PMID: 8917498Nov 12, 1996

Mössbauer and electron paramagnetic resonance studies of chloroperoxidase following mechanism-based inactivation with allylbenzene

Proceedings of the National Academy of Sciences of the United States of America
P DebrunnerLowell P. Hager

Abstract

We have used Mössbauer and electron paramagnetic resonance (EPR) spectroscopy to study a heme-N-alkylated derivative of chloroperoxidase (CPO) prepared by mechanism-based inactivation with allylbenzene and hydrogen peroxide. The freshly prepared inactivated enzyme ("green CPO") displayed a nearly pure low-spin ferric EPR signal with g = 1.94, 2.15, 2.31. The Mössbauer spectrum of the same species recorded at 4.2 K showed magnetic hyperfine splittings, which could be simulated in terms of a spin Hamiltonian with a complete set of hyperfine parameters in the slow spin fluctuation limit. The EPR spectrum of green CPO was simulated using a three-term crystal field model including g-strain. The best-fit parameters implied a very strong octahedral field in which the three 2T2 levels of the (3d)5 configuration in green CPO were lowest in energy, followed by a quartet. In native CPO, the 6A1 states follow the 2T2 ground state doublet. The alkene-mediated inactivation of CPO is spontaneously reversible. Warming of a sample of green CPO to 22 degrees C for increasing times before freezing revealed slow conversion of the novel EPR species to two further spin S = 1/2 ferric species. One of these species displayed g = 1.82, 2.25, 2.60 indis...Continue Reading

References

Sep 23, 1975·Biochemistry·R ChiangLowell P. Hager
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Jan 1, 1987·Archives of Biochemistry and Biophysics·H B DunfordM Pickard
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May 31, 1996·The Journal of Organic Chemistry·Frederick J. Lakner, Lowell P. Hager

Citations

Jul 26, 2016·Frontiers in Pharmacology·Kelath Murali ManojAvanthika Venkatachalam
Feb 11, 2003·The Journal of Biological Chemistry·Xianwen YiLowell P. Hager
Mar 11, 2010·The Journal of Biological Chemistry·Lowell P. Hager
Dec 22, 2005·Drug Metabolism and Disposition : the Biological Fate of Chemicals·Anna L Blobaum

Related Concepts

Second Right Posterolateral Artery
Allyl Compounds
Benzene Derivatives
Chloride Peroxidase
Hyphomycetes
Enzyme Inhibitors
Oxydol
Porphyrins
Spectroscopy, Mossbauer

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