Evidence for H-bonding interactions to the μ-η2:η2-peroxide of oxy-tyrosinase that activate its coupled binuclear copper site

Ioannis Kipouros; Agnieszka Stańczak; Martin Culka; Erik Andris; Timothy R. Machonkin; Lubomír Rulíšek; Edward I. Solomon

doi:10.1039/D2CC00750A

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Evidence for H-bonding interactions to the μ-η²:η²-peroxide of oxy-tyrosinase that activate its coupled binuclear copper site†

Ioannis Kipouros,

‡^a Agnieszka Stańczak,

‡^bc Martin Culka,^b Erik Andris,

^b Timothy R. Machonkin,^d Lubomír Rulíšek

*^b and Edward I. Solomon

*^ae

Author affiliations

* Corresponding authors

^a Department of Chemistry, Stanford University, Stanford, California 94305, USA
E-mail: edward.solomon@stanford.edu

^b Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Flemingovo náměstí 2, 166 10, Praha 6, Czech Republic
E-mail: lubos@uochb.cas.cz

^c Faculty of Science, Charles University, Albertov 2038/6, 128 00 Praha 2, Czech Republic

^d Department of Chemistry, Whitman College, Walla Walla, WA 99362, USA

^e Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Stanford University, Menlo Park, California 94025, USA

Abstract

The factors that control the diverse reactivity of the μ-η²:η²-peroxo dicopper(II) oxy-intermediates in the coupled binuclear copper proteins remain elusive. Here, spectroscopic and computational methods reveal H-bonding interactions between active-site waters and the μ-η²:η²-peroxide of oxy-tyrosinase, and define their effects on the Cu(II)₂O₂ electronic structure and O₂ activation.

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Article information

DOI: https://doi.org/10.1039/D2CC00750A
Article type: Communication
Submitted: 06 Feb 2022
Accepted: 22 Feb 2022
First published: 23 Feb 2022

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Chem. Commun., 2022,58, 3913-3916

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Evidence for H-bonding interactions to the μ-η²:η²-peroxide of oxy-tyrosinase that activate its coupled binuclear copper site

I. Kipouros, A. Stańczak, M. Culka, E. Andris, T. R. Machonkin, L. Rulíšek and E. I. Solomon, Chem. Commun., 2022, 58, 3913 DOI: 10.1039/D2CC00750A

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