Faculty |
Pavel Anzenbacher, Jr., Ph. D.
Associate Professor, Chemistry Department
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411 Physical Sciences Laboratory Building
419.372.2080
pavel@bgsu.edu
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Joined the faculty in 2000
Ph.D., Czech Academy of Sciences, Prague (1997)
M.S., Charles University at Prague (1992)
Our work is focused on synthesis of novel pigments, chromophores, photoluminescent
and electroluminescent materials as well as investigation of optical properties
of materials capable of changes in color and luminescence for various real-life
applications. More specifically we develop photonic materials and devices
in two main areas: supramolecular materials for molecular sensing and materials
that can be used in fabrication of OLEDs.
In the first area of research, we synthesize new supramolecular materials
with interesting photonic and/or conductor properties. These polymeric materials
are designed to change their photophysical or electrical properties as a
result of association with other materials and species. As a part of this
research we prepare new conjugated and/or semiconducting polymers with backbone-integrated
receptors that are known to bind and sense biologically important materials
such as anions, nucleotide phosphates and nucleotide-phosphonate based virostatics.
Additionally, we are exploring self-assembled organometallic dendrimers capable
of vectorial energy transfer, which is used to relay the information about
the presence of various analyte.
The second main research area in the group is oriented toward the design
and synthesis of new chromophores for applications in flat displays and development
of OLED materials. Here we focus on synthesis of electroluminescent coordination
polymers.
Takizawa, S.; Montes, V. A.; Anzenbacher Jr., P.: Phenylbenzimidazole-Based New Bipolar Host Materials for Efficient Phosphorescent OLEDs. Chem. Mater. 2009, in press.
Benor, A.; Takizawa, S.; Chen, P.; Perez-Bolivar, C.; Anzenbacher Jr., P.: Dramatic efficiency improvement in phosphorescent OLEDs with ultraviolet-ozone treated PEDOT:PSS. Appl. Phys. Lett. 2009, 94, in press.
Anzenbacher Jr, P.; Palacios, M. A.: Polymer nanofibre junctions of attolitre volume serve as zeptomole-scale chemical reactors. Nature Chem. 2009, 1, 80-86. DOI: 10.1038/nchem.125. This article was highlighted in The New York Times, Nature, Chemistry & Engineering News, ChemWorld, MIT Technology Review, Spektrumdirekt, C2W, and others.
Montes, V. A.; Zyryanov, G. V.; Danilov, E.; Agarwal N.; Palacios, M.; Anzenbacher Jr., P.: Ultrafast Energy Transfer in Oligofluorene-Aluminum Bis(8-hydroxyquinoline)acetylacetone Coordination Polymers. J. Am. Chem. Soc. 2009, 131, 1787-1795; DOI: 10.1021/ja805175w.
Anzenbacher Jr., P.; Montes, V. A.; Takizawa S.: High-purity white light from a simple single dopant host-guest white organic light-emitting diode architecture. Appl. Phys. Lett. 2008, 93, 163302. DOI: 10.1063/1.3005424.
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George Bullerjahn, Ph. D.
Professor, Department of Biological Sciences
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Ph.D., University of Virginia, Biology, 1984
A.B., Dartmouth College, Biology, 1977
Our work is currently
focused on the regulation of nutrient-stress-inducible genes
in cyanobacteria. We have identified genes and gene products
inducible under nutrient (N, S, P) limitation and stationary
phase conditions, and this work has aided in the development
of whole-cell biosensors detecting the bioavailability of nutrients
in environmental samples. Secondly, we examine the composition
and dynamics of cyanobacterial communities in aquatic systems.
Third, we are examining the structural requirements for productive
electron transport in photosynthesis by studying the protein-protein
interactions occurring between the copper protein plastocyanin
and its reaction partners (Photosystem I and cytochrome f).
Hulsker, R., M. Baranova, G.S. Bullerjahn and M. Ubbink. 2008. Dynamics in the transient Prochlorothrix hollandica plastocyanin-cytochrome f complex. J. Amer. Chem. Soc. 130: 1985-1991.
Piunova, P., D. Berger, D.C. Neckers, G.S. Bullerjahn, R.M McKay and A.V. Fedorov. 2008. Biocidal performance of acrylated glyphosate in a model photopolymerizable coating formulation. Photochem. Photobiol. Sci. 7: 1565-1569.
Ilikchyan, I.N., R.M.L. McKay, J.P. Zehr, S.T. Dyhrman and G.S. Bullerjahn. 2009. Detection and expression of the phosphonate transporter gene phnD in marine and freshwater picocyanobacteria. Environ. Microbiol. 11: 1314-1324.
Sharma, A.K., K. Sommerfeld, G.S. Bullerjahn, A. Matteson, S.W. Wilhelm, J. Jezbera, U. Brandt, W.F. Doolittle and M.W. Hahn. 2009. Widespread distribution of actinorhodopsin genes in freshwater habitats and among diverse actinobacterial lineages. ISME J. 3: 726-737.
Hassler, C.S., S.M. Havens, G.S. Bullerjahn, R.M.L. McKay and M.R. Twiss. 2009. An evaluation of iron bioavailability and speciation in western Lake Superior with the use of combined physical, chemical, and biological assessment. Limnol. Oceanogr. 54: 987-1001.
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John R. Cable, Ph. D.
