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

被引:41
作者
Domratcheva, Tatiana [1 ]
Fedorov, Roman [1 ]
Schlichting, Ilme [1 ]
机构
[1] Max Planck Inst Med Res, Dept Biomol Mech, D-69120 Heidelberg, Germany
关键词
D O I
10.1021/ct0600114
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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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收藏
页码:1565 / 1574
页数:10
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