个人简介

Education B.S., Saginaw Valley State University (1989) Ph.D., University of Michigan (1996) NIH Postdoctoral Fellow, Northwestern University (1996-2000)

研究领域

Physical inorganic and bioinorganic chemistry

We have three interrelated research areas: (1) Synthesis and spectroscopy of high-spin Fe(II) and Co(II) coordination complexes. (2) Paramagnetic resonance spectroscopy of Co(II)-substituted Zn(II) proteins. (3) X-ray absorption spectroscopy of Zn(II) proteins and their Co(II)-substituted analogs. Our main focus is in the bioinorganic chemistry of zinc, geared to the elucidation of structure/function relationships in metalloenzyme active sites to gain a deeper understanding of enzyme mechanism. Our overriding interest is in the use of Co(II) as a spectroscopic probe of metal sites in proteins. The Co(II) ion is particularly well-suited to the study of Zn biochemistry, as substitution of Co(II) for Zn(II) usually returns an enzyme that is fully functional. Unlike the colorless, non-magnetic 3d10 Zn(II) ion, Co(II) (3d7) is paramagnetic in all environments and it's complexes are highly colored. Favorable electronic properties make Co(II) complexes accessible by nearly all magnetic resonance techniques. However, the extraction of structural properties from spectroscopic observations is often hindered by the complicated electronic structure of high-spin Co(II), including the presence of substantial spin-orbit coupling in the ground state and thermally accessible excited states. To better understand the correlation between structure and spectroscopy, we are involved the preparation of an ever-growing library of Co(II) model compounds, encompassing four-, five- and six-coordination, with varying contributions from N, O and S donors (examples below). Development of these structural correlations involves characterization of both the physical and electronic structure of the metal site. We use X-ray crystallography to determine the three-dimensional structure of a complex, and UV-visible-near infrared spectroscopy to determine the ground state electronic structure. This information is necessary to understand the magnetic resonance properties of the molecule.

