectric-Polymer Composite Materials.” Chem. Mater., (2009): 21, 1303–1310.

Roof, I.P., Smith, M.D., Park, S., zur Loye, H.-C. “EuKNaTaO5: Crystal Growth, Structure and Photoluminescence Property.” J. Am. Chem. Soc., (2009): 131, 4202–4203.

zur Loye, H.-C., Hansen, T.J., Zhao, Q., Mugavero III, S.J., Withers, R.L., Smith, M.D. “Crystal Growth of Novel Lanthanide Containing Platinates K4[Ln6Pt2O15] (Ln = La, Pr, Nd, Sm) with a Unique Framework Structure.” Inorg. Chem., (2009): 48, 414–416.

h A n s - c o n r A D Z U r l oy e d AV I d W. R O B I N S O N pA l M e T TO p R O F e S S O Rzurloye@chem.sc.edu

i n o r g A n i c

Sc.B., 1983, Brown University; Ph.D., 1988, University of California at Berkeley; post-doctoral, Fellow 1988–1989, Northwest-ern University.

Camille and Henry dreyfus New Faculty Award, 1989; Exxon Award in Solid State Chemistry, 1994; Visiting Professor, Université de Picar-die, Jules Verne, France, 1999; Guest Profes-sor, Shandong Normal University, China, 2001; Associate Editor, Journal of Solid State Chemis-try; Editor for the Journal of the South Carolina Academy of Science; Board of Editors, Jour-nal of Alloys and Compounds; Visiting  Profes-sor at the ICMCB-CNRS-Bordeaux, France, 2003; Guest professor, Shandong Normal Uni-versity, 2001;  Visiting  professor, Sun yat-sen University, 2008; Visiting Scientist, NIMS, Tsu-kuba, japan, 2010; IpMI Henry j. Albert Award, 2009; elected to the rank of fellow of the AAAS, 2009; South Carolina Section of the ACS Out-standing Chemist 2010.

Figure 1. Optical image of the red room temperature photoluminescence in euKNaTaO5

Figure 2. Crystal image of Ba2NiUO6 with superim-posed cubic double perovskite structure

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“ The best thing about this department is the people in it. The staff are always excited to provide assistance. Professors are pas-sionate about their research and are will-ing to offer insightful suggestions toward the progression of my research. I espe-cially appreciate my advisor, who cre-ates an encouraging work environment.” —Khaleh Thomas, biochemistry

Our Ph.D. program focuses on hands-on research to prepare you to become an independent researcher in either an industrial or academic setting. Dur-ing the first year, you will spend a large part of your time taking advanced course work, but thereafter, you will spend most of your time in the lab-oratory doing cutting-edge research. You might construct molecular wires for connecting nanoscale electronics or unravel the diabetes-related glycal-ation of proteins. The importance of the research done at USC is reflected in strong funding by a variety of granting agencies.

The department typically receives $4 million annually in research grants.

In addition to developing your own research skills, you will participate in a worldwide scientific community that is advancing the frontiers of knowl-edge. You will publish papers on your work in major scientific journals. The department also encourages and supports your attendance at national and international conferences to present your work to other interested scientists. An active seminar program brings in top scientists from around the world to discuss their work with all members of the department.

You will learn a great deal about research from the thesis advisor that you choose from the faculty. However, you will also learn from advanced grad-uate students, postdocs, and visiting scientists who work with you in the same research group. These groups, typically consisting of 3–10 research-ers working on closely related projects, expose you to the skills and experi-ences of a variety of other scientists.

Communications skills are also an important part of your development. You will give presentations to your research group and your division of the department. Every spring, the department holds a poster competition for advanced students, with the finalist presenting a departmental seminar and going on to a University-wide competition. With this experience, you will approach presentations outside the University with confidence.

each year our graduate students make dozens of presentations at scientific conferences.

D e v e l o P i n g A s A s c i e n t i s t

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s e m i n A r P ro g r A m

Departmental seminars occur weekly and feature outstanding speakers from industry and other institutions. One such recent speaker was Steven Zim-merman of the University of Illinois.

Divisional seminars are offered by each of the five divisions of the department. These seminars are given by visitors from industry and academia as well as by first- and second-year graduate students delivering their required seminars.

H. Willard Davis Lectures honor a former chair of the department who retired in 1977. The 2009–2010 lecturer was Dr. Sharon Hammes-Schiffer of Penn State University.

Ronald R. Fisher Lectures in the Biochemical Sciences honor a former chair of the department who died in 1985. The 2009–2010 lecturer was Dr. JoAnne Stubbe of the Massachusetts Institute of Technology.

Guy Fleming Lipscomb Lectures in Chemistry and Biochemistry honor a former department chair and founder of Continental Chemical Company and Anchor Continental. The 2009–2010 lecturers were Dr. Rod Tweten of the University of Oklahoma and Dr. Stephen J. Lippard of the Massa-chusetts Institute of Technology.

