β-Deuterium Isotope Effects on Firefly Luciferase Bioluminescence.

ABSTRACT: A 5,5-d₂ -luciferin was prepared to measure isotope effects on reactions of two intermediates in firefly bioluminescence: emission by oxyluciferin and elimination of a putative luciferyl adenylate hydroperoxide to dehydroluciferin. A negligible isotope effect on bioluminescence provides further support for the belief that the emitting species is the keto-phenolate of oxyluciferin and rules out its excited-state tautomerization, one potential contribution to a bioluminescence quantum yield less than unity. A small isotope effect on dehydroluciferin formation supports a single-electron-transfer mechanism for reaction of the luciferyl adenylate enolate with oxygen to form the hydroperoxide or dehydroluciferin. Partitioning between the dioxetanone intermediate (en route to ox

SUBMITTER: Pirrung MC 

PROVIDER: S-EPMC5715289 | biostudies-literature | 2017 Dec

REPOSITORIES: biostudies-literature