Associate Professor, Chemistry Department
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510 Physical Sciences Laboratory Building
419.372.8439
cable@bgsu.edu
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Joined the faculty in 1989
Ph.D., Cornell University (1986)
M.S., University of California – Riverside (1980)
B.S., University of California – Riverside (1979)
Our research is focused on determining the structures of conformationally flexible molecules and the effect that solvation and hydrogen bonding has on these structures. To carry out these investigations we make use of vibrationally resolved electronic spectroscopy in the ultracold environment of a supersonic jet expansion. Electronic spectroscopy permits structural information to be obtained on both ground and excited electronic states through analysis of the resolved vibrational structure that appears under these conditions.
We are currently investigating a number of phenyl substituted amines and amides. These types of molecules form strong hydrogen bonds with a variety of partners, including water, and have the potential to act as both donors and acceptors. By studying hydrogen bonded clusters at high spectral resolution it is possible to determine the mode of binding between the solute and solvent as well as to characterize the structural perturbations that arise from the strong interaction.
“Conformations of Isolated Model Dipeptides in Supersonic Jet Expansions”, Cable, J. R.; Sharp, J. C.; Miller, N. J. Phys. Chem A, submitted.
“The infrared spectroscopy of H-bonded bridges stretched across the cis-amide group: II. Ammonia and mixed ammonia/water bridges”, Fedorov, A. V.; Cable, J. R.; Carney, J. R.; Zwier, T. S. J. Phys. Chem A2001, 105, 8162.
“The infrared spectroscopy of H-bonded bridges stretched across the cis-amide group: I. Water bridges”, Carney, J. R.; Fedorov, A. V.; Cable, J. R.; Zwier, T. S. J. Phys. Chem A2001, 105, 3487.
“Spectroscopy of hydrogen-bonded formanilide clusters in a supersonic jet: Solvation of a model trans amide”, Fedorov, A. V.; Cable, J. R. J. Phys. Chem. A2000, 104, 4943.
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Felix N. Castellano, Ph. D.
Professor, Chemistry Department
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509 Physical Sciences Laboratory Building
419.372.7513
castell@bgsu.edu
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Joined the faculty in 1998
Ph.D., The Johns Hopkins University (1996)
M.A., The Johns Hopkins University (1993)
B.A., Clark University (1991)
Since
the end of 2002, a significant focus of our "basic" research program involves
the investigation of supra-nanosecond and ultrafast photophysical processes
in platinum(II) polyimine chromophores bearing a variety of carbon-based ligands.
These strongly-coupled metal-organic systems are of fundamental interest
and may serve in a variety of applications including optical power limiting,
solar energy conversion, and photocatalysis. We are currently developing new
synthetic methodologies for the preparation of novel platinum structures.
Our interest in the design and photophysical characterization of metal-organic
chromophores facilitates our fruitful collaboration with the Ziessel group
(Strasbourg, France), where we continue to investigate the photophysical properties
of p-conjugated metal-organic complexes. On the more "applied" side my group
continues to develop novel inorganic compounds with pendant photochromic
quenchers and their associated polymeric materials for nondestructive luminescence
readout, potentially useful for binary optical data storage in both read-only
and read-write-erase formats. In these systems, the luminescence response
from the metal complex indirectly signals the photochromic state of the quencher,
circumventing direct interrogation of the photochemically active species
(nondestructive readout). Collaborators at the NMRC in Cork, Ireland have
used our molecules in near-field spectroscopy in an effort to produce ultrahigh
density binary memory systems with information bits of sub-micron size. A
recent extension of our work in this area demonstrated the concept of optical
data storage using luminescence lifetime modulation/readout. In 2005 we started
to explore the solid-state vapochromism (color changes in response to VOCs)
inherent in some of the platinum(II) MLCT complexes described above. We recently
illustrated the concept of low power photon upconversion using simple photochemical
concepts, highlighted as "News of the Week" in C & EN (August 8, 2005).
This year we also established a new program in solar energy conversion, focusing
largely on the design and synthesis of new Ru(II) inorganic chromophores
for dye sensitized solar cells.
Influence of Temperature on Low-Power Upconversion in Rubbery Polymers. Singh-Rachford, T.N.; Lott, J.; Weder, C.; Castellano, F.N. J. Am. Chem. Soc. 2009, 131, 12007-12014.
Nonlinear Photochemistry Squared: Quartic Light-Power Dependence Realized in Photon Upconversion. Singh-Rachford, T.N.; Castellano, F.N. J. Phys. Chem. A 2009, 113, 9266-9269.
Evolution of the Triplet Excited State in PtII Perylenediimides. Danilov, E.O.; Rachford, A.A. Goeb, S.; Castellano, F.N. J. Phys. Chem. A 2009, 113, 5763-5768.
Solvent-induced Configuration Mixing and Triplet Excited State Inversion: Insights from Transient Absorption and Transient DC Photoconductivity Measurements. She, C.; Rachford, A.A.; Wang, X.; Goeb, S.; El-Ballouli, A.O.; Castellano, F.N.; Hupp, J.T. Phys. Chem. Chem. Phys. 2009, 11, 8586-8591.
[Pt(mesBIAN)(tda)]: A Near-Infrared Emitter and Singlet Oxygen Sensitizer. Rachford, A.A.; Hua, F.; Adams, C.J.; Castellano, F.N. Dalton Trans. 2009, 3950-3954.
