A proposed mechanism for light emission by bacterial luciferase involving dissociative electron transfer

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Abstract

A new mechanism that involves dissociative electron transfer in the energy transducing step is set forward for bacterial luciferase catalyzed light emission. The proposal involves (1) dissociation of the 4a-hydroperoxyflavin to a flavin radical and O2-, accounting for 570 and 620nm absorption, (2) O2- addition to the aldehyde carbonyl to form a peroxyl radical, (3) abstraction of H from an enzyme thiol group to form RCH(OOH)OH, (4) thiyl radical abstraction of the H on C in RCH(OOH)OH, a step which can show a kH kD of ca. 4, and (5) dissociative electron- transfer, a highly exothermic step that leads to a protonated flavin excited state, a carboxylic acid and water.

Original languageEnglish
Pages (from-to)356-364
Number of pages9
JournalBiochemical and Biophysical Research Communications
Volume92
Issue number2
DOIs
StatePublished - 29 Jan 1980

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