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Issue 46, 2020

Nature of the copper-nitrosyl intermediates of copper nitrite reductases during catalysis

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Abstract

The design and synthesis of copper complexes that can reduce nitrite to NO has attracted considerable interest. They have been guided by the structural information on the catalytic Cu centre of the widespread enzymes Cu nitrite reductases but the chemically novel side-on binding of NO observed in all crystallographic studies of these enzymes has been questioned in terms of its functional relevance. We show conversion of NO2 to NO in the crystal maintained at 170 K and present ‘molecular movies’ defining events during enzyme turnover including the formation of side-on Cu-NO intermediate. DFT modelling suggests that both true {CuNO}11 and formal {CuNO}10 states may occur as side-on forms in an enzymatic active site with the stability of the {CuNO}10 side-on form governed by the protonation state of the histidine ligands. Formation of a copper-nitrosyl intermediate thus needs to be accommodated in future design templates for functional synthetic Cu-NiR complexes.

Graphical abstract: Nature of the copper-nitrosyl intermediates of copper nitrite reductases during catalysis

Supplementary files

Article information


Submitted
31 Aug 2020
Accepted
19 Oct 2020
First published
20 Oct 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 12485-12492
Article type
Edge Article

Nature of the copper-nitrosyl intermediates of copper nitrite reductases during catalysis

M. A. Hough, J. Conradie, R. W. Strange, S. V. Antonyuk, R. R. Eady, A. Ghosh and S. S. Hasnain, Chem. Sci., 2020, 11, 12485 DOI: 10.1039/D0SC04797J

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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