2014
DOI: 10.1038/srep05938
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Excited singlet molecular O2 (1Δg) is generated enzymatically from excited carbonyls in the dark

Abstract: In mammalian tissues, ultraweak chemiluminescence arising from biomolecule oxidation has been attributed to the radiative deactivation of singlet molecular oxygen [O2 (1Δg)] and electronically excited triplet carbonyl products involving dioxetane intermediates. Herein, we describe evidence of the generation of O2 (1Δg) in aqueous solution via energy transfer from excited triplet acetone. This involves thermolysis of 3,3,4,4-tetramethyl-1,2-dioxetane, a chemical source, and horseradish peroxidase-catalyzed oxid… Show more

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Cited by 58 publications
(56 citation statements)
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“…2c). Thus, replacing 16 The O 2 -dependence of the Trp to cis-WOOH conversion was confirmed by a small but significant increase in cis-WOOH when the reaction mixture was saturated with O 2 , whereas displacing O 2 in the reaction mixture with argon decreased cis-WOOH (and NFK) but not oxyindolylalanine ( Fig. 2d).…”
mentioning
confidence: 75%
See 1 more Smart Citation
“…2c). Thus, replacing 16 The O 2 -dependence of the Trp to cis-WOOH conversion was confirmed by a small but significant increase in cis-WOOH when the reaction mixture was saturated with O 2 , whereas displacing O 2 in the reaction mixture with argon decreased cis-WOOH (and NFK) but not oxyindolylalanine ( Fig. 2d).…”
mentioning
confidence: 75%
“…5a-c), thus establishing cis-WOOH as a precursor of NFK. Thermal decomposition of cis-WOOH also led to emission of light with maxima at 489 nm, characteristic of activated carbonyls 16 (Extended data, fig. 5d).…”
mentioning
confidence: 95%
“…[27] So far, only the reactions of O 2 ( 1 Δ g ) with olefins and aromatic compounds that have electron-rich conjugated double bonds leading to the formation of allylic hydroperoxide, dioxetanes or endoperoxides have been reported. [28] Because of its chemical inertness and electrophilic nature, the contribution of O 2 ( 1 Δ g ) to the oxidation of carbenium ions may be minor. The third-order association reaction of triplet O( 3 P) with triplet O 2 ( 3 Σ g À ) to form singlet O 3 [reaction (16)] is spin-allowed.…”
Section: Resultsmentioning
confidence: 99%
“…33 Both cis,cis and cis,trans isomers of the muconic acid are observed in the experiments. 34 Although the dioxetane-like species has been discarded based on 18 O 2 labelling studies 35 and theoretical calculations, 36,37 it is still worth analyzing the reactivity of these species because they have been suggested as intermediates for both dioxygenase model systems and for the carotenoid oxygenases. 38,39 The argument that lack of light emission excludes a dioxetane mechanism 40 might not be correct because the O-O bond can be either cleaved with the help of an electron donor, or possibly by the involvement of dark photochemistry.…”
Section: Introductionmentioning
confidence: 99%