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Ksenija D. Glusac, Ph. D.
Assistant Professor, Chemistry Department
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211 Physical Sciences Laboratory Building
419.372.3229
kglusac@bgsu.edu
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Joined the faculty in 2006
Ph.D., University of Florida, 2003
B.A., Belgrade University, Yugoslavia, 1999
I am interested in a study of coupled proton and electron motion in
hydrogen-bonded D/A systems. Electron transfer (ET) mediated by hydrogen
bonds (H-bonds) is essential to the function of redox proteins in many biological
processes, particularly photosynthesis and respiration. Apart from providing
a medium for ET, H-bonds in ET proteins have other functions. For example,
ET in biological systems is often accompanied with a proton transfer along
a certain H-bonded surface with the goal to achieve catalytic activity or
drive proton pumps. Even though some insight into the general ET and proton
transfer pathways in proteins has been obtained, a full understanding of
the coupled effects that proton and electron motion have on each other is
yet to be achieved.
Apart from its significance in biological
systems, the understanding of ET through H-bonded systems will be valuable
for the development of future devices. For example, the design of an efficient
solar cell requires a donor/acceptor (D/A) system with a long-lived charge
separated state. To achieve this goal, a specific H-bonded D/A system can
be envisioned in which the initial charge separation induces the proton motion
along the H-bonded surface and makes the charge recombination highly inefficient.
In other words, the H-bonded surface could act as a unidirectional gate for
the electron flow in D/A systems.
In order to obtain information on both
electron and proton dynamics, we use two techniques: VIS pump-VIS probe and
VIS pump-IR probe spectroscopy. After excitation using a VIS pump beam, the
ET processes is studied by probing the transient species in the VIS spectral
region, while the proton motion is observed by probing the vibrational modes
of the transient species in the IR region. The model compounds are designed
with the goal to elucidate the mechanism of coupled electron and proton motion
both along H-bonded D/A systems and along H-bonded D/water/A systems.
G. Li, K. Parimal, S. Vyas, C. M. Hadad, A. H. Flood, K. D. Glusac, "Pinpointing the Extent of Electronic Delocalization in the Re(I)-to-Tetrazine Charge Separated Excited State Using Time-Resolved Infrared Spectroscopy", J. Am. Chem. Soc, 2009, 131, 11656-11657.
G. Li, K. D. Glusac, "The Role of Adenine in Fast Excited-State Deactivation of FAD: a Femtosecond Mid-IR Transient Absorption Study", J. Phys. Chem. B, 2009, 113, 9059-9061.
P. Kucheryavy, G. Li, S. Vyas, C. M. Hadad, K. D. Glusac, "Electronic Properties of 4-Substituted Naphthalimides", J. Phys. Chem. A, 2009, 113, 6453-6461.
G. Li, V. Sichula, K. D. Glusac, "Role of Adenine in Thymine-dimer Repair by Reduced Flavine-Adenine Dinucleotide", J. Phys. Chem. B, 2008, 112, 10758-10764.
G. Li, K. D. Glusac, "Light-Triggered Proton and Electron Transfer in Flavin Cofactors", J. Phys. Chem. A, 2008, 112(20); 4573-4583.
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Thomas H. Kinstle, Ph. D.
Distinguished Teaching Professor, Chemistry Department
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409 Physical Sciences Laboratory Building
419.372.8678
tkinstl@bgsu.edu
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Joined the faculty in 1971
Ph.D., University of Illinois (1963)
A.B., Bowling Green State University (1958)
Our program in natural products/bio-organic chemistry is concerned with the synthesis and biological evaluation analogs of plant derived phenolic compounds known to be inhibitors of tumor formation. Ellagic acid, present in various fruits and vegetables, particularly strawberries, is a planar biaryl polyphenol. Epigallocatechin gallate (EGCG) is a flavanoid polyphenol found in high concentration in brewed green tea. Analogs, chosen on the basis of computerized molecular modeling studies, are being synthesized.
A long- term program in the chemistry of strained bicyclic ring compounds is proceeding in the areas of synthesis, mechanism and spectroscopy. We are particularly interested in partially fluorinated bicyclo[2.1.0] pentanes. Flash vacuum pyrolysis techniques have allowed us to synthesize several novel non-natural molecules.
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Neocles B. Leontis, Ph. D.
Professor, Chemistry Department
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212 Physical Sciences Laboratory Building
419.372.8663/2753
leontis@bgsu.edu
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Joined the faculty in 1987
Ph.D., Yale University, New Haven (1986)
A.M., Harvard University (1980)
B.S., Ohio State University (1977)
Nucleic Acids (DNA and RNA) play diverse roles in living organisms. Not only do they encode genetic information but they actively participate in its readout from transcription to translation, including splicing, editing, and regulation at each stage. Single-stranded DNA and RNA molecules fold into complex 3-dimensional structures to carry out these roles. We are investigating the logic of the 3D architecture of these molecules using an integrated biophysical, biochemical, and bioinformatic approach. These complex structures are able to specifically bind other molecules, including potential drug molecules. Photosensitizers that can specifically bind DNA or RNA molecules have tremendous potential for overcoming present limitations of photodynamic therapy, by directing damage to molecules specific to the target cells. We are investigating the binding of potent photosensitizers to complex nucleic acids using biophysical and biochemical methods. See also: Geometric Classification of Non-Canonical Basepairing.
