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Physicochemical Study of a Metastable-State Photoacid

机译:亚稳态光酸的理化研究

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摘要

A photoacid that possesses a metastable acidic state induced by visible light is studied. Previous work showed that this photoacid can reversibly produce a large pH change capable of controlling chemical reactions, altering material properties, and killing bacteria. In this work, we studied the relaxation kinetics of the metastable acidic state in different solvents including water, ethanol, and DMSO. In all of these solvents, the kinetic data can be fitted well to a second-order rate equation, which indicates that protonation is involved in the rate-limiting step. The rate constants in water, ethanol, and DMSO are 73, 1.6, and 0.034 M~(?1) s~(?1), respectively. The slow relaxation in DMSO allowed us to fully characterize the structure of the metastable acidic state using proton NMR. We also measured the quantum yield of the photoreaction, which is as high as 0.37.
机译:研究了具有可见光诱导的亚稳态酸性状态的光酸。先前的工作表明,这种光酸可以可逆地产生较大的pH变化,从而能够控制化学反应,改变材料特性并杀死细菌。在这项工作中,我们研究了在不同溶剂(包括水,乙醇和DMSO)中亚稳态酸性状态的弛豫动力学。在所有这些溶剂中,动力学数据都可以很好地拟合二阶速率方程,这表明质子化参与了限速步骤。在水,乙醇和DMSO中的速率常数分别为73、1.6和0.034 M〜(?1)s〜(?1)。 DMSO中的缓慢弛豫使我们能够使用质子NMR全面表征亚稳态酸性状态的结构。我们还测量了光反应的量子产率,该产率高达0.37。

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