Enhancing the Signal-to-Noise of Diagnostic Fragment Ions of Unsaturated Glycerophospholipids via Precursor Exclusion Ultraviolet Photodissociation Mass Spectrometry (PEx-UVPD-MS).
Enhancing the Signal-to-Noise of Diagnostic Fragment Ions of Unsaturated Glycerophospholipids via Precursor Exclusion Ultraviolet Photodissociation Mass Spectrometry (PEx-UVPD-MS).
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DOI：
10.1021/acs.analchem.2c02128
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发表时间：
2022-08-16
影响因子：
7.4
通讯作者：
Brodbelt, Jennifer S.
中科院分区：
文献类型：
--
作者：
Shields, Samuel W. J.;Sanders, James D.;Brodbelt, Jennifer S.
了解和阐明脂质的不同结构和功能，激发了许多创新的串联质谱（MS/MS）策略的发展。高能活化方法，如紫外光解离（UVPD），从甘油磷脂中产生独特的碎片离子，可用于进行深入的结构分析，并促进复杂样品中异构脂质结构的去卷积。虽然详细的表征是核心的脂质结构的相关性，生物功能，它往往是阻碍了缺乏足够的仪器灵敏度高生物活性，但低丰度磷脂。在这里，我们提出了前体排除（PEx）UVPD，一个简单而强大的技术，以提高信号噪声比（S/N）的信息低丰度碎片离子从UVPD的甘油磷脂。通过用MS 3策略排除大量未解离的前体离子，与单独的UVPD相比，对于PEx-UVPD，来自PC 18：0/18：2（9 Z，12 Z）的诊断碎片离子的S/N平均增加高达13倍。这些增强被扩展到复杂的混合物的脂质从牛肝提取物，以确定35个独特的结构，使用液相色谱PEX-UVPD。这种方法有可能通过提供更深入的结构解析和生物活性脂质的可靠鉴定来推进脂质组学研究。
Understanding and elucidating the diverse structures and functions of lipids has motivated the development of many innovative tandem mass spectrometry (MS/MS) strategies. Higher-energy activation methods, such as ultraviolet photodissociation (UVPD), generate unique fragment ions from glycerophospholipids that can be used to perform in-depth structural analysis and facilitate the deconvolution of isomeric lipid structures in complex samples. Although detailed characterization is central to the correlation of lipid structure to biological function, it is often impeded by the lack of sufficient instrument sensitivity for highly bioactive but low-abundance phospholipids. Here, we present precursor exclusion (PEx) UVPD, a simple yet powerful technique to enhance the signal-to-noise (S/N) of informative low-abundance fragment ions produced from UVPD of glycerophospholipids. Through the exclusion of the large population of undissociated precursor ions with an MS3 strategy, the S/N of diagnostic fragment ions from PC 18:0/18:2(9Z, 12Z) increased up to an average of 13x for PEx-UVPD compared to UVPD alone. These enhancements were extended to complex mixtures of lipids from bovine liver extract to confidently identify 35 unique structures using liquid chromatography PEx-UVPD. This methodology has the potential to advance lipidomics research by offering deeper structure elucidation and confident identification of biologically active lipids.
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DOI：
10.1016/j.bbalip.2017.04.006
发表时间：
2017-08
期刊：
Biochimica et biophysica acta. Molecular and cell biology of lipids
影响因子：
--
作者：
Gross RW
通讯作者：
Gross RW
DOI：
10.1021/jasms.0c00001
发表时间：
2020-04-01
影响因子：
3.2
作者：
Franklin, Elissia T.;Shields, Samuel W. J.;McLuckey, Scott A.
通讯作者：
McLuckey, Scott A.
影响因子：
7.4
作者：
Klein DR;Brodbelt JS
通讯作者：
Brodbelt JS
影响因子：
7.4
作者：
Feng, Yu;Chen, Bingming;Li, Lingjun
通讯作者：
Li, Lingjun
影响因子：
6.5
作者：
Fahy, Eoin;Subramaniam, Shankar;Dennis, Edward A.
通讯作者：
Dennis, Edward A.