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在 AOT 反胶束中受限效应对萤火虫生色团 D-荧光素激发态质子转移的影响。

Effect of confinement on excited-state proton transfer of firefly's chromophore D-luciferin in AOT reverse micelles.

机构信息

Department of Chemistry, Indian Institute of Technology , Kharagpur 721302, WB, India.

出版信息

J Phys Chem B. 2014 Mar 27;118(12):3401-8. doi: 10.1021/jp500210n. Epub 2014 Mar 13.

DOI:10.1021/jp500210n
PMID:24624892
Abstract

Excited-state intermolecular proton transfer of D-luciferin in reverse micelles has been investigated using steady-state and time-resolved fluorescence spectroscopy measurement. The different polar cores have been chosen for the study of proton transfer dynamics in aerosol-OT (AOT) reverse micelles. It is shown that aqueous reverse micelle is the suitable environment for the photoprotolytic reaction of D-luciferin. The neutral form of the chromophore is present both in ground and excited state at W0 = 0. The proton transfer in nanometer size water pool of water/AOT/n-heptane begins at W0 = 8 and increases with increasing W0 values. However, the intermolecular excited-state proton transfer (ESPT) of D-luciferin is inhibited in nonaquous reverse micelles with DMF and DMSO as a polar core. Thus, the requirement of ESPT of D-luciferin to take place in reverse micelles consists of polar protic solvent like water as a polar core.

摘要

利用稳态和时间分辨荧光光谱测量研究了 D-荧光素在反胶束中的激发态分子间质子转移。选择不同极性核研究了气溶胶-OT(AOT)反胶束中的质子转移动力学。结果表明,水相反胶束是 D-荧光素光解反应的合适环境。生色团的中性形式在基态和激发态均存在于 W0=0 处。水/AOT/正庚烷纳米级水腔中的质子转移在 W0=8 时开始,并随 W0 值的增加而增加。然而,在以 DMF 和 DMSO 为极性核的非水反胶束中,D-荧光素的分子间激发态质子转移(ESPT)受到抑制。因此,D-荧光素发生 ESPT 的反胶束需要包含水等质子极性溶剂作为极性核。

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