Quantification of hydroxyl radical-derived oxidation products in peptides containing glycine, alanine, valine, and proline
Quantification of hydroxyl radical-derived oxidation products in peptides containing glycine, alanine, valine, and proline
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DOI：
10.1016/j.freeradbiomed.2011.10.448
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发表时间：
2012-01-15
影响因子：
7.4
通讯作者：
Davies, Michael J.
中科院分区：
文献类型：
--
作者：
Morgan, Philip E.;Pattison, David I.;Davies, Michael J.
蛋白质是氧化的主要目标，因为它们的丰度和高反应性。尽管多年来进行了广泛的研究，但只有有限的定量数据存在于不同途径对肽和蛋白质氧化的贡献。本研究旨在获得由原型氧化系统（HO-/O-2）在有限但已知的氨基酸组成的小肽上形成的氧化产物（醇、羰基、氢过氧化物、片段物种）的性质和产率的定量数据。研究人员对由Gly、Ala、Val和Pro组成的多肽进行了研究，特别强调了肽Val-Gly-Val-Ala-Pro-Gly，这是弹性蛋白中的一个重复基序，具有趋化活性和金属蛋白酶调节特性。获得的数据表明，过氧化氢的形成是非随机发生的（Pro > Val > Ala > Gly），这与羰基产率（肽结合和释放）呈负相关。在侧链和主链位点都生成了多个醇。骨架断裂的特征是在多个位置，与Pro残基相邻的位点是重要的。产物浓度的总和为暴露于HO-/O-2的肽中发生连锁反应提供了明确的证据，总体产物产量超过了最初产生的HO-。(C) 2011爱思唯尔公司版权所有。
Proteins are a major target for oxidation due to their abundance and high reactivity. Despite extensive investigation over many years, only limited quantitative data exist on the contributions of different pathways to the oxidation of peptides and proteins. This study was designed to obtain quantitative data on the nature and yields of oxidation products (alcohols, carbonyls, hydroperoxides, fragment species) formed by a prototypic oxidant system (HO-/O-2) on small peptides of limited, but known, amino acid composition. Peptides composed of Gly, Ala, Val, and Pro were examined with particular emphasis on the peptide Val-Gly-Val-Ala-Pro-Gly, a repeat motif in elastin with chemotactic activity and metalloproteinase regulation properties. The data obtained indicate that hydroperoxide formation occurs nonrandomly (Pro > Val > Ala > Gly) with this inversely related to carbonyl yields (both peptide-bound and released). Multiple alcohols are generated at both side-chain and backbone sites. Backbone fragmentation has been characterized at multiple positions, with sites adjacent to Pro residues being of major importance. Summation of the product concentrations provides clear evidence for the occurrence of chain reactions in peptides exposed to HO-/O-2, with the overall product yields exceeding that of the initial HO- generated. (C) 2011 Elsevier Inc. All rights reserved.