20115-09-7Relevant articles and documents
β-Deuterium Isotope Effects on Firefly Luciferase Bioluminescence
Pirrung, Michael C.,Dorsey, Allyson,Howitt, Natalie De,Liao, Jiayu
, p. 697 - 700 (2017/09/13)
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 oxyluciferin) and dehydroluciferin is determined, not by the fate of the hydroperoxide, but by that of the radical formed from luciferyl adenylate, and the kinetic isotope effect (KIE) reflects H-atom abstraction by superoxide.
Chemi- and Bioluminescence of Firefly Luciferin
White, Emil H.,Steinmetz, Mark G.,Miano, Jeffrey D.,Wildes, Peter D.,Morland, Robert
, p. 3199 - 3208 (2007/10/02)
Chemiluminescence of ethoxyvinyl ester of 5,5-dimethylluciferin (3b) with base and 18O2 gave carbon dioxide in 39percent yield enriched with 57-83percent of 18O.The corresponding experiment with luciferin (3a) gave carbon dioxide in 20percent yield with 7
