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荧光探针法测定磷酸酯与羟基自由基的反应速率常数

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基于香豆素与羟基自由基(·OH)反应后产生的7-羟基香豆素具有强荧光性的特点,使用香豆素作为荧光探针,对不同浓度磷酸三丁酯(TBP)和磷酸三异戊酯(TiAP)水溶液经γ射线辐照后的·OH产额进行了研究,并通过准一级动力学拟合分别测定了TBP及TiAP与·OH室温下的反应速率常数,测得kTBP=(9.0±0.2)×109 L/(mol·s),kTiAP=(5.3±0.2)×109 L/(mol·s).由于TiAP的疏水性比TBP强,其与·OH的反应速率常数小于TBP,导致加入相同浓度的磷酸酯后,产生的·OH产额高于TBP体系.该工作为研究萃取剂与·OH反应提供了简单、方便、有效的方法.
Reaction rate constant of phosphate esters with hydroxyl radicals investigated using fluorescence probe method
The strong fluorescence of 7-hydroxycoumarin yielded by the reaction of coumarin with hydroxyl radicals(·OH)was used as a fluorescent probe to determine the yield of 7-hydroxycoumarin aqueous solutions with different concentrations of TBP and TiAP after gamma ray irradiation.The reaction rate constants of TBP and TiAP with·OH at room temperature were determined via pseudo-first order kinetic fitting(kTBP=(9.0±0.2)×109 L/(mol·s)and kTiAP=(5.3±0.2)×109 L/(mol·s)),respectively.Owing to the stronger hydrophobicity of TiAP compared with that of TBP,its reaction rate constant with·OH is lower than that of TBP,thus resulting in a higher yield of·OH in the TiAP solution compared to the TBP solution with the same concentration.This study provides a simple,convenient and efficient method for investigating the reactions between extractants and·OH.

Coumarin fluorescent probeHydroxyl radicalGamma irradiationExtractantReaction rate constant

杨运佳、吴翼茜、彭静、翟茂林、李久强

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北京大学化学与分子工程学院 放射化学与辐射化学重点学科实验室 北京分子科学国家研究中心 北京 100871

香豆素荧光探针 羟基自由基 γ辐照 萃取剂 反应速率常数

2024

辐射研究与辐射工艺学报
中国科学院上海应用物理研究所

辐射研究与辐射工艺学报

CSTPCD
影响因子:0.527
ISSN:1000-3436
年,卷(期):2024.42(6)