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引用次数: 0
摘要
质盐是一类特殊的甘油磷脂,其特点是在甘油骨架的sn-1位置有一个乙烯基醚键(-C = C-O-)。在神经退行性疾病和癌症中已经观察到质粒卤素谱的改变。质谱分析需要指定乙烯基醚键,并将它们与各种类型的异构体和同分异构体区分开来。在此,我们通过离线帕特诺-布奇(Paternò-Büchi)反应将 C = C 衍生化与液相色谱-串联质谱联用,开发出一种灵敏的工作流程,用于分析生物样本中的质卤素。以牛心脏脂质提取物为模型系统,我们在 C = C 位置水平上分析了 100 多种不同结构的质子乙醇胺(PE-Ps)和质子胆碱(PC-Ps),远远超过了之前的报道。对人类胶质瘤和正常脑组织样本的分析表明,胶质瘤组织样本中 PE-Ps 的 n-10 C = C 异构体含量升高。这些发现表明,所开发的工作流程在帮助研究临床样本中质氨酸代谢改变方面具有潜力。
Deep profiling of plasmalogens by coupling the Paternò-Büchi derivatization with tandem mass spectrometry.
Plasmalogens are a special class of glycerophospholipids characterized by a vinyl ether bond (-C = C-O-) at the sn-1 position of the glycerol backbone. Altered plasmalogen profiles have been observed in neurodegenerative diseases and cancers. Profiling of plasmalogens requires specifying the vinyl ether bond and differentiating them from various types of isobars and isomers. Herein, by coupling C = C derivatization via offline Paternò-Büchi reaction with liquid chromatography-tandem mass spectrometry, we have developed a sensitive workflow for analysis of plasmalogens from biological samples. Using bovine heart lipid extract as a model system, we profiled more than 100 distinct structures of plasmenylethanolamines (PE-Ps) and plasmenylcholines (PC-Ps) at the C = C location level, far exceeding previous reports. Analysis of human glioma and normal brain tissue samples revealed elevated n-10 C = C isomers of PE-Ps in the glioma tissue samples. These findings suggest that the developed workflow holds potential in aiding the study of altered metabolism of plasmalogens in clinical samples.
期刊介绍:
Analytical and Bioanalytical Chemistry’s mission is the rapid publication of excellent and high-impact research articles on fundamental and applied topics of analytical and bioanalytical measurement science. Its scope is broad, and ranges from novel measurement platforms and their characterization to multidisciplinary approaches that effectively address important scientific problems. The Editors encourage submissions presenting innovative analytical research in concept, instrumentation, methods, and/or applications, including: mass spectrometry, spectroscopy, and electroanalysis; advanced separations; analytical strategies in “-omics” and imaging, bioanalysis, and sampling; miniaturized devices, medical diagnostics, sensors; analytical characterization of nano- and biomaterials; chemometrics and advanced data analysis.