Počet záznamů: 1
On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase
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SYSNO ASEP 0379013 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase Tvůrce(i) Shleev, S. (RU)
Andoralov, V. (SE)
Falk, M. (SE)
Reimann, C. T. (SE)
Ruzgas, T. (SE)
Srnec, Martin (UOCHB-X) RID
Ryde, U. (SE)
Rulíšek, Lubomír (UOCHB-X) RID, ORCIDCelkový počet autorů 8 Zdroj.dok. Electroanalysis. - : Wiley - ISSN 1040-0397
Roč. 24, č. 7 (2012), s. 1524-1540Poč.str. 17 s. Jazyk dok. eng - angličtina Země vyd. DE - Německo Klíč. slova bilirubin oxidase ; intramolecular electron transfer ; rate-limiting catalytic step ; reorganization energy ; QM/MM calculations Vědní obor RIV CF - Fyzikální chemie a teoretická chemie CEZ AV0Z40550506 - UOCHB-X (2005-2011) UT WOS 000305999200006 DOI 10.1002/elan.201200188 Anotace The detailed characterization of the kinetic and electrochemical properties of bilirubin oxidase (BOx) - a member of the MCO family - is reported. The experimental results strongly indicate that under certain conditions, e.g. in alkaline solutions, the intramolecular electron transfer (IET) can be the rate-limiting step in the BOx catalytic cycle. The data also suggest that one of the catalytically relevant intermediates (most likely characterized by an intermediate oxidation state of the TNC) formed during the catalytic cycle of BOx has a redox potential close to 0.4 V, indicating an uphill IET process from the T1 copper site (0.7 V) to the Cu-T23. These suggestions are supported by calculations of the IET rate, based on the experimentally observed Gibbs free energy change and theoretical estimates of reorganization energy obtained by combined quantum and molecular mechanical (QM/MM) calculations. Pracoviště Ústav organické chemie a biochemie Kontakt asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418 Rok sběru 2013
Počet záznamů: 1