Highly selective fluorescent OFF-ON thiol probes based on dyads of BODIPY and potent intramolecular electron sink 2,4-dinitrobenzenesulfonyl subunits
Highly selective fluorescent OFF-ON thiol probes based on dyads of BODIPY and potent intramolecular electron sink 2,4-dinitrobenzenesulfonyl subunits
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DOI：
10.1039/c0ob00910e
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发表时间：
2011-01-01
影响因子：
3.2
通讯作者：
Kan, Yanyan
中科院分区：
文献类型：
--
作者：
Guo, Huimin;Jing, Yingying;Kan, Yanyan
基于BODIPY（作为光诱导电子转移的电子供体，即PET）和2,4-二硝基苯磺酰基（DNBS）二联体，两种在可见光谱中具有强吸收的高选择性OFF-ON绿色发射荧光硫醇探针（1和2）（摩尔消光系数e在509 nm处高达73 800 M-1 cm(-1)） （作为 PET 过程的电子受体）被设计出来。确定了两种探针的单晶结构。探针2的电子供体（BODIPY荧光团）和电子受体（DNBS）之间的距离比探针1大，因此探针2的对比度（或PET效率）比探针1小。然而，在半胱氨酸存在下，探针1和探针2都观察到荧光OFF-ON切换效应（探针1和探针1的发射增强是300倍） 探针 2) 的 54 倍。通过 DFT/TDDFT 计算使荧光 OFF-ON 传感机制合理化。我们通过 DFT 计算证明 DNBS 大约是。比马来酰亚胺部分接受电子的能力高 0.76 eV。该探针用于细胞硫醇的荧光成像。
Two highly selective OFF-ON green emitting fluorescent thiol probes (1 and 2) with intense absorption in the visible spectrum (molar extinction coefficient e is up to 73 800 M-1 cm(-1) at 509 nm) based on dyads of BODIPY (as electron donor of the photo-induced electron transfer, i.e. PET) and 2,4-dinitrobenzenesulfonyl (DNBS) (as electron acceptor of the PET process) were devised. The single crystal structures of the two probes were determined. The distance between the electron donor (BODIPY fluorophore) and the electron acceptor (DNBS) of probe 2 is larger than that of probe 1, as a result the contrast ratio (or the PET efficiency) of probe 2 is smaller than that of probe 1. However, fluorescence OFF-ON switching effects were observed for both probe 1 and probe 2 in the presence of cysteine (the emission enhancement is 300-fold for probe 1 and 54-fold for probe 2). The fluorescence OFF-ON sensing mechanism is rationalized by DFT/TDDFT calculations. We demonstrated with DFT calculations that DNBS is ca. 0.76 eV more potent to accept electrons than the maleimide moiety. The probes were used for fluorescent imaging of cellular thiols.