The Molybdenum Cofactor and Pyranopterin Mo Enzyme Catalysis

The Molybdenum Cofactor and Pyranopterin Mo Enzyme Catalysis

The Molybdenum Cofactor and Pyranopterin Mo Enzyme Catalysis (#76)

Martin Kirk ¹

The University of New Mexico, Albuquerque, NM, United States

Pyranopterin molybdenum enzymes possess a unique Mo-bound pyranopterin dithiolene (Mo-MPT = Moco) cofactor.¹These critical enzymes are essential to human health and life processes, catalyzing important chemical transformations in the metabolic pathways of sulfur, nitrogen, and carbon compounds.² New work from our laboratories has contributed to a greater understanding of DMSO reductase family enzyme catalysis,³ new types of molybdenum enzyme catalyzed chemical transformations that extend beyond simple oxygen atom transfer reactivity,⁴ and new roles for the pyranopterin dithiolene component of the Mo cofactor (Moco) in catalysis.^5-7 Here, we will highlight our synthetic, structural, spectroscopic, computational, and molecular biology approaches to solving some of the most important problems in this exciting field.

1. Probst C., Yang J., Krausz J., Hercher T.W., Richers C.P., Spatzal T., Khadanand KC, Giles L.J., Rees D.C., Mendel R.R., Kirk M.L., Kruse T., Nature Chemistry, 2021, 13, 758-765.
2. Ingersol L.J., Kirk M.L., in Comprehensive Coordination Chemistry III, eds. E. C. Constable, G. Parkin and L. Que Jr, Elsevier, Oxford, 2021, Ch. 8.31, pp. 790-811.
3. Yang, J., Mintmier, B., KC, K., Metzger, M.; Radhakrishnan, M., McGarry, J., Wilcoxen, J., Basu, P.; Kirk , M.L., 2024. Inorganic Chemistry, 63, 29, 13191-13196.
4. Struwe, M., Yang, J., Kolanji, K., Mengell, J., Scheidig, A., Clement, B., Kirk, M. L., 2024. Inorganic Chemistry, 63, 41, 19063–19073.
5. Gates C., Varnum H., Getty C., Loui N., Chen J., Kirk M.L., Yang J., Nieter Burgmayer S.J., Inorg. Chem., 2022, 61, 13728-13742.
6. Burgmayer S.J.N., Kirk M.L., in Metallocofactors that Activate Small Molecules: With Focus on Bioinorganic Chemistry, ed. M. W. Ribbe, Springer International Publishing, Cham, 2019, vol. 179, pp. 101-151.
7. Burgmayer, S., Kirk, M.L., Advancing our Understanding of Pyranopterin-Dithiolene Contributions to Moco Enzyme Catalysis, Molecules, 2023 28, 22. 7456.

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Authors contributing to this presentation.

Kirk, M

Martin L. Kirk is Distinguished University Professor of Chemistry and Chemical Biology at The University of New Mexico. His research program focuses on (1) spectroscopic, synthetic, biochemical, and computational studies of pyranopterin molybdenum enzymes and models, (2) detailed magnetic, spectroscopic, and theoretical studies of spin containing molecular systems in the context of molecular electronics, and (3) optical generation of multiple spin qubits for quantum information science (QIS) applications. He was a National Science Foundation Postdoctoral Fellow (1990-1993, Stanford University) with E. I. Solomon, completed his Ph.D. in 1990 at The University of North Carolina at Chapel Hill with W. E. Hatfield, and obtained his B.S. in 1985 at West Virginia University performing undergraduate research with Naresh Dalal. He was guest Editor (with Prof. D. A. Shultz) for Molecular Spintronics: a web themed issue of Chemical Communications and an Editor of Molybdenum and Tungsten Enzymes; a three volume Metallobiology Series sponsored by the Royal Society of Chemistry. Prof. Kirk has served on the Editorial Board of Inorganic Chemistry, was a prior ACS Inorganic Division Chair of the Bioinorganic Subdivision, and a Chair of the Gordon Research Conference on Molybdenum and Tungsten Enzymes. He was a former Chair of UNM’s Department of Chemistry and Chemical Biology and Adjunct Professor of Chemistry at New Mexico Institute of Mining and Technology. Prof. Kirk is currently a member of UNM’s Center for High Technology Materials, Center for Computational Chemistry, and Center for Quantum Information and Control.

The Molybdenum Cofactor and Pyranopterin Mo Enzyme Catalysis (#76)

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