On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase
Identifikátory výsledku
Kód výsledku v IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F12%3A00379013" target="_blank" >RIV/61388963:_____/12:00379013 - isvavai.cz</a>
Výsledek na webu
<a href="http://dx.doi.org/10.1002/elan.201200188" target="_blank" >http://dx.doi.org/10.1002/elan.201200188</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/elan.201200188" target="_blank" >10.1002/elan.201200188</a>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase
Popis výsledku v původním jazyce
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.
Název v anglickém jazyce
On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase
Popis výsledku anglicky
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.
Klasifikace
Druh
J<sub>x</sub> - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)
CEP obor
CF - Fyzikální chemie a teoretická chemie
OECD FORD obor
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Návaznosti výsledku
Projekt
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Návaznosti
Z - Vyzkumny zamer (s odkazem do CEZ)
Ostatní
Rok uplatnění
2012
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
Electroanalysis
ISSN
1040-0397
e-ISSN
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Svazek periodika
24
Číslo periodika v rámci svazku
7
Stát vydavatele periodika
DE - Spolková republika Německo
Počet stran výsledku
17
Strana od-do
1524-1540
Kód UT WoS článku
000305999200006
EID výsledku v databázi Scopus
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