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          Institute: MPI für medizinische Forschung     Collection: Coherent diffractive imaging     Display Documents



ID: 568458.0, MPI für medizinische Forschung / Coherent diffractive imaging
Analysis of the Primary Photocycle Reactions Occurring in the Light, Oxygen, and Voltage Blue−Light Receptor by Multiconfigurational Quantum−Chemical Methods
Translation of Title:Analysis of the Primary Photocycle Reactions Occurring in the Light, Oxygen, and Voltage Blue−Light Receptor by Multiconfigurational Quantum−Chemical Methods
Authors:Domratcheva, Tatiana; Fedorov, Roman; Schlichting, Ilme
Language:English
Date of Publication (YYYY-MM-DD):2006-11-01
Title of Journal:J. Chem. Theory Comput.
Journal Abbrev.:J. Chem. Theory Comput.
Volume:2
Issue / Number:6
Start Page:1565
End Page:1574
Review Status:Peer-review
Audience:Experts Only
Intended Educational Use:No
Abstract / Description:The photocycle reactions occurring between the flavin mononucleotide cofactor and the reactive cysteine residue in the blue−light photoreceptor domain light, oxygen, and voltage (LOV) were modeled for a system consisting of lumiflavin and thiomethanol. The electronic structure and energies of the reactive species were estimated using the CASSCF and MCQDPT2 quantum−chemical methods. The reaction pathway for the S−C4a covalent adduct formation in the triplet state was determined. Concerted electron and proton transfer from the thiol to the flavin in the triplet electronic state results in a biradical complex that is, however, unstable because its structure corresponds to a triplet−singlet crossing. The covalent adduct dissociation in the ground electronic state is a reverse of the photoreaction proceeding via a single energy barrier for hydrogen transfer. Thus, both photo− and dark reactions were found to be single−step chemical transformations occurring without stable intermediates. The photoreaction yielding the S−C4a covalent adduct is an intrinsic property of the isoalloxazine−thiol complex in the specific geometry arranged by the protein in LOV. The S−C4a covalent adduct between lumiflavin and thiomethanol is rather stable implying that in LOV its dissociation is facilitated by the protein
Last Change of the Resource (YYYY-MM-DD):--
External Publication Status:published
Document Type:Article
Communicated by:Wulf Kaiser
Affiliations:MPI für medizinische Forschung/Abteilung Biophysik
MPI für medizinische Forschung/Abteilung Biomolekulare Mechanismen
MPI für medizinische Forschung/Abteilung Biomolekulare Mechanismen/Heme and Flavin Enzymes
MPI für medizinische Forschung/Abteilung Biomolekulare Mechanismen/Coherent diffractive imaging
MPI für medizinische Forschung/Abteilung Biomolekulare Mechanismen/Computational Photobiology
Identifiers:LOCALID:6800
URI:http%3A%2F%2Fpubs.acs.org%2Fcgi-bin%2Farticle.cgi%...
URI:http%3A%2F%2Fpubs.acs.org%2Fcgi-bin%2Farticle.cgi%...
URI:http%3A%2F%2Fpubs.acs.org%2Fcgi-bin%2Fabstract.cgi...
DOI:10.1021%2Fct0600114
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