Professor Education Education: Postdoctoral - MIT, 2005-2007 Ph.D. - University of California, Santa Cruz, 2004 B.S. - Saint Mary's College of California, 1998 Research Research Areas: Inorganic Chemistry Biological Chemistry Environmental/Atmospheric Chemistry Research Interests: The research in the Harrop group focuses on aspects in the area of bioinorganic chemistry. These interests include the rational design and synthesis of structural and functional models of metalloenzyme active sites involved in small molecule activation, especially the superoxide detoxifying enzymes like superoxide reductase (SOR, a non-heme iron enzyme) and the nickel containing superoxide dismutase (Ni-SOD). The goal is to design and develop synthetic routes for ligand sets that structurally mimic the spatial disposition and donor strength (imidazole-N and cysteine-S) observed at the active site of these enzymes. We intend to perform and understand the reactivity of the model systems with superoxide and other ROS species in order to gain insight on the mechanism of superoxide detoxification. Additionally, the lab aims to systematically construct organic molecules with applications in environmental remediation and sensing of toxic heavy metal ions like arsenic (As3+) and lead (Pb2+). The aim of this project is to construct ligand frames utilizing metal specific donor groups that will form supramolecular coordination complexes with these particular toxic ions. Synthetic tweeking of the receptor molecules with fluorescent reporter groups will then allow us to detect the presence of these ions in an aqueous environment. Collectively, the proposed research fuses together many areas of chemistry providing multidisciplinary projects that should be of broad interest to students from diverse backgrounds. Selected Publications Selected Publications: 2018 Ezeh, V. C., & Harrop, T. C. (2013). Synthesis and Properties of Arsenic(III)-Reactive Coumarin-Appended Benzothiazolines: A New Approach for Inorganic Arsenic Detection. INORGANIC CHEMISTRY, 52(5), 2323-2334. doi:10.1021/ic301730z Ezeh, V. C., & Harrop, T. C. (2009). Role of the Zn1 and Zn2 Sites in Metallo-beta-lactamase L1. Unknown Journal, 21, 350-363. Retrieved from http://www.datatrace.com/e-chemtracts/ Cheatum, W. H., & Harrop, T. C. (2008). Reactions of a Copper(II) Superoxo Complex Lead to C-H and O-H Substrate Oxygenation: Modeling Copper-Monooxygenase C-H Hydroxylation. Reaction of a Copper-Dioxygen Complex With Nitrogen Monoxide (•NO) Leads to a Copper(II)-Peroxynitrite Species. Unknown Journal, 20, 362-370. Retrieved from http://www.datatrace.com/e-chemtracts/ Gale, E. M., & Harrop, T. C. (2008). Raman-Assisted Crystallography Reveals End-On Peroxide Intermediates in a Nonheme Iron Enzyme. Unknown Journal, 20, 117-124. Retrieved from http://www.datatrace.com/e-chemtracts/ Harrop, T. C. (n.d.). Nickel: Models of Protein Active Sites. Encyclopedia of Inorganic and Bioinorganic Chemistry/Wiley. Harrop, T. C. (2014, July 20). Iron- and Cobalt-Mediated Transformations of NOx Species. In 41st International Conference on Coordination Chemistry (ICCC-41). Singapore. Harrop, T. C. (2015, December 15). Iron- and Cobalt-Mediated Reactions of NOx Species. In International Congress of Pacific Basin Societies 2015. Honolulu, HI. Harrop, T. C., & Mascharak, P. K. (n.d.). Co-Containing Proteins. Encyclopedia of Metalloproteins/Springer. 