20115-09-7Relevant academic research and scientific papers
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.
A new synthesis of dehydroluciferin [2-(6′-hydroxy-2′- benzothiazolyl)-thiazole-4-carboxylic acid] from 1,4-benzoquinone
Ciuffreda, Pierangela,Casati, Silvana,Meroni, Giuseppe,Santaniello, Enzo
, p. 5893 - 5897 (2013/07/27)
A new synthesis of dehydroluciferin [2-(6′-hydroxy-2′- benzothiazolyl)-thiazole-4-carboxylic acid], the oxidative product of luciferin, has been realized starting from 1,4-benzoquinone. Reaction of this compound with l-cysteine ethyl ester, followed by an oxidation-cyclization step afforded 2-carbethoxy-6-hydroxybenzothiazole that was in situ hydrolyzed and decarboxylated to 6-hydroxybenzothiazole. The tert-butyl(dimethyl)silyl ether of this key intermediate was subjected to α-lithiation followed by formylation with DMF, and the resulting aldehyde condensed with l-cysteine ethyl ester. Dehydrogenation of the intermediate thiazolidine followed by deprotection afforded dehydroluciferin in 35% overall yield from 1,4-benzoquinone (69% from 6-hydroxybenzothiazole).
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
