On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase
The result's identifiers
Result code in 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>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase
Original language 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.
Czech name
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Czech description
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Classification
Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CF - Physical chemistry and theoretical chemistry
OECD FORD branch
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Result continuities
Project
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Continuities
Z - Vyzkumny zamer (s odkazem do CEZ)
Others
Publication year
2012
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Electroanalysis
ISSN
1040-0397
e-ISSN
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Volume of the periodical
24
Issue of the periodical within the volume
7
Country of publishing house
DE - GERMANY
Number of pages
17
Pages from-to
1524-1540
UT code for WoS article
000305999200006
EID of the result in the Scopus database
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