Structural characterization of sphingomyelins from tissue using electron-induced dissociation

IF 1.8 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry Pub Date : 2024-06-27 DOI:10.1002/rcm.9844

Tingting Yan, Boone M. Prentice

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引用次数: 0

Abstract

Rationale

Sphingomyelins (SMs) and resulting metabolic products serve important functional and cell signaling roles and can act as potential biomarkers and therapeutic targets in many pathological disorders. SMs each contain a sphingoid base, an amide-linked fatty acyl chain, and a phosphocholine headgroup. Despite these simple building blocks, variations and modifications of both the sphingoid base and the fatty acyl chain result in a diverse array of structurally complicated SM compounds. Conventional tandem mass spectrometry (MS/MS) using the collision-induced dissociation (CID) method only provides limited structural information, necessitating other tools to unravel the structural complexity of these lipids.

Methods

We utilize electron-induced dissociation (EID) and sequential CID/EID approaches to elucidate detailed structural features of SMs. Integrating the CID/EID method into an imaging MS workflow enables accurate identification of SMs directly from kidney tissue.

Results

The application of EID enables identification of SMs at the molecular species level, identifying the sphingosine base and the amide-linked fatty acyl chains. Furthermore, removal of the phosphocholine headgroup via CID followed by sequential EID in an MS³ analysis (CID/EID) enhances the structural information obtained. CID/EID provides diagnostic fragmentation patterns revealing the hydroxylation site and double bond position in both the sphingosine base and amide-linked fatty acyl chains.

Conclusions

Detailed structural information of SMs from synthetic standards and biological tissue samples is obtained using an alternative electron-based dissociation method. Accurate characterization of SMs promises to better inform studies of tissue biochemistry, lipid metabolism, and molecular pathology.

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利用电子诱导解离法确定组织中鞘磷脂的结构特征。

理论依据：鞘磷脂（SMs）及其代谢产物具有重要的功能和细胞信号转导作用，可作为许多病理疾病的潜在生物标记物和治疗靶标。每种鞘磷脂都含有一个鞘磷脂基、一个酰胺链脂肪酰基链和一个磷脂酰胆碱头基。尽管这些结构单元很简单，但鞘氨醇基和脂肪酰基链的变化和修饰会产生一系列结构复杂的 SM 化合物。使用碰撞诱导解离（CID）方法的传统串联质谱法（MS/MS）只能提供有限的结构信息，因此有必要使用其他工具来揭示这些脂质的复杂结构：方法：我们利用电子诱导解离（EID）和顺序 CID/EID 方法来阐明 SMs 的详细结构特征。将 CID/EID 方法整合到成像质谱工作流程中，可直接从肾组织中准确鉴定 SMs：结果：应用 EID 可以在分子物种水平上鉴定 SMs，识别鞘磷脂基和酰胺连接的脂肪酰基链。此外，在 MS3 分析（CID/EID）中通过 CID 去除磷脂酰胆碱头基，然后进行连续 EID，可增强所获得的结构信息。CID/EID 提供的诊断碎片模式揭示了鞘磷脂基和酰胺链脂肪酰基链中的羟基化位点和双键位置：结论：使用另一种基于电子的解离方法从合成标准和生物组织样本中获得了SMs的详细结构信息。SMs 的准确表征有望为组织生物化学、脂质代谢和分子病理学研究提供更好的信息。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Rapid Communications in Mass Spectrometry 化学-分析化学

CiteScore

4.10

自引率

5.00%

发文量

219

审稿时长

2.6 months

期刊介绍： Rapid Communications in Mass Spectrometry is a journal whose aim is the rapid publication of original research results and ideas on all aspects of the science of gas-phase ions; it covers all the associated scientific disciplines. There is no formal limit on paper length ("rapid" is not synonymous with "brief"), but papers should be of a length that is commensurate with the importance and complexity of the results being reported. Contributions may be theoretical or practical in nature; they may deal with methods, techniques and applications, or with the interpretation of results; they may cover any area in science that depends directly on measurements made upon gaseous ions or that is associated with such measurements.