Počet záznamů: 1
Theoretical studies of the active-site structure, spectroscopic and thermodynamic properties, and reaction mechanism of multicopper oxidases
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SYSNO ASEP 0391780 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Theoretical studies of the active-site structure, spectroscopic and thermodynamic properties, and reaction mechanism of multicopper oxidases Tvůrce(i) Rulíšek, Lubomír (UOCHB-X) RID, ORCID
Ryde, U. (SE)Celkový počet autorů 2 Zdroj.dok. Coordination Chemistry Reviews. - : Elsevier - ISSN 0010-8545
Roč. 257, č. 2 (2013), s. 445-458Poč.str. 14 s. Jazyk dok. eng - angličtina Země vyd. NL - Nizozemsko Klíč. slova multi-copper oxidases ; QM/MM calculations ; multireference calculations ; theoretical spectroscopy Vědní obor RIV CA - Anorganická chemie Institucionální podpora UOCHB-X - RVO:61388963 UT WOS 000312762200011 EID SCOPUS 84870390826 DOI 10.1016/j.ccr.2012.04.019 Anotace In this article, we review recent theoretical work that has complemented the extensive experimental data available for the multicopper oxidases (MCO) and led to the elucidation of the reaction mechanism of this class of enzymes. The MCOs couple four one-electron oxidations of substrates at the mononuclear type 1 copper (Cu-T1) site with the four-electron reduction of dioxygen at the trinuclear copper cluster (TNC). The TNC consists of three copper ions arranged in a unique triangular fashion. In its oxidised form and in some experimentally observed intermediates (the peroxy and native intermediates), this leads to a magnetic coupling of the unpaired electrons of the three copper ions, resulting in unusual spectroscopic features. By correlating experimental and theoretical data, an unambiguous mapping between the structural, energetic and spectroscopic properties of the various intermediates in the MCO reaction cycle can be established. In terms of theory, these studies involved quantum mechanics (QM; density-functional theory and multi-reference self-consistent field) calculations, combined QM and molecular mechanics (QM/MM) modelling, ranging from standard QM/MM optimisations to the combination of QM/MM optimisation with EXAFS spectroscopy and QM/MM free-energy perturbations to accurately address phenomena such as the Cu-T1 -> TNC electron transfer, as well as the reduction potentials and acid constants of all the putative intermediates in the MCO reaction cycle. In summary, we try to demonstrate in this review that the MCOs are not only an attractive playground for theoretical methods, but the results of the calculations (when carefully correlated with and benchmarked against experimental data) can also be used to draw unambiguous conclusions about MCO structure and reactivity. Pracoviště Ústav organické chemie a biochemie Kontakt asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Viktorie Chládková, Tel.: 232 002 434 Rok sběru 2014
Počet záznamů: 1