研究领域

Bioinorganic Chemistry Bioorganic Chemistry Biophysical Chemistry Chemical Biology Energy Science Environmental Chemistry Inorganic Chemistry Organometallic Chemistry Sensor Science Sustainable Chemistry Synthetic Inorganic and Bioinorganic Chemistry

Our research group has programs in three areas of bioinorganic chemistry and one in the preparation and characterization of inorganic clusters. Students can receive training in synthetic inorganic chemistry and physical characterization of molecules [X-ray crystallography, NMR (multidimensional, paramagnetic and heteronuclear such as 51V or 23Na), electrochemistry, epr and uv/vis spectroscopy, etc.] or emphasize more biologically related topics. In the latter case, students gain experience in molecular biology as well as in the physical techniques described above. Our group recently discovered a new class of metal chelating agents that have been named metallacrowns based on the structural similarity of these materials to organic crown ethers. The group is developing this new area of molecular recognition agent in numerous ways including determining stability constants for metal complexation, the ability to polymerize metallacrowns to form new materials, such as metallomesogens, and investigating the reactivity of these compounds as possible catalysts. Manganese plays an important role in the metabolism of dioxygen and its reduced forms. Two enzymes which contain multinuclear manganese assemblies at the active site are the manganese catalases and the oxygen evolving complex. We have attempted to provide a better understanding of the structure, spectral features and reactivity patterns of small molecules that may act as models for each of these categories of enzymes. An analogous project focuses on biological vanadium chemistry, a newly emerging field in the bioinorganic sphere. Vanadium has special significance in the marine environment where it is concentrated nearly a million-fold by tunicates and forms the heart of vanadium bromoperoxidase, an enzyme that performs important halogenation reactions for marine natural products. In addition, vanadium complexes may represent an effective treatment for diabetes. The group has expanded its synthetic interests into a bioorganic/bioinorganic hybrid program aimed at synthesizing small peptides that adopt controlled secondary structures into which metal ion binding sites can be engineered. These alpha-helical peptides aggregate into two, three or four helix bundles. The hydrophobic interior is modified to serve as a binding site for metals as diverse as mercury or cadmium or biologically important centers such as the Fe2S2 and Fe4S4 clusters.