2017 Truong, P. T. ; Gale, E. M. ; Dzul, S. P. ; Stemmler, T. L. ; Harrop, T. C. Steric Enforcement about One Thiolate Donor Leads to New Oxidation Chemistry in a NiSOD Model Complex. Inorganic Chemistry 2017, 56, 7761 - 7780. Steiner, R. A. ; Dzul, S. P. ; Stemmler, T. L. ; Harrop, T. C. Synthesis and Speciation-Dependent Properties of a Multimetallic Model Complex of NiSOD That Exhibits Unique Hydrogen-Bonding. Inorganic Chemistry 2017, 56, 2849 - 2862. 2016 Walter, M. R. ; Dzul, S. P. ; Rodrigues, A. V. ; Stemmler, T. L. ; Telser, J. ; Conradie, J. ; Ghosh, A. ; Harrop, T. C. Synthesis of Co II -NO – Complexes and Their Reactivity as a Source of Nitroxyl. Journal of the American Chemical Society 2016, 138, 12459–12471. 2015 Rhine, M. A. ; Sanders, B. C. ; Patra, A. K. ; Harrop, T. C. Overview and New Insights into the Thiol Reactivity of Coordinated NO in {MNO} 6/7/8 (M = Fe, Co) Complexes. Inorganic Chemistry 2015, 54, 9351 - 9366. Long, G. J. ; Grandjean, F. ; Harrop, T. C. ; Petroccia, H. M. ; Papaefthymiou, G. C. Combined Mössbauer Spectral and Density Functional Study of an Eight-Coordinate Iron(II) Complex. Inorganic Chemistry 2015, 54, 8415 - 8422. Broering, E. P. ; Dillon, S. ; Gale, E. M. ; Steiner, R. A. ; Telser, J. ; Brunold, T. C. ; Harrop, T. C. Accessing Ni(III)-Thiolate Versus Ni(II)-Thiyl Bonding in a Family of Ni–N2S 2 Synthetic Models of NiSOD. Inorganic Chemistry 2015, 54, 3815 - 3828. Conradie, J. ; Patra, A. K. ; Harrop, T. C. ; Ghosh, A. Square-Antiprismatic Eight-Coordinate Complexes of Divalent First-Row Transition Metal Cations: A Density Functional Theory Exploration of the Electronic–Structural Landscape. Inorganic Chemistry 2015, 54, 1375 - 1383. Harrop, T. C. New Insights on {FeNO}n (n=7, 8) Systems as Enzyme Models and HNO Donors. Advances in Inorganic Chemistry 2015, 67, 243 - 263. 2014 Sanders, B. C. ; Hassan, S. M. ; Harrop, T. C. NO 2 – Activation and Reduction to NO by a Nonheme Fe(NO 2 ) 2 Complex. Journal of the American Chemical Society 2014, 136, 10230 - 10233. Rhine, M. A. ; Rodrigues, A. V. ; Urbauer, R. J. Bieber; Urbauer, J. L. ; Stemmler, T. L. ; Harrop, T. C. Proton-Induced Reactivity of NO – from a {CoNO} 8 Complex. Journal of the American Chemical Society 2014, 136, 12560-12563. Sanders, B. C. ; Rhine, M. A. ; Harrop, T. C. Properties of {FeNO}8 and {CoNO}9 Metal Nitrosyls in Relation to Nitroxyl Coordination Chemistry. Structure and Bonding 2014, 160, 57-88. 2013 Ezeh, V. C. ; Harrop, T. C. Synthesis and Properties of Arsenic(III)-Reactive Coumarin-Appended Benzothiazolines: A New Approach for Inorganic Arsenic Detection. Inorganic Chemistry 2013, 52, 2323-2334. Sanders, B. C. ; Patra, A. K. ; Harrop, T. C. Synthesis, Properties, and Reactivity of a Series of Non-Heme {FeNO}7/8 Complexes: Implications for Fe-Nitroxyl Coordination. Journal of Inorganic Biochemistry 2013, 118, 115-127. Broering, E. P. ; Truong, P. T. ; Gale, E. M. ; Harrop, T. C. Synthetic Analogues of Nickel Superoxide Dismutase: A New Role for Nickel in Biology. Biochemistry 2013, 52, 4-18. 