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利用气相电荷反转离子/离子反应和红外多光子解离对成像质谱中的脂质异构体进行相对定量。

Relative Quantification of Lipid Isomers in Imaging Mass Spectrometry Using Gas-Phase Charge Inversion Ion/Ion Reactions and Infrared Multiphoton Dissociation.

机构信息

Department of Chemistry, University of Florida, Gainesville, Florida 32611, United States.

出版信息

Anal Chem. 2023 Dec 5;95(48):17766-17775. doi: 10.1021/acs.analchem.3c03804. Epub 2023 Nov 22.

Abstract

Accurate structural identification of lipids in imaging mass spectrometry is critical to properly contextualizing spatial distributions with tissue biochemistry. Gas-phase charge inversion ion/ion reactions alter the ion type prior to dissociation to allow for more structurally informative fragmentation and improve lipid identification at the isomeric level. In this work, infrared multiphoton dissociation (IRMPD) was interfaced with a commercial hybrid Qh-FT-ICR mass spectrometer to enable the rapid fragmentation of gas-phase charge inversion ion/ion reaction products at every pixel in imaging mass spectrometry experiments. An ion/ion reaction between phosphatidylcholine (PC) monocations generated from rat brain tissue via matrix-assisted laser desorption/ionization (MALDI) and 1,4-phenylenediproprionic acid reagent dianions generated via electrospray ionization (ESI) followed by IRMPD of the resulting product ion complex produces selective fatty acyl chain cleavages indicative of fatty acyl carbon compositions in the lipid. Ion/ion reaction images using this workflow allow for mapping of the relative spatial distribution of multiple PC isomers under a single sum composition lipid identification. Lipid isomers display significantly different relative spatial distributions within rat brain tissue, highlighting the importance of resolving isomers in imaging mass spectrometry experiments.

摘要

准确识别成像质谱中的脂质结构对于正确将空间分布与组织生物化学联系起来至关重要。气相电荷反转离子/离子反应在解离前改变离子类型,从而实现更具结构信息的碎片化,并提高在异构体水平上的脂质识别能力。在这项工作中,红外多光子解离(IRMPD)与商业混合 Qh-FT-ICR 质谱仪联用,能够在成像质谱实验的每个像素中快速碎裂气相电荷反转离子/离子反应产物。通过基质辅助激光解吸/电离(MALDI)从大鼠脑组织中生成的磷脂酰胆碱(PC)单阳离子与通过电喷雾电离(ESI)生成的 1,4-亚苯基二丙二酸试剂二阴离子之间的离子/离子反应,然后对生成的产物离子复合物进行 IRMPD,产生选择性的脂肪酸链断裂,表明脂质中的脂肪酸碳组成。使用此工作流程的离子/离子反应图像允许在单个总和组成脂质识别下对多个 PC 异构体的相对空间分布进行映射。脂质异构体在大鼠脑组织内的相对空间分布存在显著差异,突出了在成像质谱实验中解析异构体的重要性。

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