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Zaleski, C.; S. Tricard; E. C. Depperman; W. Wernsdorfer; T. Mallah; M. L. Kirk; and V. L. Pecoraro, “Single-molecule magnet behavior of a pentanuclear Mn-based metallacrown complex: solid state and solution magnetic studies” Inorg. Chem., 2011, 50 (22), pp 11348–11352. Zastrow, M.L.; Peacock, A.F.A.; Stuckey, J.A.; Pecoraro, V.L. “Hydrolytic Catalysis and Structural Stabilization in a Designed Metalloprotein” Nature: Chemistry, 2012, 4, 118-123. Zampella, G.; Neupane, K.P.; DeGioia, L.; Pecoraro, V.L. “The Importance of Stereochemically Active Lone Pairs For Influencing Pb(II) and As(III) Protein Binding” Chem. Eur. J, 2012, 18, 2040-2050. Chakraborty, S.; Iranzo, O.; Zuiderweg, E.R.P.; Pecoraro, V.L. “An Experimental and Theoretical Evaluation of Multi-site Cd(II) Exchange in Designed Three-Stranded Coiled Coils” J. Amer. Chem. Soc., 2012, 134, 6191-6203. Jankolovits, J.; Lim, C.S.; Mezei, G.; Kampf, J.W.; Pecoraro, V.L. “Influencing the Size and Anion Selectivity of Dimeric Ln3+[15-Metallacrown-5] Compartments through Systematic Variation of the Host Side Chains and Central Metal” Inorg. Chem., 2012, 51, 4527-4538. Sanna, D.; Pecoraro, V.L.; Micera, G.; Garribba, E. “Application of DFT methods to the Study of Coordination Environment of VO2+ ion in V-proteins” J. Biol. Inorg. Chem. 2012, 17, 773-790. Grant, J.T.; Jankolovits, J.; Pecoraro, V.L. “Enhanced Guest Affinity and Enantioselectivity through Variation of the Gd3+[15-Metallacrown-5] Side Chain” Inorg. Chem. 2012, 51, 8034–8041. Tegoni, M.; Yu, F.; Berseloni, M.; Pecoraro, V.L. “Designing functional type 2 copper centers within alpha-helical coiled coils that have nitrite reductase activity” Proc. Nat. Acad. Sci. (USA), 2012, 109, 21234–21239. Lim, C.S.; Tegoni, M.; Kampf, J.W.; Pecoraro, V.L. “Clarifying the Mechanism of Cation Exchange in Ca(II)[15-MCCu(II)Ligand-5] Complexes” Inorg. Chem., 2012, 51, 11533–11540. Jankolovits, J.; Kampf, J.W.; Pecoraro, V.L. “Comparison of Structural Constraints on the Ln(III)[15-MC-5] Topology using Ni(II), Cu(II), or Zn(II) Ring Metals”, Polyhedron, 2013, 52, 491-499. DOI: 10.1016/j.poly.2012.08.046. Zastrow, M.; Pecoraro, V.L. “Designing functional metalloproteins: from structural to catalytic metal sites” Coord. Chem. Rev. 2013, 257, 2565-2588. Peacock, A.F.A.; Pecoraro, V.L. “Natural and Artificial Proteins Containing Cadmium”, Chapter 10 in Cadmium: From Toxicity to Essentiality, Metal Ions in Life Sciences, A. Sigel, H. Sigel, and R. K. O. Sigel (eds.), 2013, 11, 303–337. DOI: 10.1007/978-94-007-5179-8_10. Zastrow, M.; Pecoraro, V.L. “The Influence of Active Site Location on Catalytic Activity in de Novo Designed Zinc Metalloenzymes” J. Amer. Chem. Soc., 2013, 135, 5895-5903. uczkowski, M.; Zeider, B.A.; Stachura, M.; Chakraborty, S.; Hemmingsen, L.; Huffman, D.L. Pecoraro, V.L. “Probing the Coordination Environment of the Human Copper Chaperone HAH1: Characterization of Hg(II) bridged Homodimeric Species in Solution” Chem.: Eur. J., 2013, 19, 9042-9049. Yu, F.; Pecoraro, V.L. “Use of the Mechanistic Probe 2-methyl-1-phenylpropan-2-yl hydroperoxide (MPPH) to Discriminate Between the Formation of MnIVMnIV(O.) and MnIVMnV=O species” Polyhedron, accepted (special issue honoring George Christou). Jankolovits, J.; Kampf, J.W.; Pecoraro, V. L. “Isolation of Elusive Tetranuclear and Pentanuclear M(II)-Hydroximate Intermediates in the Assembly of Lanthanide [15-Metallacrown-5] Complexes--” Inorg. Chem.,2013, 52, 5063-5076. Lassalle-Kaiser, B.; Boron III, T.T.; Krewald, V.; Kern, J.; Beckwith, M.A.; Schroeder, H.; Mori, R.A.; Weng, T.-C.; Sokaras, D.; Neese, F.; Bergmann, U.; Yachandra, V.K; DeBeer, S.; Pecoraro, V.L.; Yano, J. “Experimental and Computational X-ray Emission Spectroscopy as a Direct Probe of Protonation States in Oxo-Bridged MnIV-Dimers Relevant to Redox-active Metalloproteins” Inorg. Chem. in press. Glatzel, P.; Schroeder, H.; Pushkar, Y.; Boron, T.T., III; Mukerjee, S.; Christou, G.; Pecoraro, V.L.; Messinger, J.; Yachandra, V.K.; Bergmann, U.; Yano, J. “--Electronic Structural Changes of Mn in the Oxygen-Evolving Complex of Photosystem II During the Catalytic Cycle”, Inorg. Chem., 2013, 52, 5642-5644. Krewald, V.; Lassalle-Kaiser, B.; Boron III, T.T.; Kern, J.; Beckwith, M.A.; Yachandra, V.K. Pecoraro, V.L.; Yano, J.; Neese, F.; DeBeer, S. “The Protonation States of an Oxo-Bridged MnIV-Dimer Resolved by Experimental and Computational Mn K Pre-Edge X-Ray Absorption Spectroscopy” submitted to Inorg. Chem. Deb, A; Boron, III, T.T.; Itou, M.; Sakurai, Y.; Jankolovits, J.; Mallah, T.; Pecoraro, V.L.; Penner-Hahn, J.E. “Understanding Spin Structure in Metallacrown Single-Molecule Magnets using Magnetic Compton Scattering” to be submitted to J. Phys. Chem.