Online Ozonolysis Combined with Ion Mobility-Mass Spectrometry Provides a New Platform for Lipid Isomer Analyses.
Online Ozonolysis Combined with Ion Mobility-Mass Spectrometry Provides a New Platform for Lipid Isomer Analyses.
复制标题
在线臭氧分解与离子淌度质谱联用为脂质异构体分析提供了新平台。
DOI：
10.1021/acs.analchem.7b04091
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发表时间：
2018-01-16
影响因子：
7.4
通讯作者：
Blanksby SJ
中科院分区：
文献类型：
--
作者：
Poad BLJ;Zheng X;Mitchell TW;Smith RD;Baker ES;Blanksby SJ
当代脂质组学中最重要的挑战之一在于分离和鉴定仅在碳-碳双键的不饱和位点或几何构型上不同的脂质异构体。虽然分析分离技术，包括离子迁移谱（IMS）和液相色谱（LC）可以在适当的条件下分离异构脂质，传统的串联质谱不能提供明确的鉴定。为了应对这一挑战，我们已经实现了臭氧诱导解离（OzID）与LC，IMS和高分辨率质谱仪在线。修改IMS-功能的四极杆飞行时间质谱仪进行，以允许引入臭氧到高压捕获离子漏斗区之前的IMS单元。这实现了新的LC-OzID-IMS-MS配置，其中电离脂质的臭氧分解快速发生（10 ms），而无需事先进行质量选择。LC-洗脱时间对准结合准确的质量和臭氧分解产物的到达时间提取促进了前体和产物离子的相关性，而没有质量选择（以及占空比的相关降低）。使用该工作流程在正离子和负离子模式下检查了11类不饱和脂质，并且在所有情况下，基于可预测的OzID转换明确分配了碳-碳双键的位置。在这些条件下，几何异构体表现出不同的IMS到达时间分布和不同的OzID产品离子比提供了一种手段，用于歧视复杂的脂质中的顺式/反式双键。OzID与多维分离的组合显示出对包括人血浆在内的复杂脂质体内的不饱和模式的简易分析的显著希望。
One of the most significant challenges in contemporary lipidomics lies in the separation and identification of lipid isomers that differ only in site(s) of unsaturation or geometric configuration of the carbon-carbon double bonds. While analytical separation techniques including ion mobility spectrometry (IMS) and liquid chromatography (LC) can separate isomeric lipids under appropriate conditions, conventional tandem mass spectrometry cannot provide unequivocal identification. To address this challenge, we have implemented ozone-induced dissociation (OzID) in-line with LC, IMS and high resolution mass spectrometry. Modification of an IMS-capable quadrupole time-of-flight mass spectrometer was undertaken to allow the introduction of ozone into the high-pressure trapping ion funnel region preceding the IMS cell. This enabled the novel LC-OzID-IMS-MS configuration where ozonolysis of ionized lipids occurred rapidly (10 ms) without prior mass-selection. LC-elution time alignment combined with accurate mass and arrival time extraction of ozonolysis products facilitated correlation of precursor and product ions without mass-selection (and associated reductions in duty cycle). Unsaturated lipids across 11 classes were examined using this workflow in both positive and negative ion modalities and in all cases the positions of carbon-carbon double bonds were unequivocally assigned based on predictable OzID transitions. Under these conditions geometric isomers exhibited different IMS arrival time distributions and distinct OzID product ion ratios providing a means for discrimination of cis/trans double bonds in complex lipids. The combination of OzID with multidimensional separations shows significant promise for facile profiling of unsaturation patterns within complex lipidomes including human plasma.
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影响因子：
4.2
作者：
Pham, Huong T.;Maccarone, Alan T.;Blanksby, Stephen J.
通讯作者：
Blanksby, Stephen J.
影响因子：
1.5
作者：
GREENE, CR;ATKINSON, R
通讯作者：
ATKINSON, R
影响因子：
13.1
作者：
Cajka, Tomas;Fiehn, Oliver
通讯作者：
Fiehn, Oliver
影响因子：
1.3
作者：
Kozlowski, Rachel L.;Mitchell, Todd W.;Blanksby, Stephen J.
通讯作者：
Blanksby, Stephen J.
影响因子：
2.7
作者：
Nakanishi, Hiroki;Iida, Yasuhiro;Taguchi, Ryo
通讯作者：
Taguchi, Ryo