The RNA structure alignment ontology.
Brown JW, Birmingham A, Griffiths PE, Jossinet F, Kachouri-Lafond R, Knight R, Lang BF, Leontis N, Steger G, Stombaugh J, Westhof E.
RNA. 2009 Sep;15(9):1623-31. Epub 2009 Jul 21.
Frequency and isostericity of RNA base pairs.
Stombaugh J, Zirbel CL, Westhof E, Leontis NB.
Nucleic Acids Res. 2009 Apr;37(7):2294-312. Epub 2009 Feb 24.
Classification and energetics of the base-phosphate interactions in RNA.
Zirbel CL, Sponer JE, Sponer J, Stombaugh J, Leontis NB.
Nucleic Acids Res. 2009 Aug;37(15):4898-918. Epub 2009 Jun 14.
Annotation of tertiary interactions in RNA structures reveals variations and correlations.
Xin Y, Laing C, Leontis NB, Schlick T.
RNA. 2008 Dec;14(12):2465-77. Epub 2008 Oct 28.
TokenRNA: a new type of sequence-specific, label-free fluorescent biosensor for folded RNA molecules.
Afonin KA, Danilov EO, Novikova IV, Leontis NB.
Chembiochem. 2008 Aug 11;9(12):1902-5.
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H. Peter Lu, Ph. D.
Ohio Eminent Scholar and Professor, Chemistry Department
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Joined the faculty in 2006
Ph.D., Columbia University (1991)
M.S., Peking University, P.R. China (1984)
Our research is focused on the use of single molecule techniques to understand molecular dynamic processes and the effects of the local environment on these processes. We have been developing and applying time-resolved, nanoscale site-specific, single molecule methods that are an effective alternative to conventional methods, providing information under conditions most applicable to the natural processes underlying the area of research interest. Single-molecule approaches are useful and unique in studying heterogeneous and complex systems because the inhomogeneity can be identified and/or removed by studying one molecule at a time. Single molecules and molecular complexes can be observed as they traverse a wide range of energy states in real-time and the effect of this ever changing "system configuration" on chemical/biological reactions and other dynamical processes can be mapped.
Our current research work has been focused on (1) conformational dynamics and reaction in proteins and protein complexes under physiological conditions, and our long-term goal is to study single-molecule protein conformational dynamics and reactions in living cells; and (2) inhomogeneous interfacial chemical and biological reaction dynamics in solar energy conversion, bioremediation, and environmental systems, focusing on fundamental understanding of the controlling physical and chemical properties, such as, Franck-Condon coupling and barrier, vibrational and solvent relaxation energetics, molecular distributions, redox states identification, and molecular motions.
Yufan He, Xiaohua Zeng, Saptarshi Mukherjee, Suneth Rajapaksha, Samuel Kaplan, H. Peter Lu, "Revealing Linear Aggregates of Light Harvesting Antenna Proteins in Photosynthetic Membranes," Langmuir (2009) ASAP electronically published.
Yuanmin Wang, Xuefei Wang, and H. Peter Lu, "Probing single-molecule interfacial geminate electron-cation recombination dynamics." J. Am. Chem. Soc. 131, 9020-9025 (2009).
H. Peter Lu, "Single-Molecule Protein Interaction Conformational Dynamics," Current Pharmaceutical Biotechnology, 10, 522-531 (2009).
H. Peter Lu, "Combined Single-Molecule Electrical Recording and Single-Molecule Spectroscopy Studies of Ion Channel Conformational Dynamics," an invited book chapter in Methods in Nano Cell Biology, edited by Bhanu Jena, ELSEVIER (2009).
Yuanmin Wang, Xuefei Wang, Sujit Kumar Ghosh, H. Peter Lu, "Probing single-molecule interfacial electron transfer dynamics of porphyrin on TiO2 nanoparticles," J. Am. Chem. Soc. 131, 1479-1487 (2009).
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Douglas C. Neckers, Ph. D.
McMaster Distinguished Research Professor
Chemistry Department
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Joined the faculty in 1973
Ph.D., University of Kansas (1963)
A.B., Hope College (1960)
Retired in 2009
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Michael Y. Ogawa, Ph. D.
Professor and Chair, Chemistry Department
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Joined the faculty in 1991
Ph.D., Northwestern University (1988)
M.S., Northwestern University (1983)
B.A., Oberlin College, Ohio (1980)
Our group is developing a new class of hybrid inorganic/biological materials possessing novel photochemical properties.
In one project we are using the principles of “metalloprotein design” to prepare a new class of miniature metalloproteins containing luminescent Cu(I) centers. The photophysical properties of these systems have been found to mimic many features found in natural photosynthetic reaction centers and can be used to develop new routes towards solar energy conversion. A related project uses supramolecular coordination chemistry to direct the assembly of novel peptide structures. We have found that such metal-mediated peptide assemblies possess a diverse range of morphologies ranging from nanometer-scale hollow spheres to nano-cylinders, making them possible candidates for drug delivery vehicles. Thus, a central theme of our laboratory is to combine inorganic coordination chemistry/photochemistry with protein design in order to prepare new types of hybrid materials which possess potentially useful chemical properties.
