School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, United States.
NSF/NASA Center for Chemical Evolution, Atlanta, Georgia 30332, United States.
Anal Chem. 2021 Apr 6;93(13):5468-5475. doi: 10.1021/acs.analchem.0c05145. Epub 2021 Mar 15.
Lipids play a critical role in cell membrane integrity, signaling, and energy storage. However, in-depth structural characterization of lipids is still challenging and not routinely possible in lipidomics experiments. Techniques such as collision-induced dissociation (CID) tandem mass spectrometry (MS/MS), ion mobility (IM) spectrometry, and ultrahigh-performance liquid chromatography are not yet capable of fully characterizing double-bond and -chain position of lipids in a high-throughput manner. Herein, we report on the ability to structurally characterize lipids using large-area triboelectric nanogenerators (TENG) coupled with time-aligned parallel (TAP) fragmentation IM-MS analysis. Gas-phase lipid epoxidation during TENG ionization, coupled to mobility-resolved MS via TAP IM-MS, enabled the acquisition of detailed information on the presence and position of lipid C═C double bonds, the fatty acyl -chain position and composition, and the / geometrical C═C isomerism. The proposed methodology proved useful for the shotgun lipidomics analysis of lipid extracts from biological samples, enabling the detailed annotation of numerous lipid isobars.
脂质在细胞膜完整性、信号传递和能量存储中起着至关重要的作用。然而，深入的脂质结构特征分析仍然具有挑战性，在脂质组学实验中也无法常规进行。碰撞诱导解离（CID）串联质谱（MS/MS）、离子淌度（IM）谱和超高效液相色谱等技术目前还无法以高通量的方式全面表征脂质的双键和链位置。在此，我们报告了使用大面积摩擦纳米发电机（TENG）与时间对齐平行（TAP）碎裂 IM-MS 分析相结合来对脂质进行结构特征分析的能力。TENG 电离过程中的气相脂质环氧化，通过 TAP IM-MS 与淌度分辨 MS 耦合，使我们能够获取关于脂质 C═C 双键的存在和位置、脂肪酸酰基链位置和组成以及 / 几何 C═C 异构体的详细信息。所提出的方法对于生物样本脂质提取物的鸟枪法脂质组学分析非常有用，能够详细注释许多脂质同量异位体。
