This review describes the mass spectral fragmentation of trimethylsilyl (TMS) and related alkylsilyl derivatives used for preparing samples for analysis, mainly by combined gas chromatography and mass spectrometry (GC/MS). The review is divided into three sections. The first section is concerned with the TMS derivatives themselves and describes fragmentation of derivatized alcohols, thiols, amines, ketones, carboxylic acids and bifunctional compounds such as hydroxy- and amino-acids, halo acids and hydroxy ethers. More complex compounds such as glycerides, sphingolipids, carbohydrates, organic phosphates, phosphonates, steroids, vitamin D, cannabinoids, and prostaglandins are discussed next. The second section describes intermolecular reactions of siliconium ions such as the TMS cation and the third section discusses other alkylsilyl derivatives. Among these latter compounds are di- and trialkyl-silyl derivatives, various substituted-alkyldimethylsilyl derivatives such as the tert-butyldimethylsilyl ethers, cyclic silyl derivatives, alkoxysilyl derivatives, and 3-pyridylmethyldimethylsilyl esters used for double bond location in fatty acid spectra. © 2019 Wiley Periodicals, Inc. Mass Spec Rev 0000:1-107, 2019.

中文翻译：

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三甲基甲硅烷基和相关的烷基甲硅烷基衍生物的质谱分馏。

这篇综述描述了三甲基甲硅烷基（TMS）和相关烷基甲硅烷基衍生物用于制备样品的质谱碎片化方法，主要是通过气相色谱和质谱联用（GC / MS）进行的。该评论分为三个部分。第一部分涉及TMS衍生物本身，并描述了衍生化的醇，硫醇，胺，酮，羧酸和双官能化合物（例如羟基和氨基酸，卤代酸和羟基醚）的裂解。接下来讨论更复杂的化合物，例如甘油酯，鞘脂，碳水化合物，有机磷酸盐，膦酸酯，类固醇，维生素D，大麻素和前列腺素。第二部分描述了硅离子（如TMS阳离子）的分子间反应，第三部分讨论了其他烷基甲硅烷基衍生物。这些后者化合物中有二烷基和三烷基甲硅烷基衍生物，各种取代的烷基二甲基甲硅烷基衍生物，例如叔丁基二甲基甲硅烷基醚，环状甲硅烷基衍生物，烷氧基甲硅烷基衍生物和3-吡啶基甲基二甲基甲硅烷基酯，它们用于脂肪酸光谱中的双键定位。分级为4 +©2019 Wiley Periodicals，Inc.Mass Spec Rev 0000：1-107，2019。