The Three-spin Intermediate at the O-O Cleavage and Proton-pumping Junction in Heme-Cu Oxidases

Overview

Journal Science

Specialty Science

Date 2021 Sep 13

PMID 34516790

Citations 9

Authors

Anex Jose

Andrew W Schaefer

Antonio C Roveda Jr

Wesley J Transue

Sylvia K Choi

Ziqiao Ding

Robert B Gennis

Edward I Solomon

Affiliations

Soon will be listed here.

Abstract

Understanding the mechanistic coupling of molecular oxygen reduction and proton pumping for adenosine triphosphate synthesis during cellular respiration is the primary goal of research on heme-copper oxidases—the terminal complex in the membrane-bound electron transport chain. Cleavage of the oxygen-oxygen bond by the heme-copper oxidases forms the key intermediate P, which initiates proton pumping. This intermediate is now experimentally defined by variable-temperature, variable-field magnetic circular dichroism spectroscopy on a previously unobserved excited state feature associated with its heme iron(IV)-oxo center. These data provide evidence that the iron(IV)-oxo in P is magnetically coupled to both a copper(II) and a cross-linked tyrosyl radical in the active site. These results provide new insight into the oxygen-oxygen bond cleavage and proton-pumping mechanisms of heme-copper oxidases.

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