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评价模型肽骨架中硫醚基团邻近性的羟基自由基反应活性：蛋氨酸与 S-甲基半胱氨酸。

Evaluation of Hydroxyl Radical Reactivity by Thioether Group Proximity in Model Peptide Backbone: Methionine versus S-Methyl-Cysteine.

机构信息

Center for Advanced Technology, Adam Mickiewicz University, Uniwersytetu Poznanskiego 10, 61-614 Poznan, Poland.

ISOF, Consiglio Nazionale delle Ricerche, Via P. Gobetti 101, 40129 Bologna, Italy.

出版信息

Int J Mol Sci. 2022 Jun 11;23(12):6550. doi: 10.3390/ijms23126550.

DOI:10.3390/ijms23126550
PMID:35742994
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9224496/
Abstract

Hydroxyl radicals (HO) have long been regarded as a major source of cellular damage. The reaction of HO with methionine residues (Met) in peptides and proteins is a complex multistep process. Although the reaction mechanism has been intensively studied, some essential parts remain unsolved. In the present study we examined the reaction of HO generated by ionizing radiation in aqueous solutions under anoxic conditions with two compounds representing the simplest model peptide backbone CHC(O)NHCHXC(O)NHCH, where X = CHCHSCH or CHSCH, i.e., the Met derivative in comparison with the cysteine-methylated derivative. We performed the identification and quantification of transient species by pulse radiolysis and final products by LC-MS and high-resolution MS/MS after γ-radiolysis. The results allowed us to draw for each compound a mechanistic scheme. The fate of the initial one-electron oxidation at the sulfur atom depends on its distance from the peptide backbone and involves transient species of five-membered and/or six-membered ring formations with different heteroatoms present in the backbone as well as quite different rates of deprotonation in forming α-(alkylthio)alkyl radicals.

摘要

羟基自由基 (HO) 长期以来一直被认为是细胞损伤的主要来源。HO 与肽和蛋白质中蛋氨酸残基 (Met) 的反应是一个复杂的多步骤过程。尽管已经对反应机制进行了深入研究，但仍有一些关键部分尚未解决。在本研究中，我们研究了在缺氧条件下离子辐射产生的 HO 与两种化合物的反应，这两种化合物代表最简单的模型肽骨架 CHC(O)NHCHXC(O)NHCH，其中 X = CHCHSCH 或 CHSCH，即 Met 衍生物与半胱氨酸甲基化衍生物的反应。我们通过脉冲辐射解法鉴定和定量了瞬态物种，并在 γ 辐射后通过 LC-MS 和高分辨率 MS/MS 确定了最终产物。结果允许我们为每个化合物绘制一个机制方案。硫原子上的初始单电子氧化的命运取决于其与肽骨架的距离，并涉及五元环和/或六元环形成的瞬态物种，其中骨架中存在不同的杂原子，以及形成 α-(烷基硫代)烷基自由基的不同去质子化速率。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9846/9224496/b6db8ca6133c/ijms-23-06550-g006.jpg
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