Number of the records: 1

On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase

SYSNO ASEP	0379013
Document Type	J - Journal Article
R&D Document Type	Journal Article
Subsidiary J	Článek ve WOS
Title	On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase
Author(s)	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, ORCID}
Number of authors	8
Source Title	Electroanalysis. - : Wiley - ISSN 1040-0397 Roč. 24, č. 7 (2012), s. 1524-1540
Number of pages	17 s.
Language	eng - English
Country	DE - Germany
Keywords	bilirubin oxidase ; intramolecular electron transfer ; rate-limiting catalytic step ; reorganization energy ; QM/MM calculations
Subject RIV	CF - Physical ; Theoretical Chemistry
CEZ	AV0Z40550506 - UOCHB-X (2005-2011)
UT WOS	000305999200006
DOI	10.1002/elan.201200188
Annotation	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.
Workplace	Institute of Organic Chemistry and Biochemistry
Contact	asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Viktorie Chládková, Tel.: 232 002 434
Year of Publishing	2013

Number of the records: 1