2012 Ezeh, V. C. ; Harrop, T. C. A Sensitive and Selective Fluorescence Sensor for Detection of Arsenic(III) in Organic Media. Inorganic Chemistry 2012, 51, 1213-1215. Harrop, T. C. Nickel: Models of Protein Active Sites; Scott, R. A. ; Encyclopedia of Inorganic and Bioinorganic Chemistry; Wiley & Sons: New York, 2012. Patra, A. K. ; Dube, K. S. ; Sanders, B. C. ; Papaefthymiou, G. C. ; Conradie, J. ; Ghosh, A. ; Harrop, T. C. A Thermally Stable {FeNO}8 Complex: Properties and Biological Reactivity of Reduced MNO Systems. Chemical Science 2012, 3, 364-369. 2011 Dube, K. S. ; Harrop, T. C. Structure and Properties of an Eight-Coordinate Mn(II) Complex that Demonstrates a High Water Relaxivity. Dalton Transactions 2011, 40, 7496-7498. Gale, E. M. ; Cowart, D. M. ; Scott, R. A. ; Harrop, T. C. Dipeptide Based Models of Nickel Superoxide Dismutase: Solvent Effects Highlight a Critical Role to Ni-S Bonding and Active Site Stabilization. Inorganic Chemistry 2011, 50, 10460-10471. Gale, E. M. ; Simmonett, A. C. ; Telser, J. ; Schaefer, H. F. ; Harrop, T. C. Toward Functional Ni-SOD Biomimetics: Achieving a Structural/Electronic Correlation with Redox Dynamics. Inorganic Chemistry 2011, 50, 9216-9218. 2010 Gale, E. M. ; Narendrapurapu, B. S. ; Simmonett, A. C. ; Schaefer, H. F. ; Harrop, T. C. Exploring the Effects of H-Bonding in Synthetic Analogues of Nickel Superoxide Dismutase (Ni-SOD): Experimental and Theoretical Implications for Protection of the Ni-SCys Bond. Inorg. Chem. 2010, 49, 7080-7096. Patra, A. K. ; Dube, K. S. ; Papaefthymiou, G. C. ; Conradie, J. ; Ghosh, A. ; Harrop, T. C. Stable Eight-Coordinate Iron(III/II) Complexes. Inorg. Chem. (Washington, DC, U. S.) 2010, 49, 2032-2034. Ezeh, V. C. ; Patra, A. K. ; Harrop, T. C. Four-Coordinate AsIII-N,S Complexes: Synthesis, Structure, Properties, and Biological Relevance. Inorg. Chem. 2010, 49, 2586-2588. 2009 Gale, E. M. ; Patra, A. K. ; Harrop, T. C. Versatile Methodology Toward NiN2S2 Complexes as Nickel Superoxide Dismutase Models: Structure and Proton Affinity. Inorg. Chem. 2009, 48, 5620-5622. 2008 Harrop, T. C. ; Tonzetich, Z. J. ; Reisner, E. ; Lippard, S. J. Reactions of Synthetic [2Fe-2S] and [4Fe-4S] Clusters with Nitric Oxide and Nitrosothiols. J. Am. Chem. Soc. 2008, 130, 15602-15610. 2007 Conradie, J. ; Quarless, Duncan A., J. ; Hsu, H. - F. ; Harrop, T. C. ; Lippard, S. J. ; Koch, S. A. ; Ghosh, A. Electronic Structure and FeNO Conformation of Nonheme Iron-Thiolate-NO Complexes: An Experimental and DFT Study. J. Am. Chem. Soc. 2007, 129, 10446-10456. Harrop, T. C. ; Song, D. ; Lippard, S. J. Reactivity pathways for nitric oxide and nitrosonium with iron complexes in biologically relevant sulfur coordination spheres. J. Inorg. Biochem. 2007, 101, 1730-1738. 