Complex lipids, phospholipids (PLs) and triacylglycerides (TAGs), are prone to modifications induced by reactive nitrated species and reactive oxygen species, generating a range of nitrated, nitrosated or nitroxidized derivatives, as nitro PLs and nitro TAGs. These modified lipids (epilipids) have been reported in vitro and in vivo using lipidomics approaches. However, their detection in living systems remains a challenge hampered by its complexity, high structural diversity, and low abundance. The advances in high-resolution mass spectrometry combined with the higher sensitivity of the instruments like Orbitrap-based mass spectrometers opened new opportunities for the detection of these modified complex lipids. This review summarizes the challenges and findings behind the identification of nitrated, nitrosated and nitroxidized PLs and TAGs fragmentation fingerprints based on collision-induced dissociation (CID) and higher energy CID (HCD) MS/MS approaches. Following what has already been reported for nitrated fatty acids, these complex lipids are found to act as endogenous mediators with potential electrophilic properties and can express bioactivities such as anti-inflammatory and antioxidant actions. This information can be used to design untargeted and targeted lipidomics strategies for these modified complex lipids in biological samples as well as in pathological, food and industrial settings, further unveiling their biological and signalling roles.

复杂的脂质、磷脂 (PL) 和三酰基甘油酯 (TAG) 容易受到活性硝化物质和活性氧物质诱导的修饰，产生一系列硝化、亚硝化或硝基氧化衍生物，如硝基 PL 和硝基 TAG。已在体外和体内报道了这些修饰的脂质（表脂质）使用脂质组学方法。然而，由于其复杂性、高结构多样性和低丰度，它们在生命系统中的检测仍然是一项挑战。高分辨率质谱技术的进步与基于 Orbitrap 的质谱仪等仪器的更高灵敏度相结合，为检测这些修饰的复杂脂质开辟了新的机会。本综述总结了基于碰撞诱导解离 (CID) 和高能 CID (HCD) MS/MS 方法识别硝化、亚硝化和硝化 PL 和 TAG 碎片指纹背后的挑战和发现。继已报道的硝化脂肪酸之后，这些复杂的脂质被发现充当具有潜在亲电特性的内源性介质，并且可以表达抗炎和抗氧化作用等生物活性。这些信息可用于为生物样品以及病理、食品和工业环境中的这些修饰的复杂脂质设计非靶向和靶向脂质组学策略，进一步揭示它们的生物学和信号传导作用。