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  Analysis of the primary photocycle reactions occurring in the light, oxygen, and voltage blue-light receptor by multiconfigurational quantum-chemical methods

Domratcheva, T., Fedorov, R., & Schlichting, I. (2006). Analysis of the primary photocycle reactions occurring in the light, oxygen, and voltage blue-light receptor by multiconfigurational quantum-chemical methods. Journal of Chemical Theory and Computation, 2(6), 1565-1574. doi:10.1021/ct0600114.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0001-DDFE-9 Version Permalink: http://hdl.handle.net/21.11116/0000-0001-DDFF-8
Genre: Journal Article

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 Creators:
Domratcheva, Tatiana1, Author              
Fedorov, Roman1, Author              
Schlichting, Ilme1, Author              
Affiliations:
1Department of Biomolecular Mechanisms, Max Planck Institute for Medical Research, Max Planck Society, ou_1497700              

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 Abstract: 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.

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Language(s): eng - English
 Dates: 2006-01-082006-09-142006-09-14
 Publication Status: Published in print
 Pages: 10
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 Rev. Type: Peer
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Title: Journal of Chemical Theory and Computation
  Other : J. Chem. Theory Comput.
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 2 (6) Sequence Number: - Start / End Page: 1565 - 1574 Identifier: Other: 1549-9618
CoNE: https://pure.mpg.de/cone/journals/resource/111088195283832