Chemically initiated electron exchange luminescence. A new chemiluminescent reaction path for organic peroxides

Koo, Jachoon; Schuster, Gary B.

doi:10.1021/ja00460a050

Cited by 155 publications

(110 citation statements)

References 2 publications

(2 reference statements)

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“…The chemiluminescent exciplex emission in this case is identical in all respects to the emission generated by photoexcitation of mixtures of benzocoumarin and triphenylamine. We have designated this sequence of reactions leading to light emission "chemically initiated electron exchange luminescence (CIEEL)" (2).…”

Section: Methodsmentioning

confidence: 99%

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Bioluminescence of the firefly: key steps in the formation of the electronically excited state for model systems.

Koo¹,

Schmidt²,

Schuster³

1978

Proc. Natl. Acad. Sci. U.S.A.

152

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The chemical mechanism for formation of electronically excited-state molecules from the thermal reaction of dimethyldioxetanone was studied. Light production in the presence of certain easily oxidized aromatic hydrocarbons was found not to conform to the classical mechanistic schemes for chemiexcitation. Detailed investigation of the dioxetanone s stem revealed light formation by the recently discovered, chemically initiated electron-exchange process. This result is extrapolated to bioluminescent systems. In particular, the key high-energy molecule involved in firefly luminescence, which has been identified as a dioxetanone, is postulated to form excited states as a result of intramolecular electron transfer from the phenoxythiazole moiety to the dioxetanone. Subsequent rapid decarboxylation results in direct formation of an excited singlet state of the emitting amide. Bioluminescent organisms are widely distributed throughout terrestrial and aquatic environments. Although the biological purpose of luminescence varies from species to species, the chemical mechanism for generation of the electronically excited state, which subsequently emits light, appears to be general in a wide variety of organisms. In nearly all of the bioluminescent processes that have been investigated, high-energy cyclic peroxide molecules are implicated as providing the energy necessary for excited state generation (1). In the study of bioluminescent mechanisms the central concerns have been: (i) identification of the molecule capable of undergoing a reaction with a free energy change sufficient to permit excited state generation, (ii) characterization of the emitting species, and (iii) identification of the molecular process that converts the high-energy reactant to an electronically excited product molecule.Our recent investigations (2) of chemiluminescence have led to the discovery of a general mechanism of excited state formation identified as chemically initiated electron exchange luminescence. Studies of exergonic chemical reactions that model bioluminescent systems now permit us to suggest that this mechanism is operative in the formation of electronically excited states in living organisms. The light-forming reaction of the North American firefly (Photinus pyralis) will serve as the prototypical case. The conclusions reached from this system are readily extended to other bioluminescent reactions.Many excellent studies of bioluminescence from the firefly have led to the characterization of the enzyme/substrate system involved in the light generation step (3). In summary, the substrate luciferin has been identified as 1 and independently synthesized. Reaction of 1 with oxygen in the presence of the enzyme luciferase generates a high-energy content molecule that has been identified as the dioxetanone (2) by 180 labeling studies (4, 5). In order to produce bioluminescence, 2 loses the The costs of publication of this article were defrayed in part by the payment of page charges. This article must therefore be hereby marked "adv...

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Section: Methodsmentioning

confidence: 99%

“…Our recent investigations (2) Many excellent studies of bioluminescence from the firefly have led to the characterization of the enzyme/substrate system involved in the light generation step (3). In summary, the substrate luciferin has been identified as 1 and independently synthesized.…”

mentioning

confidence: 99%

Bioluminescence of the firefly: key steps in the formation of the electronically excited state for model systems.

Koo¹,

Schmidt²,

Schuster³

1978

Proc. Natl. Acad. Sci. U.S.A.

152

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“…(iii) substituição de H por D no anel do tetrafe nildioxetano não produziu efeito isotópico secundário mensurável na cinética de sua termólise (Koo e Schuster, 1977) o mecanismo "concerted" prevê um efeito isotópico pOiSI no es tado de transição ocorre mudança de hibridização do anel de 3 2 sp para sp .…”

Section: H+-+hunclassified

“…Resta a possibilidade de que este comportamento divergente de TMOD se deva a uma mudança no mecanismo de clivagem para "concerted" (McCapra, 1968) ou via "transferen cia de eletrons" (McCapra, 1977;Koo e Schuster, 1977). (E = 25 ±l kcal moI-I) era provavelmente devido à diferena ça na configuração eletrônica dos produtos correspondentes (nn*, em vez de nn*) o que resultaria numa mudança do mecanismo de "diradical" para "concerted".…”

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“…(E = 25 ±l kcal moI-I) era provavelmente devido à diferena ça na configuração eletrônica dos produtos correspondentes (nn*, em vez de nn*) o que resultaria numa mudança do mecanismo de "diradical" para "concerted". A outra possibilidd e, mais interessante, seria uma mudança do mecanismo decli vagem de "diradical" para CIEEL "chemically initiated electron exchange luminescence"; Koo e Schuster, 1977 a)-erro na determinação da concentração de dioxetano (méto do via GPGL é mais preciso e exato que NMR ou titulação iodométrica; secção 3.5), b)-erro na constante de velocidade k l , já que as determind 3 1 -çoes e~e~sao feitas a baixa temperatura para evitar decomposição apreciável de dioxetano; nestas condiç6es catálise "escura" por traços de metal pesado representam sério processo competitivo (Bartlett eoolab. , 1974; c)-os valores de~TE nao são conhecidos para todos os trios cetona triplete/DBA ou Eu (TTA) 3Phen/solvente; assume-se nos cálculos~TE = 0,20, determinado para triplete/DBA/benzeno (Berenfel'd e colab., 1970;Wilson, 1976 9 -1 -1 = k dif .…”

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Efeitos de substituintes alquílicos nas propriedades de dioxetanos

Bechara¹

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Mechanisms of the effect of xenobiotics on bacterial bioluminescence

Kudryasheva

1999

Luminescence

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The influence of xenobiotics on the bioluminescent enzyme system is considered in terms of molecular action on the primary physicochemical processes—energy, electron and hydrogen (e− + H+) transduction. Dyes, non‐fluorescent chemically inert organic compounds, redox‐active organic compounds and metallic salts were investigated. The influence of the different xenobiotics depends in a complex way on physicochemical characteristics of the xenobiotic molecules (spectral‐luminescent characteristics, electron‐acceptation energy and redox potential). Copyright © 1999 John Wiley & Sons, Ltd.

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Chemically initiated electron exchange luminescence. A new chemiluminescent reaction path for organic peroxides

Cited by 155 publications

References 2 publications

Bioluminescence of the firefly: key steps in the formation of the electronically excited state for model systems.

Bioluminescence of the firefly: key steps in the formation of the electronically excited state for model systems.

Efeitos de substituintes alquílicos nas propriedades de dioxetanos

Mechanisms of the effect of xenobiotics on bacterial bioluminescence

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