CHEMILUMINESCENCE OF BENZO[a]PYRENE‐7,8‐DIOL *-猫眼课题宝

苯并[a]芘-7,8-二醇的化学发光*

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发表时间：

1982

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作者：

H. H. Seliger;Ambler Thompson;J. P. Hamman;G. Posner

摘要苯并[a]芘-7，8-二醇(BP-7，8-diol)的化学发光(CL)最初是在肝微粒体提取物中观察到的，它与NaOCl+H_2O_2反应，以高于104的产率产生化学发光。NaOCl/H_2O_2引发的CL与Rose Bengal光敏化CL的动力学和底物浓度依赖关系相同。在后一种单线态制氧体系中，化学发光被β-胡萝卜素以1.20×1010M−1 S−1的扩散控制速率猝灭。BP-7，8-二醇的化学引发的化学发光光谱与微体化学发光相同。化学发光的长寿命(τ=240 S)、1O2产生化学发光以及电子给体对化学发光衰变有效速率常数的影响与二氧杂环己烷中间体的形成是一致的。CL与底物浓度的线性关系表明，发射来自单体激发态，而不是先前提出的激基缔合物。在相同的化学条件下，苯并[a]芘及其12个单羟基衍生物和其他二氢二醇衍生物的相对光产率从BP-7，8-二醇的CL的10−2到10−5不等。BP-7，8-二醇化学引发化学发光的特异性可能为该代谢物提供一种灵敏的分析方法。

Abstract 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 104 higher yield by reaction with NaOCl + H2O2. The kinetics and the substrate concentration dependence for the NaOCl/H2O2 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 × 1010M−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 1O2 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.

Specificity of chemiluminescence in the metabolism of benzo[a]pyrene to its carcinogenic diol epoxide.