Resonance Raman spectroscopy of oxoiron(IV) porphyrin pi-cation radical and oxoiron(IV) hemes in peroxidase intermediates

Journal of Inorganic Biochemistry
James TernerCharles M Hosten

Abstract

The catalytic cycle intermediates of heme peroxidases, known as compounds I and II, have been of long standing interest as models for intermediates of heme proteins, such as the terminal oxidases and cytochrome P450 enzymes, and for non-heme iron enzymes as well. Reports of resonance Raman signals for compound I intermediates of the oxo-iron(IV) porphyrin pi-cation radical type have been sometimes contradictory due to complications arising from photolability, causing compound I signals to appear similar to those of compound II or other forms. However, studies of synthetic systems indicated that protein based compound I intermediates of the oxoiron(IV) porphyrin pi-cation radical type should exhibit vibrational signatures that are different from the non-radical forms. The compound I intermediates of horseradish peroxidase (HRP), and chloroperoxidase (CPO) from Caldariomyces fumago do in fact exhibit unique and characteristic vibrational spectra. The nature of the putative oxoiron(IV) bond in peroxidase intermediates has been under discussion in the recent literature, with suggestions that the Fe(IV)O unit might be better described as Fe(IV)-OH. The generally low Fe(IV)O stretching frequencies observed for proteins have been diff...Continue Reading

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Citations

Aug 10, 2006·Proceedings of the National Academy of Sciences of the United States of America·Kari L StoneMichael T Green
Feb 15, 2007·Analytical Chemistry·Kevin R WardJames Terner
Apr 28, 2007·Journal of the American Chemical Society·Piotr J MakJames R Kincaid
Oct 7, 2009·Proceedings of the National Academy of Sciences of the United States of America·Ariel Lewis-BallesterSyun-Ru Yeh
Apr 20, 2011·The Journal of Biological Chemistry·Changyuan Lu, Syun-Ru Yeh
Feb 15, 2008·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Tatyana SpolitakDavid P Ballou
Dec 17, 2015·Proceedings of the National Academy of Sciences of the United States of America·Piotr J MakJames R Kincaid
Jan 21, 2016·Proceedings of the National Academy of Sciences of the United States of America·Georges ChreifiThomas L Poulos
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Nov 30, 2016·Nature Communications·Hanna KwonEmma L Raven
May 31, 2014·Journal of the American Chemical Society·Timothy H YoscaMichael T Green
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Oct 31, 2008·Chemistry & Biodiversity·Hans-Petter HerslethK Kristoffer Andersson
Jun 15, 2007·The Journal of Biological Chemistry·Hans-Petter HerslethK Kristoffer Andersson

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