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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Solvatochromic Effects on the Electron Exchange Chemiluminescence (CIEEL) of Spiroadamantyl-Substituted Dioxetanes and the Fluorescence of Relevant Oxyanions
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Solvatochromic Effects on the Electron Exchange Chemiluminescence (CIEEL) of Spiroadamantyl-Substituted Dioxetanes and the Fluorescence of Relevant Oxyanions

机译：溶剂变色作用对螺金刚烷基取代的二氧杂环丁烷的电子交换化学发光（CIEEL）和相关氧氰酸根的荧光

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摘要

A comparative spectral study on the intramolecular chemically initiated electron exchange luminescence (CIEEL) of five spiroadamantyl-substituted dioxetanes by various enzymatic and chemical triggers (alkaline phosphatase, HO~-, and F~-) in protic (h-2O, D_2O, and MeOH) and aprotic (MeCN and DMSO) solvents and the fluorescence of the authentic methyl m-oxybenzoate anion in the same media is reported. The present study reveals that the CIEEL spectral maxima are independent of the reaction medium and the means of triggering, whereas the fluorescence spectrum of the authentic CIEEL emitter depends on the solvent. In the aprotic solvents the CIEEL and the fluorescence spectra coincide, while in the protic media the fluorescence maxima of the authentic methyl m-oxybenzoate ion are blue-shifted by ca. 50 nm relative to those of the CIEEL emission. Neither exciplex formation nor specific environmental influence of the enzyme on the chemiexcited oxybenzoate accounts for the spectral shift between the CIEEL and the fluorescence emissions. The substitution pattern of the fluorophore is decisive for the observed solvent effects. For the odd-substituted methyl oxybenzoate, in which the oxy and the ester functionalities are cross-conjugated, a blue shift applies in the protic media, but not for the even-patterned methyl oxynaphthoate, with the oxy and ester groups extendedly conjugated. These divergent spectral observations are rationalized in terms of hydrogen-bonding effects, which are qualitatively substantiated by the semiempirical AMl calculations.
机译：质子分子（h-2O，D_2O和报告了MeOH）和非质子溶剂（MeCN和DMSO）以及纯正的间氧基苯甲酸甲酯阴离子在相同介质中的荧光。本研究表明，CIEEL光谱最大值与反应介质和触发方式无关，而真实CIEEL发射体的荧光光谱取决于溶剂。在非质子传递溶剂中，CIEEL和荧光光谱一致，而在质子传递介质中，真实的间氧基苯甲酸甲酯离子的荧光最大值发生蓝移约。相对于CIEEL发射的50 nm。激基复合物的形成或酶对化学激发的氧基苯甲酸酯的特定环境影响都不能解释CIEEL和荧光发射之间的光谱偏移。荧光团的取代模式对于所观察到的溶剂效果起决定性作用。对于其中氧基和酯官能团交叉共轭的奇数取代的氧基苯甲酸甲酯，在质子介质中施加蓝移，但对于偶合构图的羟基萘甲酸甲酯则不适用，并且氧和酯基团延长地共轭。这些发散的光谱观察根据氢键效应被合理化，其通过半经验的AM1计算定性地证实。

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