Rational principles for modulating fluorescence properties of fluorescein
Rational principles for modulating fluorescence properties of fluorescein
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DOI：
10.1021/ja048241k
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发表时间：
2004-11-03
影响因子：
15
通讯作者：
Nagano, T
中科院分区：
文献类型：
--
作者：
Ueno, T;Urano, Y;Nagano, T
基于实用的荧光调控机制的合理设计策略将使我们能够快速开发出针对目标分子的新型荧光探针。在这里，我们提出了一个实用和通用的原理来调节荧光素的荧光性质。我们假设(A)荧光素分子可以分为两个部分，即作为荧光基团的黄原烯部分和作为荧光控制部分的苯部分，尽管它们之间没有明显的连接体结构，以及(B)荧光性质可以通过从被激发的荧光团到可还原的苯部分(给体激发的pET；d-pET)的光诱导电子转移(PET)过程来调节。为了评价苯基的还原电势与荧光性质的关系，我们设计并合成了多种通过在苯基上引入吸电子基团来微调苯基的还原电势的衍生物。我们的结果清楚地表明，荧光素衍生物的荧光性质确实被精细地调制，这取决于苯基团的还原电位。这一信息为合理设计新型功能荧光探针提供了实用策略的基础。
Rational design strategies based on practical fluorescence modulation mechanisms would enable us to rapidly develop novel fluorescence probes for target molecules. Here, we present a practical and general principle for modulating the fluorescence properties of fluorescein. We hypothesized that (a) the fluorescein molecule can be divided into two moieties, i.e., the xanthene moiety as a fluorophore and the benzene moiety as a fluorescence-controlling moiety, even though there is no obvious linker structure between them, and (b) the fluorescence properties can be modulated via a photoinduced electron transfer (PeT) process from the excited fluorophore to a reducible benzene moiety (donor-excited PeT; d-PeT). To evaluate the relationship between the reduction potential of the benzene moiety and the fluorescence properties, we designed and synthesized various derivatives in which the reduction potential of the benzene moiety was fine tuned by introducing electron-withdrawing groups onto the benzene moiety. Our results clearly show that the fluorescence properties of fluorescein derivatives were indeed finely modulated depending upon the reduction potential of the benzene moiety. This information provides a basis for a practical strategy for rational design of novel functional fluorescence probes.