Metal-mediated Peptide Assembly:
Use of Metal Coordination to Change the Oligomerization State of an
α-helical Coiled-coil, Tsurkan, M. V. and Ogawa, M Y., Inorg. Chem. 2007, 46, 6849-6851.
Electron-Transfer Functionality into Synthetic Metalloproteins from the
Bottom-up, (Inorganic Forum Article), Hong, J, Kharenko, O. A. and
Ogawa, M. Y., Inorg. Chem. 2006, 45, 9974-9984.
Electron-Transfer Functionality of Synthetic Coiled-coil
Metalloproteins, Ogawa, M. Y., Fan, J., Fedorova, A., Hong, J.
Kharenko, O. A., Kornilova, A. Y., Lasey, R. C., Xie, F. J. Braz. Chem. Soc. 2006, 17, 1516-1521.
A Miniature Cu(I) Metalloprotein Undergoes Collisional
Electron-transfer in the Inverted Marcus Region, J. Hong, O. A.
Kharenko, A. K. Petros, B. R. Gibney, and M. Y. Ogawa, Angew. Chem. Int. Ed. 2006, 37, 6137-6140.
Cu(I) Luminescence from the Tetranuclear Cu4S4 Cofactor of a Synthetic
4-Helix Bundle O. A. Kharenko, D. C. Kennedy, B. Demeler, M. J.
Maroney, and M. Y. Ogawa, J. Am.
Chem. Soc. 2005, 127,
7678.
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Massimo Olivucci, Ph. D.
Research Professor
Director, Laboratory for Computational Photochemistry
Chemistry Department
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302 Physical Sciences Laboratory Building
419.372.7606
molivuc@bgsu.edu
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Joined the faculty in 2006
Ph.D., M.S., University of Bologna, Italy (1988)
We use conventional and novel computational tools to investigate the reactivity of organic and biological molecules in their electronically excited states. One major target of our work is the mapping of the photon-induced "force field" which sets an equilibrium molecular structure into motion in realistic molecular environments (e.g. in solution or in a protein cavity). This force field can be calculated and represented in terms of photochemical reaction paths: ie. paths that start on an excited state potential energy surface and end on the ground state energy surface. Photochemical reaction paths comprise mechanistic elements that are not involved in the description of thermal reactions. These correspond to real crossings of different potential energy surfaces. For photochemical reactions prompted by direct irradiation these crossings often correspond to conical intersections that are regarded as the photochemical analogues of transition states. Given the central role of photochemical reaction paths and conical intersections (as well as singlet/triplet surface crossings) in the investigation of the excited state reactivity of proteins (e.g. biological photoreceptors) or solvated molecules (e.g. dyes in solution), we also develop computational strategies based on a combination of ab-initio quantum chemical methods and molecular mechanics methods that allow to study the effects of light irradiation on complex molecular systems.
Pär Söderhjelm, Charlotte Husberg, Angela Strambi, Massimo Olivucci, Ulf Ryde, Protein Influence on the Electronic Spectra Modeled by Multipoles and Polarizabilities, 2009 J. Chem. Theo. Comp. 5, 649-658.
Rivado-Casas, L.; Sampedro, D.; Campos, P. J.; Fusi, S.; Zanirato, V.; Olivucci, M. J Org Chem 2009, 74, 4666-4674.
Andruniów, T.; Olivucci, M. Journal of Chemical Theory and Computation 2009, 55-90.
IN PRESS Pistolesi, S.; Sinicropi, A.; Pogni, R.; Basosi, R.; Ferré, N.; Olivucci, M. J Phys Chem B 2009.
IN PRESS Adalgisa Sinicropi, Caterina Bernini, Riccardo Basosi and Massimo Olivucci, A novel biomimetic photochemical switch at work: design of a photomodulable peptide, Photochem. Photobiol. Sci., 2009, DOI: 10.1039/b906271h.
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Michael A. J. Rodgers, Ph. D.
Professor and Eminent Scholar, Chemistry Department
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Joined the faculty in 1988
Ph.D., University of Manchester, UK (1966)
Retired in 2009
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Deanne L. Snavely, Ph. D.
Professor, Chemistry Department
Interim Vice Provost for Research
and Dean of the Graduate College
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Joined the faculty in 1985
Ph.D., Physical Chemistry, Yale University (1983)
B.S., Chemistry, Ohio State University (1977)
The research group of Professor Deanne Snavely has developed a radical chain
polymerization method that uses the absorption of visible light by vibrational
overtone states to initiate polymerization reactions. Vibrational overtone
absorptions of the fifth and third CH stretching vibrational transitions
are used to activate a radical precursor capable of initiating polymerization.
This new photopolymerization process does not use typical excited electronic
state photochemistry that governs most photopolymerization processes. Vibrational
overtone photochemistry is initiated through excited vibrational states of
the ground electronic state, so initiators employed in thermal polymerization
processes are used. This distinction between excited electronic state and
excited vibrational state means that the photon energies needed for initiation
can be lower that those needed in electronic state photopolymerization. Furthermore
it is possible to vary the rate of the polymerization reaction by tuning
the excitation laser wavelength to different vibrational overtone absorption
features or wavelengths where no absorption occurs. Vibrational overtone
polymerization offers the possibility of long wavelength photoinitiation,
laser selective photo-degeneration and wavelength selectivity.
