Current Research

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

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.
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.
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.
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.
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. ; 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.
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.
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.
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.
Harrop, T. C. Nickel: Models of Protein Active Sites; Scott, R. A. ; Encyclopedia of Inorganic and Bioinorganic Chemistry; Wiley & Sons: New York, 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.
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.
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.
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.
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.
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.
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.
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.