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CHEMILUMINESCENCE OF BENZO[a]PYRENE‐7,8‐DIOL *
Author(s) -
Seliger H. H.,
Thompson A.,
Hamman J. P.,
Posner G. H.
Publication year - 1982
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1982.tb04387.x
Subject(s) - chemistry , chemiluminescence , diol , pyrene , rose bengal , reaction rate constant , substrate (aquarium) , dioxetane , photochemistry , singlet oxygen , benzo(a)pyrene , kinetics , yield (engineering) , medicinal chemistry , stereochemistry , oxygen , organic chemistry , physics , oceanography , quantum mechanics , geology , materials science , metallurgy
The chemiluminescence (CL) of benzo[ a ]pyrene‐7,8‐diol (BP‐7,8‐diol), originally observed in liver microsomal extracts, has been produced in greater than 10 4 higher yield by reaction with NaOCl + H 2 O 2 . The kinetics and the substrate concentration dependence for the NaOCl/H 2 O 2 initiated CL are the same as those for Rose Bengal photosensitization of CL. In this latter singlet oxygen generating system the CL is quenched by β‐carotene at a diffusion controlled rate of 1.2 × 10 10 M −1 s −1 . The chemically‐initiated CL emission spectrum of BP‐7,8‐diol appears to be the same as that of the microsomal CL. The long lifetime of the CL (τ= 240 s), the production of CL by 1 O 2 and the effects of electron donors upon the effective rate constant for decay of CL are consistent with the formation of a dioxetane intermediate. The linear dependence of CL upon substrate concentration indicates that the emission is from a monomer excited state rather than from an exciplex as suggested previously. Under the same chemical conditions the relative light yields from benzo[ a ]pyrene, its 12 monohydroxy derivatives and its other dihydro‐diol derivatives range from 10 −2 to 10 −5 of the CL from BP‐7,8‐diol. The specificity of the chemically‐initiated CL of BP‐7,8‐diol may provide a sensitive assay for this metabolite.