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Kinetics and Mechanism of L-Tryptophan Oxidation by Chloramine-T in Basic Medium: A Spectrofluorometric Study

机译:碱性介质中氯胺-T氧化L-色氨酸的动力学和机理:荧光光谱法研究

摘要

One of the greatest challenges in oxidation research today is the determination ofin vivo oxidative stresses. In this investigation, the spectrofluorometry is used to monitor the kinetics of chloramine-T (CAT) oxidation of L-tryptophan (Trp) in basic solutions. The Trp-CAT reaction progress has been monitored at λmax = 485 nm (after using the excitation wavelength of 360 nm) over the temperature range, 293-313 K. The redox reaction follows a first-order dependence of the rate each on [CAT] and [Trp], and an inverse fractional-order on [OH-]. Variations of the ionic strength and the solvent dielectric constant have no effect on the rate. An addition of the reduction product of CAT, p-toluenesulfonamide, to the reaction mixture also has no influence on the rate. Based on the temperature effect, activation parameters are evaluated. A mechanism consistent with the observed kinetic and activation data has been proposed and the rate-law derived.
机译:当今氧化研究的最大挑战之一是体内氧化应激的测定。在这项研究中,荧光光谱法用于监测碱性溶液中L-色氨酸(Trp)的氯胺T(CAT)氧化动力学。在293-313 K的温度范围内,在λmax= 485 nm(使用360 nm的激发波长后)上监测了Trp-CAT反应进程。氧化还原反应遵循速率对[CAT]的一阶依赖性]和[Trp],以及[OH-]上的反分数阶。离子强度和溶剂介电常数的变化对速率没有影响。将CAT的还原产物对甲苯磺酰胺添加到反应混合物中也对速率没有影响。基于温度影响,评估激活参数。已经提出了与观察到的动力学和活化数据一致的机理,并推导了速率定律。

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