The post-translational modification of proteins by electrophilic oxylipids is emerging as an important mechanism that contributes to the complexity of proteomes. Enzymatic and non-enzymatic oxidation of biological lipids results in the formation of chemically diverse electrophilic carbonyl compounds, such as 2-alkenals and 4-hydroxy alkenals, epoxides, and eicosanoids with reactive cyclopentenone structures. These lipoxidation products are capable of modifying proteins. Originally considered solely as markers of oxidative insult, more recently the modifications of proteins by lipid peroxidation products are being recognized as a new mechanism of cell signaling with relevance to redox homeostasis, adaptive response and inflammatory resolution. The growing interest in protein modifications by reactive oxylipid species necessitates the availability of methods that are capable of detecting, identifying and characterizing these protein adducts in biological samples with high complexity. However, the efficient analysis of these chemically diverse protein adducts presents a considerable analytical challenge. We first provide an introduction into the chemistry and biological relevance of protein adductions by electrophilic lipoxidation products. We then provide an overview of tandem mass spectrometry approaches that have been developed in recent years for the interrogation of protein modifications by electrophilic oxylipid species.

中文翻译：

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亲电脂肪氧化产物的蛋白质修饰：加合物形成、化学策略和串联质谱法检测和鉴定。

亲电氧化脂质对蛋白质的翻译后修饰正在成为导致蛋白质组复杂性的重要机制。生物脂质的酶促和非酶促氧化导致形成化学上多样化的亲电羰基化合物，例如 2-链烯醛和 4-羟基链烯醛、环氧化物和具有反应性环戊烯酮结构的类花生酸。这些脂肪氧化产物能够修饰蛋白质。最初仅被认为是氧化损伤的标志物，最近脂质过氧化产物对蛋白质的修饰被认为是一种与氧化还原稳态、适应性反应和炎症消退相关的细胞信号传导的新机制。对活性氧脂类蛋白质修饰的兴趣日益浓厚，因此需要能够检测、鉴定和表征具有高度复杂性的生物样品中的这些蛋白质加合物的方法的可用性。然而，对这些化学上多样化的蛋白质加合物的有效分析提出了相当大的分析挑战。我们首先介绍了亲电脂肪氧化产物对蛋白质加合物的化学和生物学相关性。然后，我们概述了近年来开发的串联质谱方法，用于询问亲电子氧脂物种的蛋白质修饰。对这些化学性质多样的蛋白质加合物进行有效分析提出了相当大的分析挑战。我们首先介绍了亲电脂肪氧化产物对蛋白质加合物的化学和生物学相关性。然后，我们概述了近年来开发的串联质谱方法，用于询问亲电子氧脂物种的蛋白质修饰。对这些化学性质多样的蛋白质加合物进行有效分析提出了相当大的分析挑战。我们首先介绍了亲电脂肪氧化产物对蛋白质加合物的化学和生物学相关性。然后，我们概述了近年来开发的串联质谱方法，用于询问亲电子氧脂物种的蛋白质修饰。