Investigation into the mechanism for high enantioselectivity of the thioesterification enzyme

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Firefly is an insect which is felt familiar and attractive to us because with which the word of lighting insect is closely associated. Thus firefly luciferase is generally supposed to be bioluminescence enzyme, however, we have found another catalytic activity, "enantioselective thioesterification activity", in this enzyme. When ketoprofen, which has an asymmetric center in the molecule, was subjected to firefly luciferase catalyzed thioester formation reaction, R-form would be preferentially transferred to the corresponding thioester. In this research, by detailed kinetics measurements, MD simulation and X-ray crystallographic analysis we could have throw light on a reason why firefly luciferase can distinguish the absolute configuration in the molecule.