A computational analysis of the interaction between flavin and thiol(ate) groups. Implications for flavoenzyme catalysis

作者：Dmitrenko Olga^*; Thorpe Colin

来源：Journal of Sulfur Chemistry, 2008, 29(3-4): 415-C21.

DOI：10.1080/17415990802105739

• charge-transfer
• flavin
• thiolate
• DFT
• C4a-adduct

A computational analysis of the interaction between flavin and thiol(ate) groups has been performed using three density functional theory methods (B3LYP, MPW1PW91, and MPWB1K). Oxidized flavin forms a charge-transfer complex with the thiolate anion prior to the generation of a covalent-adduct at the C4a position of the isoalloxazine ring. The computed reactions require a concerted proton transfer to the N5 position of the flavin and show relatively small barriers (<13 kcal/mol). Using different model systems, it was demonstrated that this proton can be delivered to the flavin via a protonated cysteine, or from the carboxyl moiety of glutamic and aspartic acids by utilizing a series of intervening water molecules.

• 出版日期2008