Charles William Murtiashaw III Lectures honor a USC graduate who was a human disease researcher with Pfizer Inc. The 2009–2010 lecturer was Dennis A. Dougherty of the California Institute of Technology.

Frederick M. Weissman Lectures in Analytical Chemistry honor a 1936 graduate and distinguished neurologist. The 2009–2010 lecturer was Dr. George W. Luther of the University of Delaware’s College of Earth, Ocean, and Environment.

s o c i e t y f o r t h e A DvA n c e m e n t o f t h e c h e m i c A l s c i e n c e s

The Society for the Advancement of the Chemical Sciences is an active, grow-ing organization of graduate students in the department. The society was started in 1975 to aid members in their academic and social development and to encourage the exchange of ideas in the chemical sciences between the department’s students and the scientific community.

Each year, the society’s members select and sponsor a seminar speaker who has made outstanding contributions to chemistry and has influenced the chemical community. Past speakers have included such notables as Nobel Laureates Sir Geoffrey Wilkinson, Roald Hoffman, and William Lipscomb.

The society arranges for its speakers, and other speakers sponsored by the department, to be available to members in small group meetings and indi-vidual conferences. Members attend luncheon meetings each Friday with the departmental seminar speakers. This personal interaction with invited speakers is one of the most meaningful activities enjoyed by members.

Fun and recreation are also provided for society members. Each semester, members organize intramural teams and sponsor several parties, including a picnic each August to welcome incoming graduate students.

“ I came to USC for graduate studies because of its excellent reputation: close student-pro-fessor interaction and impressive research facilities. The environment in the Depart-ment of Chemistry and Biochemistry greatly facilitates the development of new skills as well as gaining the professional knowledge to pursue a career in academic research.” —Ágota Debreczeni, inorganic chemistry

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f i n A n c i A l s U P P o rt

t e Ac h i n g A s s i s tA n t s h i P s

You will probably receive a teaching assistantship for your first year in the Ph.D. program. These appointments normally involve supervision of under-graduate chemistry laboratories or recitation sections and require approx-imately 12 hours per week (including preparation and grading). The department provides intensive teacher training and pairs new teachers with experienced peer mentors.

Teaching assistantships carry a stipend of $22,000 for students entering in 2010. In addition, the department will pay teaching assistants’ tuition.

r e s e A r c h A s s i s tA n t s h i P s

After your first year, you will probably be supported by a research assistantship with your research director so that you can devote full time to your research. Research assistantships carry a stipend of $22,000 for students entering in 2010. In addition, the research grant will pay research assistants’ tuition. The cost of living in the metropolitan Columbia area is typically less than comparably sized cities on the East Coast, especially in regard to housing.

f e l l oW s h i P s

Each year, the University selects students to receive fellowships sponsored by federal programs, and these fellowships replace a research or teaching assis-tantship. Prospective graduate students with superior records will automat-ically be considered for these fellowships.

Prospective graduate students will also be considered automatically for depart-mental fellowships given in addition to a teaching or research assistantship. The Teague Fellowships honor Professor Peyton C. Teague, an organic chem-ist on our faculty who worked closely with the graduate program for many years. They are awarded to the most promising entering graduate students and provide supplements ranging from $1,000 to $4,000. The Murtiashaw Fellowship in Organic Chemistry honors Charles Murtiashaw III, a human disease researcher with Pfizer who received his Ph.D. degree in our depart-ment. One Murtiashaw Fellow is selected each year from applicants who indicate an interest in organic chemistry. The fellowship provides a sup-plement of $3,000. Other fellowships include the IRIX/David L. Coffen Fellowship, the Jerome D. Odom Fellowship in Chemistry, and USC Pres-idential Doctoral Fellowships.

Entering graduate students may also ask to be considered for the Summer Research Internship Program. Summer interns, called Copenhaver Schol-ars, serve as research assistants for 10 weeks and earn $5,500 for the sum-mer. The program honors James Copenhaver, a former faculty member in organic chemistry who encouraged undergraduate research.

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s t U D e n t s e rv i c e s

h o U s i n g

On-Campus Housing: A limited number of convenient University housing units are available for married graduate students. Married students have their choice of one-, two-, or three-bedroom unfurnished apartments at several locations ranging from $625 to $990 per month. For details, rates, and an application, contact the University Office of Graduate and Family Housing at 803-777-4571, e-mail safmgrd@mailbox.sc.edu, or go online to www.housing.sc.edu/famgrad.asp.

