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

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
Description	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. 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. (en)
Title	On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase (en)
skos:prefLabel	On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase (en)
skos:notation	RIV/61388963:_____/12:00379013!RIV13-AV0-61388963
http://linked.open...avai/predkladatel	Ústav organické chemie a biochemie AV ČR, v. v. i.
http://linked.open...avai/riv/aktivita	Z
http://linked.open...avai/riv/aktivity	Z(AV0Z40550506)
http://linked.open...iv/cisloPeriodika	7
http://linked.open...vai/riv/dodaniDat	2013
http://linked.open...aciTvurceVysledku	Rulíšek, Lubomír Srnec, Martin
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Ústav organické chemie a biochemie AV ČR, v. v. i.
http://linked.open...dnocenehoVysledku	156449
http://linked.open...ai/riv/idVysledku	RIV/61388963:_____/12:00379013
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	bilirubin oxidase; intramolecular electron transfer; rate-limiting catalytic step; reorganization energy; QM/MM calculations (en)
http://linked.open.../riv/klicoveSlovo	reorganization energy QM/MM calculations bilirubin oxidase intramolecular electron transfer rate-limiting catalytic step
http://linked.open...odStatuVydavatele	DE - Spolková republika Německo
http://linked.open...ontrolniKodProRIV	[C2CCF57026B9]
http://linked.open...i/riv/nazevZdroje	Electroanalysis
http://linked.open...in/vavai/riv/obor	CF
http://linked.open...ichTvurcuVysledku	2 (xsd:int)
http://linked.open...cetTvurcuVysledku	8 (xsd:int)
http://linked.open...UplatneniVysledku	2012
http://linked.open...v/svazekPeriodika	24
http://linked.open...iv/tvurceVysledku	Rulíšek, Lubomír Ryde, U. Srnec, Martin Shleev, S. Andoralov, V. Falk, M. Reimann, C. T. Ruzgas, T.
http://linked.open...ain/vavai/riv/wos	000305999200006
http://linked.open...n/vavai/riv/zamer	Regulace biologických procesů: Chemické modulátory vybraných systémů významných pro medicínu a zemědělství
issn	1040-0397
number of pages	17 (xsd:int)
http://bibframe.org/vocab/doi	10.1002/elan.201200188
is http://linked.open...avai/riv/vysledek of	On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase

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