Intramolecular electron transfer versus substrate oxidation in lactoperoxidase: investigation of radical intermediates by stopped-flow absorption spectrophotometry and (9-285 GHz) electron paramagnetic resonance spectroscopy

Biochemistry
Alistair J FieldingA Ivancich

Abstract

We have combined the information obtained from rapid-scan electronic absorption spectrophotometry and multifrequency (9-295 GHz) electron paramagnetic resonance (EPR) spectroscopy to unequivocally determine the electronic nature of the intermediates in milk lactoperoxidase as a function of pH and to monitor their reactivity with organic substrates selected by their different accessibilities to the heme site. The aim was to address the question of the putative catalytic role of the protein-based radicals. This experimental approach allowed us to discriminate between the protein-based radical intermediates and [Fe(IV)=O] species, as well as to directly detect the oxidation products by EPR. The advantageous resolution of the g anisotropy of the Tyr (*) EPR spectrum at high fields showed that the tyrosine of the [Fe(IV)=O Tyr (*)] intermediate has an electropositive and pH-dependent microenvironment [g(x) value of 2.0077(0) at pH >or= 8.0 and 2.0066(2) at 4.0 <or= pH <or= 7.5] possibly related to the radical stability and function. Two types of organic molecules (small aromatic vs bulkier substrates) allowed us to distinguish different mechanisms for substrate oxidation. [Fe(IV)=O Por (*+)] is the oxidizing species of benzohydroxam...Continue Reading

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Citations

Feb 11, 2014·Journal of Agricultural and Food Chemistry·Silvia H LibardiDaniel R Cardoso
Mar 25, 2014·Archives of Biochemistry and Biophysics·Jörg FlemmigJürgen Arnhold
Oct 7, 2009·Proceedings of the National Academy of Sciences of the United States of America·Andrew T SmithAnabella Ivancich
Mar 18, 2009·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Ben WisemanPeter C Loewen
Sep 14, 2010·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Marcela AyalaRafael Vazquez-Duhalt
Nov 13, 2015·Expert Opinion on Therapeutic Targets·Jörg FlemmigJürgen Arnhold
Feb 22, 2013·Journal of Inorganic Biochemistry·Abraham Vidal-LimónRafael Vazquez-Duhalt
Apr 21, 2012·Archives of Biochemistry and Biophysics·Mercedes Alfonso-PrietoCarme Rovira
Jun 27, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Rinky D ParakraElizabeth C Ledgerwood
Jul 14, 2018·Chemistry, an Asian Journal·Ryo AdachiTeruyuki Komatsu
Dec 6, 2019·Chemical Science·Ishita PalSomdatta Ghosh Dey
Jul 3, 2021·International Journal of Molecular Sciences·Amrita RaiDietmar J Manstein
Dec 21, 2010·Journal of the American Chemical Society·Arnab MukherjeeJustine P Roth
Mar 9, 2011·Journal of the American Chemical Society·M Alfonso-PrietoJ Blumberger

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