Future research in this area will capitalize on and investigate the unique aspects of vibrational overtone polymerization.
- Long wavelength initiation and monomers for
medical applications Vibrational overtone polymerization will be employed
in micro-fabrication processes or in medical application where small quantities
of polymer are required in precise locations. Often these processes require
wavelength selectivity and long wavelength initiation so as to penetrate
into flesh or not damage surrounding components.
- Average molecular mass and thermal characteristics
of vibrational overtone polymers Given the novel polymerization process,
a study of the average molecular mass and thermal characteristics should
be undertaken. The results of these studies will be compared to thermal polymerization.
- Spatial control for imaging or surface structure
Starting with a suitable monomer, vibrational overtone techniques will
be used to photo-crosslink a polymer film. Initial studies will involve a
spin-coated film with timed irradiation in order to create cross-linked patterns
on the film. The wavelength selectivity of this process will be investigated.
- Laser selective degradation of polymer films
Laser vibrational overtone irradiation will be used to degrade polymer
films. Polymers with photoreactive groups will be irradiated on their various
vibrational overtone absorption features. The surface will then be imaged
to observe the photo damage. This process will be initiated by long wavelength
light and it is anticipated that it will have the selectivity of vibrational
overtone polymerization.
“Vibrational overtone initiated photopolymerization of acrylonitrile”, H.Gu
and D.L. Snavely, J. Appl. Poly. Sci., 90(2), 565-571 (2003).
“Vibrational Overtone Activated Photo-Cross-Linking of Ethylene Glycol Dimethacrylate
Using Benzoyl Peroxide and 2,2'-(Azobis)isobutyronitrile as Initiators”,
Gu, H.; Snavely, D. L.; Macromolecule, 36(9); 3160-3165 (2003).
“Vibrational overtone spectroscopy of ethyleneglycol diacrylate and ethyleneglycol
dimethacrylate, monomer and polymer”, Timofey Gerasimov and D. L. Snavely, Appl. Spect., 56, 2, (2002).
“Vibrational Photopolymerization of methyl methacrylate and quantitative
analysis of polymerization results”, T.G. Gerasimov and D.L. Snavely, Macromolecule,
35(15) 5796-5800 (2002).
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Alexander N. Tarnovsky, Ph. D.
Assistant Professor, Chemistry Department
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309 Physical Sciences Laboratory Building
419.372.3865
atarnov@bgsu.edu
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Joined the faculty in 2005
Ph.D., S. I. Vavilov State Optical Inst, St. Petersburg, Russia (1993)
M.S., Institute of Fine Optics, St. Petersburg, Russia (1986)
The focus of our research interests is two-fold:
- Developing a molecular-level understanding of the dynamics of chemical reactions occurring in solution, and;
- Gaining a deep, detailed insight into the dynamics and
mechanisms of ultrafast (femto- and picosecond) photoinduced processes.
In our research, we use state-of-the art experimental methods of ultrafast, time-resolved spectroscopy.
Visualizing Overdamped Wavepacket Motion: Excited-State Isomerization of Pseudocyanine in Viscous Solvents, Dietzek, B.; Tarnovsky, A.N.; Yartsev, A. Chem. Phys. 2009, 357, 54-62.
Structure of the Photochemical Reaction Path Populated via Promotion of CF2I2 into Its First Excited State, El-Khoury, P. Z.; Tarnovsky, A. N.; Shapiro, I.; Ryazantsev, M. N.; Olivucci, M. J. Phys Chem. A, 2009, ASAP Article.
Photochemistry of Iodoform in Methanol: The Formation and Fate of the Iso-CHI2-I Photoproduct, El-Khoury, P. Z.; Kwok, W. M.; Guan, X.; Ma, C.; Phillips, D. L.; Tarnovsky, A. N., ChemPhysChem. 2009, 10, 1895-1900.
Photoaffinity Labeling via Nitrenium Ion Chemistry: Protonation of the Nitrene Derived from 4-Amino-3-nitrophenyl Azide to Afford Reactive Nitrenium Ion Pairs, Voskresenska, V.; Wilson, R. M.; Panov, M.; Tarnovsky, A. N.; Krause, J. A.; Vyas, S.; Winter, A. H.; Hadad, C. M., J. Am. Chem. Soc. 2009, 131, 11535-11547.
The Effect of Dielectric friction on the Rate of Charge Separation in Type II ZnSe/CdS Semiconductor Nanorods, Hewa-Kasakarage, N. N.; El-Khoury, P. Z.; Schmall, N.; Kirsanova, M.; Nemchinov, A.; Tarnovsky, A. N.; Bezryadin, A.; Zamkov, M. App. Phys. Lett. 2009, 94, 133113.
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Bruno Ullrich, Ph. D.
Associate Professor, Department of Physics and Astronomy
- Info
- Biographical Facts
- Specialties
Diploma, Technical High School of St. Polten, Austria (1981)
Diploma, University of Vienna (1985)
Ph.D., University of Vienna (1988)
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R. Marshall Wilson, Ph. D.
