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首页> 外文期刊>Chemistry: A European journal >Unraveling the mechanism of the photodeprotection reaction of 8-bromo- and 8-chloro-7-hydroxyquinoline caged acetates
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Unraveling the mechanism of the photodeprotection reaction of 8-bromo- and 8-chloro-7-hydroxyquinoline caged acetates

机译：揭示8-溴和8-氯-7-羟基喹啉笼型乙酸酯的光脱保护反应机理

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摘要

Photoremovable protecting groups (PPGs) when conjugated to biological effectors forming "caged compounds" are a powerful means to regulate the action of physiologically active messengers in vivo through 1-photon excitation (1PE) and 2-photon excitation (2PE). Understanding the photodeprotection mechanism is important for their physiological use. We compared the quantum efficiencies and product outcomes in different solvent and pH conditions for the photolysis reactions of (8-chloro-7-hydroxyquinolin-2-yl) methyl acetate (CHQ-OAc) and (8-bromo-7-hydroxyquinolin-2-yl)methyl acetate (BHQ-OAc), representatives of the quinoline class of phototriggers for biological use, and conducted nanosecond time-resolved spectroscopic studies using transient emission (ns-EM), transient absorption (ns-TA), transient resonance Raman (ns-TR ~2), and time-resolved resonance Raman (ns-TR ~3) spectroscopies. The results indicate differences in the photochemical mechanisms and product outcomes, and reveal that the triplet excited state is most likely on the pathway to the product and that dehalogenation competes with release of acetate from BHQ-OAc, but not CHQ-OAc. A high fluorescence quantum yield and a more efficient excited-state proton transfer (ESPT) in CHQ-OAc compared to BHQ-OAc explain the lower quantum efficiency of CHQ-OAc relative to BHQ-OAc.
机译：当与生物效应子缀合形成“笼状化合物”时，可光去除保护基（PPG）是通过1光子激发（1PE）和2光子激发（2PE）调节体内生理活性信使的作用的有效手段。了解光脱保护机理对其生理用途很重要。我们比较了（8-氯-7-羟基喹啉-2-基）乙酸甲酯（CHQ-OAc）和（8-溴-7-羟基喹啉-2）的光解反应在不同溶剂和pH条件下的量子效率和产物结果-基）乙酸甲酯（BHQ-OAc），是生物用途的光触发喹啉类的代表，并使用瞬态发射（ns-EM），瞬态吸收（ns-TA），瞬态共振拉曼进行了纳秒级时间分辨光谱研究（ns-TR〜2）和时间分辨共振拉曼光谱（ns-TR〜3）。结果表明，光化学机理和产物的结果存在差异，并且表明三重激发态最有可能在通往产物的途径上，并且脱卤与从BHQ-OAc释放乙酸盐竞争，而与CHQ-OAc竞争。与BHQ-OAc相比，CHQ-OAc中的高荧光量子产率和更有效的激发态质子转移（ESPT）解释了CHQ-OAc相对于BHQ-OAc较低的量子效率。

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