近期论文

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D. L. Tierney �XAS of Dinuclear Hydrolases� in Handbook of Binuclear Metallohydrolases: Structure, Function, Mechanism and Applications, G. Schenk and L. Gahan, Eds., 2013, in press. A. Mousavi, A. R. Marts, D. L. Tierney and S. Cabaniss �Geometry of Zn(II) Complexes with Dissolved Organic Matter: X-Ray Studies at Variable pH� Tox. Environ. Chem., 2013, 95, 338-44. D. L. Tierney �Jahn-Teller Dynamics in a Series of High-Symmetry Co(II) Chelates Determine Paramagnetic Relaxation Enhancements� J. Phys. Chem. A, 2012, 116, 10959-10972. K. Grubel, A. R. Marts, S. M. Greer, D. L. Tierney, C. J. Allpress, S. N. Anderson, B. J. Laughlin, R. C. Smith,A. M. Arif and L. M. Berreau �Photoinitiated Dioxygenase-Type Reactivity of Open-Shell 3d Divalent Metal Flavolonato Complexes� Eur. J. Inorg. Chem., 2012, 4750-4757. D. L. Zimbler, T. M. Park, B. A. Arivett, S. M. Greer, T. M. Woodruff, D. L. Tierney and L. A. Actis �Stress Response and Virulence of the A. Baumannii NfuA Fe-S Scaffold Protein� J. Bacter., 2012, 194, 2884-2893. H. Yang, M. Aitha, A. M. Hetrick, T. K. Richmond, D. L. Tierney and M. W. Crowder �Mechanistic and Spectroscopic Studies of Metallo-b-Lactamase NDM-1� Biochemistry, 2012, 51, 3839-3847. R. M. Breece, L. Llarrull, M. Tioni, A. J. Vila and D. L. Tierney �X-Ray Absorption Spectroscopy of Metal Site Speciation in the Metallo-b-Lactamase BcII from Bacillus cereus� J. Inorg. Biochem., 2012, 111, 182-186. M. P. Hensley, T. S. Gunasekera, J. A. Easton, T. K. Sigdel, S. A. Sugarbaker, L. Klingbeil, D. L. Tierney and M. W. Crowder �Characterization of Zn(II)-Responsive Ribosomal Proteins YkgM and L31 in E. coli� J. Inorg. Biochem., 2012, 111, 164-172. S. N. Oseback, S. W. Shim, M. Kumar, S. M. Greer, S. R. Gardner, K. M. Lemar, P. DeGregory, E. T. Papish, D. L. Tierney, M. Zeller and G. P. A. Yap "Crowded Bis-Ligand Complexes of TtzPh, Me with First Row Transition Metals Rearrange Due to Ligand Field Effects: Structural and Electronic Characterization (Ttz Ph, Me = tris(3-phenyl-5-methyl-1,2,4-triazolyl)borate)" Dalton Trans., 2012, 41, 2774-2787. M. P. Hensley, D. L. Tierney and M. W. Crowder �Zn(II) Binding to E. coli 70S Ribosomes� Biochemistry, 2011, 50, 9937-9939. D. H. Griffin, T. K. Richmond, C. Sanchez, A. J. Moller, R. M. Breece, D. L. Tierney, B. Bennett and M. W. Crowder �Structural and Kinetic Studies on Metallo-b-Lactamase IMP-1� Biochemistry, 2011, 50, 9125-9134. J. K. Angelosante, L. M. Schopp, B. J. Lewis, A. D. Vitalo, D. T. Titus, R. A. Swanson, A. N. Stanley, B. P. Abolins, M. J. Frome, L. E. Cooper, D. L. Tierney, C. Moore, A. L. Rheingold and C. J. A. Daley �Synthesis and Characterization of an Unsymmetrical Cobalt(III) Active Site Analogue of Nitrile Hydratase� J. Biol. Inorg. Chem., 2011, 16, 937-947. A. R. Marts, S. M. Greer, D. R. Whitehead, T. M. Woodruff, R. M. Breece, S. W. Shim, S. N. Oseback, E. T. Papish, F. E. Jacobsen, S. M. Cohen and D. L. Tierney �Dual Mode EPR Studies of a Kramers Ion: High-Spin Co(II) in 4-, 5- and 6-Coordination� Appl. Mag. Res., 2011, 40, 501-511. P. S. Mariano, Z. Li, Z. Liu, D. W. Cho, J. Zou, M. Gong, R. M. Breece, A. Galkin, L. Li, H. Zhao, G. D. Maestas, D. L. Tierney, O. Herzberg and D. Dunaway-Mariano �Rational Design, Synthesis and Evaluation of First Generation Inhibitors of the Giardia lamblia Fructose-1,6-biphosphate Aldolase� J. Inorg. Biochem., 2011, 105, 509-517. L. M. Berreau, T. Borowski, K. Grubel1, C. J. Allpress, J. P. Wikstrom, M. E. Germain, E. V. Rybak-Akimova and D. L. Tierney �Mechanistic Studies of the O2-dependent Aliphatic Carbon-carbon Bond Cleavage Reaction of a Nickel Enolate Complex� Inorg. Chem., 2011, 50, 1047-1057. K. Linenberger, S. Lowery Bretz, M. W. Crowder, R. McCarrick, G. A. Lorigan and D. L. Tierney �What is Fresh Meat�s True Color? A Biophysical Undergraduate Laboratory Investigating the Effects of Ligand Binding on Myoglobin Using Optical, Electron Paramagnetic Resonance and Nuclear Magnetic Resonance Spectroscopies� J. Chem. Ed., 2011, 88, 223-225. F. Xie, D. V. Zaytsev, M. Mukherjee, A. Bludin, B. Demeler, R. M. Breece, D. L. Tierney and M. Y. Ogawa �Nanometer to Millimeter-Scale Peptide-Porphyrin Materials� Biomacromolecules, 2010, 11, 2602-2609. V. A. Campos-Bermudez, J. M. Gonzalez, D. L. Tierney and A. J. Vila �Spectroscopic Signature of a Ubiquitous Metal Binding Site in the Metallo-b-Lactamase Superfamily� J. Biol. Inorg. Chem., 2010, 15, 1209-1218. E. M. Stone, E. S. Glazer, L. Chantranupong, P. Cherukuri, R. M. Breece, D. L. Tierney, S. A. Curley, B. L. Iverson and G. Georgiou �Replacing Mn2+ with Co2+ in Human Arginase I Enhances Cytotoxicity Towards L-Arginine Auxotrophic Cancer Cell Lines� ACS Chem. Biol., 2010, 5, 333-342. R. M. Breece, Z. Hu, B. Bennett, M. W. Crowder and D. L. Tierney �Motion of the Zinc Ions in Catalysis by a di-Zinc Metallo-b-Lactamase� J. Am. Chem. Soc., 2009, 131, 11642-11643.