Sökning: id:"swepub:oai:lup.lub.lu.se:80e1647d-5bd1-40b6-87f1-ddf900477d28" >
On the Possibility ...
On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase
-
- Shleev, Sergey (författare)
- Malmö högskola,Institutionen för biomedicinsk vetenskap (BMV)
-
Andoralov, Viktor (författare)
-
- Falk, Magnus (författare)
- Malmö högskola,Institutionen för biomedicinsk vetenskap (BMV)
-
visa fler...
-
- Reimann, Curt (författare)
- Lund University,Lunds universitet,Tillämpad biokemi,Centrum för tillämpade biovetenskaper,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Pure and Applied Biochemistry,Center for Applied Life Sciences,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
-
- Ruzgas, Tautgirdas (författare)
- Malmö högskola,Institutionen för biomedicinsk vetenskap (BMV)
-
Srnec, Martin (författare)
-
- Ryde, Ulf (författare)
- Lund University,Lunds universitet,Beräkningskemi,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Computational Chemistry,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
-
Rulisek, Lubomir (författare)
-
visa färre...
-
(creator_code:org_t)
- 2012-06-22
- 2012
- Engelska.
-
Ingår i: Electroanalysis. - : Wiley. - 1040-0397 .- 1521-4109. ; 24:7, s. 1524-1540
- Relaterad länk:
-
https://portal.resea... (primary) (free)
-
visa fler...
-
http://dx.doi.org/10...
-
https://lup.lub.lu.s...
-
https://lup.lub.lu.s...
-
https://doi.org/10.1...
-
https://urn.kb.se/re...
-
visa färre...
Abstract
Ämnesord
Stäng
- The catalytic cycle of multicopper oxidases (MCOs) involves intramolecular electron transfer (IET) from the Cu-T1 copper ion, which is the primary site of the one-electron oxidations of the substrate, to the trinuclear copper cluster (TNC), which is the site of the four-electron reduction of dioxygen to water. In this study we report a detailed characterization of the kinetic and electrochemical properties of bilirubin oxidase (BOx) a member of the MCO family. The experimental results strongly indicate that under certain conditions, e.g. in alkaline solutions, the 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.
Ämnesord
- NATURVETENSKAP -- Biologi -- Biokemi och molekylärbiologi (hsv//swe)
- NATURAL SCIENCES -- Biological Sciences -- Biochemistry and Molecular Biology (hsv//eng)
- NATURVETENSKAP -- Kemi -- Teoretisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)
Nyckelord
- Bilirubin oxidase
- Intramolecular electron transfer
- Rate-limiting
- catalytic step
- Reorganization energy
- QM
- MM calculations
- Bilirubin oxidase
Publikations- och innehållstyp
- art (ämneskategori)
- ref (ämneskategori)
Hitta via bibliotek
Till lärosätets databas