Research Professor, Chemistry Department
- Info
- Biographical Facts
- Research Interests
- Selected Publications
OFFICE:
PHONE:
EMAIL: |
310 Physical Sciences Laboratory Building
419.372.2035
rmw@bgsu.edu
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Joined the faculty in 2005
Ph.D., Massachusetts Institute of Technology (1965)
B.S., The Pennsylvania State University (1961)
Our
research interests are directed towards photochemical application of lasers,
primarily argon ion lasers, and fall into two broad categories: the laser
synthesis of new materials and the development of reagents for the photochemical
manipulation of biological systems. These include:
- The
use of CW laser plasmas to prepare carbon bowls, Bucky Bowls and the study
of the properties of these bowl-shaped “aromatic” hydrocarbons.
- The development of new reagents for the photochemical cross-linking of nucleic acids, primarily RNA, with proteins.
- The development of new reagents for the photochemical cleavage of nucleic acids, primarily RNA.
- The
development of the aforementioned two techniques to study the interactions
between nucleic acids and proteins using mass spectrometry to obtain detailed
structural information about the nature of these interactions
“The
Vocabulary of Organic Chemistry”, 2nd Edition, Wiley-Interscience, 2005,
with Milton Orchin, Allan Pinhas, and Roger Macomber.
“Photoaffinity
Labeling with 8-Azidoadenosine and Its Derivatives: The Chemistry of Closed
and Open Adenosine Diazaquinodimethanes”, Biochemistry, 2005, 44,
11241-11253, with Dmitrii Polshakov, Saroj Rai, Eric T. Mack, Martin Vogel,
Jeanette Krause, Gotard Burdzinski, and Matthew S. Platz.
“DNA Photocleavage and Biological Activity of a Pyrene Dihydrodioxin”, Bioorganic and Medicinal Chemistry Letters, 2005, 15, 2173-2176, with Eric T. Mack, Dagne Birzniece, Darren Veach, and William Coyle.
“Thermal and Photochemistry of a Pyrene Dihydrodioxin (PDHD) and Its Radical Cation: A Photoactivated Masking Group for ortho-Quinones”, Journal of the American Chemical Society, 2004, 126, 15324, with Eric T. Mack, A. Björn Carle, and J. T.-M. Liang, W. Coyle.
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Zhaohui Xu, Ph. D.
Assistant Professor, Department of Biological Sciences
- Info
- Research Interests
- Selected Publications
OFFICE:
PHONE:
EMAIL:
WEBSITE: |
538A Life Science Building
419.372.4645
zxu@bgu.edu
Visit |
Microorganisms represent the major portion of biomass on Earth with
enormous diversity in morphology, genetics, and metabolism, which implies huge application potentials. We are interested in
using genetic, biochemical, and photochemical approaches to develop microbial systems that can be applied to environmental
processes, such as remediation of hazardous substances, development of detection or monitoring systems, and production of
high value products from agricultural or industrial by-products or wastes. Currently, we are focusing on the following projects:
1. Genetic engineering of the surface layer (S-layer) protein RsaA of Caulobacter crescentus for heavy metal retrieval. Caulobacter crescentus is a harmless dimorphic bacterium widely found in aquatic environments. In common with many other prokaryotic organisms, Caulobacter cells are coated with an orderly structured S-layer, which is composed of identical subunits of protein or glycoprotein. Because of their external location and crystalline arrangement, S-layer proteins become ideal carriers to display foreign peptides on the surface of a host cell, allowing us to build remediation bioreactors with heavy metal removal capacity or to fabricate nano-scale constructs for photodegradation of organic pollutants.
2. Site-directed mutagenesis of bacterial sensory rhodopsin for wanted optical properties. In Anabaena (Nostoc) sp. PCC7120, the light sensory rhodopsin ASR is responsible for sensing green light and activating a cascade of light-sensitive reactions in the cell body. In this project, we aim to generate ASR mutants that can absorb light at different wavelengths. The application of the results can be foreseen in a variety of aspects, such as development of molecular light switches in nanotechnology and light-induced gene expression in biotechnology. This project is in collaboration with Dr. Massimo Olivucci at the BGSU Department of Chemistry.
3. Genetic modification of cellulases to improve the enzyme catalytic efficiency, thermostability, and substrate specificity or
stereoselectivity. Due to global energy crisis, developing renewable forms of energy like hydro, solar and bio-energy has become increasingly
important. Energy from biomass has a promising future because it ensures self-reliance through the use of local resources with simple
technologies and less production hazards. This project aims to utilize genetic tools to facilitate the hydrolysis of cellulose, which becomes
useful as a food and energy source once it is broken down into soluble cellobiose (β-1,4 glucose dimer) and glucose.
Patel J, Zhang Q, McKay RML, Vincent R, Xu Z. Genetic engineering of Caulobacter crescentus for removal of cadmium from water. Applied Biochemistry and Biotechnology. DOI 10.1007/s12010-009-8540-0. Online first. 2009.
Zhang Q, Sun M, Xu Z, Yu Z. Cloning and characterization of pBMB9741, a native plasmid of Bacillus thuringiensis subsp. kurstaki strain YBT-1520. Current Microbiology. 55: 302-307. 2007.
Dutton RJ, Xu Z, Gober JW. Linking structural assembly to gene expression: a novel mechanism for regulating the activity of a sigma-54 transcription factor. Molecular Microbiology. 58 (3), 743-757. 2005.
Xu Z, Yao B, Sun M, Yu Z. Protection of mice infected with Plasmodium berghei by Bacillus thuringiensis crystal proteins. Parasitology Research, 92(1):53-57. 2004.