Off-Campus Housing: In general, quality rental housing is plentiful in the greater Columbia area. The average one-bedroom apartment close to cam-pus costs approximately $600 per month, while the average two-bedroom apartment costs about $800. The Off-Campus Housing Service provides many support services, including assistance in locating housing, roommates, and rooms for rent. For additional information, visit the Web site at https://offcampushousing.sc.edu.

e m P l oy m e n t o P P o rt U n i t i e s f o r s t U D e n t s ’ s P o U s e s

Many graduate student spouses find part- or full-time employment with the University. Information on University employment can be obtained by vis-iting the Web at http://hr.sc.edu/employ.html. If you have questions, you can call the Employment Office at 803-777-3821.

The South Carolina Department of Employment and Workforce oper-ates several Columbia-area job banks that list a wide variety of employ-ment opportunities. After you arrive in Columbia, visit the South Carolina Employment Service at 700 Taylor Street. The job bank office is open from 8 a.m. to 5 p.m. Monday through Friday. Their Web site is http://dew.sc.gov.

All graduate students at the University are required to have health insur-ance. The University provides health insurance at a reduced group rate.

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r e c r e At i o n i n A n D A ro U n D c o l U m B i A

The Columbia area provides a variety of activities for the outdoor enthu-siast. Water sports, including boating, water skiing, wind surfing, sailing, fishing, and swimming, can be enjoyed year round. There are several large lakes nearby, three rivers course through the city, and the ocean is less than two hours away. Metropolitan Columbia has been named one of the top 10 canoe towns in the country by Paddler Magazine. Campers and hik-ers can drive to the Smokey Mountains in about three hours. Golfers can choose from more than 20 area courses, many offering reduced student rates.

To help you take advantage of all of the outdoor opportunities, there are active University clubs for canoeing, flying, sailing, skiing, scuba diving, and other sports. Students and faculty also have available, at no charge, University athletic facilities that include handball, tennis, racquetball, and squash courts, bodybuilding and gymnastic equipment, and an Olympic-sized swimming pool. The Strom Thurmond Wellness and Fitness Center provides a world-class facility to promote healthy lifestyles and recreational activities. This facility is unequivocally the best of its type in the country on a college campus. The Department of Chemistry and Biochemistry also fields intramural teams in basketball, soccer, softball, and several other sports.

As the state capital and home of the University, Columbia is a center of cul-tural activities in South Carolina. In addition to the University’s Depart-ment of Theatre and Dance, there are several active theatre groups in the vicinity that offer exciting and varied presentations of the classics, comedy, and experimental theatre. The Koger Center for the Arts on the USC cam-pus presents nationally and internationally recognized artists and groups. It is also the home of the USC Symphony and Chamber Orchestras, the South Carolina Philharmonic, and the Columbia City Ballet. The Colo-nial Center brings in major musical acts such as Prince, Shania Twain, and Jimmy Buffett.

The Riverbanks Zoo and Garden is an exceptional experience for all ages. It is home to more than 2,000 animals that represent more than 350 species from around the world. It has been recognized as one of the 10 best zoos in the country. Each animal is seen in a living area resembling its natural habi-tat. Picnic areas and nature trails surround the zoo. The Botanical Gardens feature more than 4,200 species of native and exotic plants.

The Columbia Museum of Art, located near the campus, contains an impor-tant part of the Kress Collection of Renaissance art. McKissick Museum, on the University’s historic Horseshoe, is a recognized center for folk art research and houses several permanent collections. The State Museum, also near the campus, houses a wide array of science, technology, and history exhibits.

c o l U m B i A A n D s o U t h c A ro l i n A i n f o r m At i o n

Welcome packets containing city and state maps, historical information, and current events calendars, as well as business, school, childcare, and recreational information, can be obtained by calling the Greater Colum-bia Chamber of Commerce at 803-733-1110 or by writing the Greater Columbia Chamber of Commerce, 930 Richland Street, Columbia, SC 29201. You can also read some of the same information by visiting www.columbiachamber.com on the Web.

S.C. travel guides, including attractions, maps, and information about spe-cific regions in the state, can be obtained by calling the Department of Parks, Recreation, and Tourism (PRT) at 803-734-1700. The guides are free. Upon request, PRT will also send information about particular activ-ities of interest to you, such as hiking or the arts.

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w w w . c h e m . s c . e d u

please consult our Web site for additional information,

including updates on faculty and staff appointments,

honors, and awards; information about current

graduate students, research professors, postdoctoral

associates, and emeriti faculty; and complete lists of

past seminar speakers.

f o r f U r t h e r i n f o r m A t i o n

c o n t A c t :

Graduate Admissions CommitteeDepartment of Chemistry and Biochemistry

631 Sumter St.University of South Carolina

Columbia, SC 29208

Telephone: 803-777-2579

Toll-free: 800-868-7588

Fax: 803-777-9521

E-mail: chemgradoffice@mail.chem.sc.edu

The University of South Carolina provides equal opportunity and affirmative action in education and employment for all qualified persons regardless of race, color, religion, sex, national origin, age, disability, sexual orientation, or veteran status.

10297 University publications 10/10

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