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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Kinetics and Mechanism of the Oxidation of N?Acetyl Homocysteine Thiolactone with Aqueous Iodine and Iodate
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Kinetics and Mechanism of the Oxidation of N?Acetyl Homocysteine Thiolactone with Aqueous Iodine and Iodate

机译：碘和碘酸盐氧化N N乙酰基同型半胱氨酸硫内酯的动力学及机理

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摘要

The kinetics of N-acetyl homocysteine thiolactone (NAHT) oxidation by aqueous iodine and iodate were studied by spectrophotometric techniques. The iodate?NAHT reaction is slow and results in the formation of N-acetyl homocysteine thiolactone sulfoxide as the sole product (NAHTSO). The stoichiometry of the reaction was deduced as: IO_3~? + 3NAHT → I~? + 3NAHTSO (S1). In excess iodate conditions, the iodide produced in S1 is oxidized to give iodine: IO_3~? + 5I~? + 6H~+ → 3I_2 + 3H2O (S2). Thus in excess iodate conditions the overall stoichiometry of the reaction is a linear combination of S1 and S2 that eliminates iodide, 5S1 + S2: 2IO_3~?+ 5NAHT+ 2H~+ → I_2 + 5NAHTSO + H_2O. There was a 1:1 stoichiometry for the NAHT ? I_2 reaction: NAHT+ I_2 + H_2O → NAHTSO +2I? + 2H~+ (S3). All reactions, S1, S2 and S3 occur simultaneously and since they are all comparable in rate; complex dynamics were observed. Iodide catalyzes S1 and S2 but inhibits S3. Iodide is a product of both S1 and S3. It has the most profound effect on the overall global dynamics observed. The overall reaction scheme which involved S1, S2 and S3 was modeled by a simple 12-reaction mechanistic scheme which gave a very good fit to experimental data.
机译：用分光光度法研究了碘水溶液和碘酸盐对N-乙酰基高半胱氨酸硫代内酯（NAHT）氧化的动力学。碘酸盐·NAHT反应缓慢，导致形成N-乙酰基高半胱氨酸硫代内酯亚砜作为唯一产物（NAHTSO）。该反应的化学计量推导为：IO_3〜？ + 3NAHT→我〜？ + 3NAHTSO（S1）。在过量碘酸盐条件下，S1中产生的碘化物被氧化生成碘：IO_3〜。 + 5I〜？ + 6H〜+→3I_2 + 3H2O（S2）。因此，在过量碘酸盐条件下，反应的总化学计量是S1和S2的线性组合，其消除了碘化物，5S1 + S2：2IO_3〜+ 5NAHT + 2H〜+→I_2 + 5NAHTSO + H_2O。 NAHT的化学计量比为1：1。 I_2反应：NAHT + I_2 + H_2O→NAHTSO + 2I？ + 2H〜+（S3）。所有反应S1，S2和S3均同时发生，因为它们的速率均相当。观察到复杂的动力学。碘化物催化S1和S2，但抑制S3。碘化物是S1和S3的产物。它对观察到的整体全球动态具有最深远的影响。涉及S1，S2和S3的总反应方案通过简单的12反应机理模型进行建模，该方案非常适合实验数据。

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