Trinuclear copper biocatalytic center forms an active site of thiocyanate dehydrogenase

Tamara V. Tikhonova, Dimitry Y. Sorokin, Wilfred R. Hagen, Maria G. Khrenova, Gerard Muyzer, Tatiana V. Rakitina, Ivan G. Shabalin, Anton A. Trofimov, Stanislav I. Tsallagov, Vladimir O. Popov*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

11 Citations (Scopus)
16 Downloads (Pure)

Abstract

Biocatalytic copper centers are generally involved in the activation and reduction of dioxygen, with only few exceptions known. Here we report the discovery and characterization of a previously undescribed copper center that forms the active site of a copper-containing enzyme thiocyanate dehydrogenase (suggested EC 1.8.2.7) that was purified from the haloalkaliphilic sulfur-oxidizing bacterium of the genus Thioalkalivibrio ubiquitous in saline alkaline soda lakes. The copper cluster is formed by three copper ions located at the corners of a near-isosceles triangle and facilitates a direct thiocyanate conversion into cyanate, elemental sulfur, and two reducing equivalents without involvement of molecular oxygen. A molecular mechanism of catalysis is suggested based on high-resolution three-dimensional structures, electron paramagnetic resonance (EPR) spectroscopy, quantum mechanics/molecular mechanics (QM/MM) simulations, kinetic studies, and the results of site-directed mutagenesis.

Original languageEnglish
Pages (from-to)5280-5290
JournalProceedings of the National Academy of Sciences of the United States of America
Volume117
Issue number10
DOIs
Publication statusPublished - 2020

Bibliographical note

Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care
Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public.

Keywords

  • Copper centers
  • Crystal structure
  • EPR
  • Molecular mechanism
  • Thiocyanate dehydrogenase

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