Xu Z, Mulchandani A, Chen W. Detection of benzene, toluene, ethyl benzene and xylenes (BTEX) using toluene dioxygenase-peroxidase coupling reactions. Biotechnology Progress. 19: 1812-1815. 2003.
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Weidong Yang, Ph. D.
Assistant Professor, Department of Biological Sciences
- Info
- Research Interests
- Selected Publications
My research focuses on three major projects: nucleocytoplasmic trafficking mechanism,
nuclear envelope disassembly and assembly mechanisms and application of quantum dots in biological systems. Methodologies and
techniques in my lab include single molecule methods, biotechnology, advanced imaging methods and nanotechnology. The following
are the brief introduction for each project.
In eukaryotic cells, nuclear pore complexes mediate bidirectional transport of proteins, RNAs, and
ribonucleoprotein complexes across the double-membrane nuclear envelope. Dysfunction of transport or mutation of nuclear porins
can result in numerous human diseases including leukemia, cancers, and primary biliary cirrhosis. However, the transport mechanism
is still poorly understood though numerous models have been postulated. Single molecule methods we developed have been proven to
be a powerful way to elucidate the problems. My primary focus is to continue exploring the transport mechanism.
During mitosis, a single nucleus gives rise to two nuclei that are identical to the parent nucleus. Mitosis consists of a continuous
sequence of events that must be carried out once and only once. Two such important events are the disassembly of the nuclear
envelope (also known as nuclear envelope breakdown) during the first stages of mitosis, and its accurate reassembly during the last
stages of mitosis. These mechanisms have been described by various models but are still controversial. I expect our novel techniques
to shed light on these problems.
Highly photostable fluorescent bio-probes can make a revolutionary progress for drug-delivery study and biomedical imaging. Quantum
dots are such promising candidates which have many advantages over organic dyes people used. The quantum dots attached to
specific drugs can be microinjected into living cell and small animals. Then the cyto-localization of quantum dots can be studied by
combining fluorescence microscopy and electron microscopy methods.
Ma J. and Yang W. (2009) Single-Molecule Snapshots of Three-Dimensional Distribution of Transient Interactions in the Nuclear Pore. Proc. Natl. Acad. Sci. USA, in revision.
Sun C., Yang W., Tu L and Musser M. S. (2008) Single Molecule Measurement of Importin alpha/Cargo Complex Dissociation at the Nuclear Pore, Proc. Natl. Acad. Sci. USA, 105, 8613-8618.
Yang W., and Musser M. S. (2006) Nuclear transport time and efficiency are dependent on importin β concentrations. Journal of Cell Biology, 174, 951-961.
Yang W., and Musser M. S. (2006) Visualizing single molecules transiting through nuclear pore complexes using narrow-field epifluorescence microscopy. Methods, 39, 316-328.
Yang W., Gelles J. and Musser M. S. (2004) Imaging of single-molecule translocation through nuclear pore complexes. Proc. Natl. Acad. Sci. USA, 101, 12887-12892.
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Mikhail Zamkov
Assistant Professor, Department of Physics and Astronomy
- Info
- Research Interests
- Selected Publications
OFFICE:
PHONE:
EMAIL:
WEBSITE: |
103 Physical Sciences Laboratory Building
419.372.0264
zamkovm@bgsu.edu
Visit |
Experimental work in our group addresses four major areas: (1) synthesis and characterization of novel nanoscale materials, (2) elucidation of their fundamental optoelectronic properties, (3) design and demonstration of functional nanoscale devices and integrated nanosystems, and (4) exploration of the interface/communication between biological systems and nanoscale devices. This research by is highly interdisciplinary, involving concepts and techniques from biology, chemistry, physics and the engineering sciences to achieve our goals.
Hewa-Kasakarage, N. N; El-Khoury, P.Z.; Tarnovsky, A. N.; Kirsanova, M.; Nemchinov, A.; Nemitz, I; Zamkov, M. Ultrafast carrier dynamics in type II ZnSe/CdS/ZnSe nano-barbells. Submitted (ACS nano).
Acharya, K.P.; Alabi, T. R.; Schmall, N; Hewa-Kasakarage, N. N; Kirsanova, M.; Nemchinov, A.; Khon, E.; Zamkov, M., Linker-free modification of TiO2 nanorods with PbSe nanocrystals. Accepted (J. Phys. Chem C)
Kirsanova, M.; Nemchinov, A.; Hewa-Kasakarage, N. N.; Schmall, N.; Zamkov, M. Synthesis of ZnSe/CdS/ZnSe nano-barbells showing photoinduced charge separation. Chem. Mater. 2009, 21, 4305-4309.
Hewa-Kasakarage, N. N.; El-Khoury, P.Z.; Schmall, N.; Kirsanova, M.; Nemchinov, A.; Tarnovsky, A. N.; Bezryadin, A.; Zamkov, M., The effect of dielectric friction on the rate of charge separation in type II ZnSe/CdS semiconductor nanorods. App. Phys. Lett. 2009, 94, 133113.
Hewa-Kasakarage, N. N.; Gurusinghe, P. G.; Zamkov, M.: Blue-shifted emission in CdTe/ZnSe core/shell nanocrystals. J. Phys. Chem. C 2009, 113, 4362.
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