2006 Harrop, T. C. ; Olmstead, M. M. ; Mascharak, P. K. Synthetic Analogues of the Active Site of the A-Cluster of Acetyl Coenzyme A Synthase/CO Dehydrogenase: Syntheses, Structures, and Reactions with CO. Inorg. Chem. 2006, 45, 3424-3436. Harrop, T. C. ; Song, D. ; Lippard, S. J. Interaction of Nitric Oxide with Tetrathiolato Iron(II) Complexes: Relevance to the Reaction Pathways of Iron Nitrosyls in Sulfur-Rich Biological Coordination Environments. J. Am. Chem. Soc. 2006, 128, 3528-3529. Harrop, T. C. ; Mascharak, P. K. Model complexes of Ni-containing enzymes. In Concepts and Models in Bioinorganic Chemistry; Concepts and Models in Bioinorganic Chemistry; Wiley-VCH: Weinheim, Germany, 2006; pp. 309-329. 2005 Harrop, T. C. ; Mascharak, P. K. Structural and spectroscopic models of the A-cluster of acetyl coenzyme A synthase/carbon monoxide dehydrogenase: Nature's Monsanto acetic acid catalyst. Coord. Chem. Rev. 2005, 249, 3007-3024. Harrop, T. C. ; Olmstead, M. M. ; Mascharak, P. K. Modeling the Active Site of Nitrile Hydratase: Synthetic Strategies to Ensure Simultaneous Coordination of Carboxamido-N and Thiolato-S to Fe(III) Centers. Inorg. Chem. 2005, 44, 9527-9533. Harrop, T. C. ; Olmstead, M. M. ; Mascharak, P. K. Unusual Role of Solvents in the Syntheses of {Fe-NO}6,7 Nitrosyls Derived from a Ligand with Carboxamido Nitrogen and Thiolato Sulfur Donors. Inorg. Chem. 2005, 44, 6918-6920. 2004 Harrop, T. C. ; Olmstead, M. M. ; Mascharak, P. K. Structural Models of the Bimetallic Subunit at the A-Cluster of Acetyl Coenzyme A Synthase/CO Dehydrogenase: Binuclear Sulfur-Bridged Ni-Cu and Ni-Ni Complexes and Their Reactions with CO. J. Am. Chem. Soc. 2004, 126, 14714-14715. Harrop, T. C. ; Mascharak, P. K. Fe(III) and Co(III) Centers with Carboxamido Nitrogen and Modified Sulfur Coordination: Lessons Learned from Nitrile Hydratase. Acc. Chem. Res. 2004, 37, 253-260. Harrop, T. C. ; Olmstead, M. M. ; Mascharak, P. K. Binding of CO to structural models of the bimetallic subunit at the A-cluster of acetyl coenzyme A synthase/CO dehydrogenase. Chem. Commun. (Cambridge, U. K.) 2004, 1744-1745. 2003 Harrop, T. C. ; Tyler, L. A. ; Olmstead, M. M. ; Mascharak, P. K. Change in the spin state of an FeIII center upon one N-to-O switch in the coordination of a 2,6-pyridinedicarboxamido unit: The effect of methyl thioether and methyl ether appendages at the ligand periphery. Eur. J. Inorg. Chem. 2003, 475-481. Harrop, T. C. ; Olmstead, M. M. ; Mascharak, P. K. Dioxygen activation by a dinuclear nickel thiolate complex: structural characterization of the ligand oxidized product. Chem. Commun. (Cambridge, U. K.) 2003, 410-411. Harrop, T. C. ; Rodriguez, K. ; Mascharak, P. K. Convenient one-pot synthesis of N,N'-bis(2-mercaptophenyl)pyridine-2,6-dicarboxamide and N-2-mercaptophenyl-2'-pyridinecarboxamide without protection of the Thiol Group(s). Synth. Commun. 2003, 33, 1943-1949. 2002 Harrop, T. C. ; Olmstead, M. M. ; Mascharak, P. K. Novel folding of N,N'-naphthalenebis(o-mercaptobenzamide) in nickel(II) complexes: monomeric and trimeric species with unexpected butterfly' and slant chair' structure. Inorg. Chim. Acta 2002, 338, 189-195.
