Characterization of glycerophospholipids at multiple isomer levels <i>via</i> Mn(<scp>ii</scp>)-catalyzed epoxidation

Chen, Xi; Tang, Shuli; Freitas, Dallas; Hirtzel, Erin; Cheng, Heyong; Yan, Xingru

doi:10.1039/d2an01174c

Cited by 5 publications

(3 citation statements)

References 59 publications

(94 reference statements)

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“…The formation efficacy of [L + Co] 2+ varied in the order POPE > POPC ≥ POPS > POPG but no correlation of this efficacy trend to reported gasphase basicities were observed. 58 Similar to our previous findings 53 and reports by Hale and Cramer 54 as well as the group of Yan, 59 the transition metals Co 2+ , Mn 2+ , and Fe 2+ yielded comparable intensities of [POPE + M] 2+ ions, whereas addition of Cu 2+ resulted only in the formation of low abundant signals of the doubly charged complex (Figure 1c). But also Ba 2+ , as reported before for PCs, 53,54 and Mg 2+ as well as Ca 2+ form [POPE + M] 2+ ions and the relative intensity of these complexes increase with increasing ion radii (r(Ba 2+ ) > r(Ca 2+ ) > r(Mg 2+ )).…”

Section: Methodssupporting

confidence: 89%

“…53 These structures are consistent with all available experimental results for PCs and the sn-selectivity of the fragmentation step. 53,54,59,62 As among the investigated GPLs only PEs contained these fragments, we investigated if snselective fragmentation of [PE + M] 2+ is possible, and the results of corresponding PLA 2 digestions compared to HCD-MS 2 of [PE + Co] 2+ are shown in Table 1. All available authentic PE standards but one contain the unsaturated FA in the sn-2 position, and only PE 18:1(9Z)/16:0 (OPPE) is available with oleic acid attached to sn-1.…”

Section: Proposed Fragmentation Pathways Of [L + M] 2+mentioning

confidence: 99%

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Formation and Tandem Mass Spectrometry of Doubly Charged Lipid-Metal Ion Complexes

Hormann,

Sommer,

Heiles

2023

J. Am. Soc. Mass Spectrom.

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Phospholipids are major components of most eukaryotic cell membranes. Changes in metabolic states are often accompanied by phospholipid structure variations. The structural changes of phospholipids are the hallmark of disease states, or specific lipid structures have been associated with distinct organisms. Prime examples are microorganisms that synthesize phospholipids with, for example, different branched chain fatty acids. Assignment and relative quantitation of structural isomers of phospholipids that arise from attachment of different fatty acids to the glycerophospholipid backbone are difficult with routine tandem mass spectrometry or with liquid chromatography without authentic standards. In this work, we report on the observation that all investigated phospholipid classes form doubly charged lipid-metal ion complexes during electrospray ionization (ESI) and show that these complexes can be used to assign lipid classes and fatty acid moieties, distinguish isomers of branched chain fatty acids, and relatively quantify these isomers in positive-ion mode. Use of water free methanol and addition of divalent metal salts (100 mol %) to ESI spray solutions afford highly abundant doubly charged lipid-metal ion complexes (up to 70 times of protonated compounds). Higher-energy collisional dissociation and collision-induced dissociation of doubly charged complexes yield a diverse set of lipid class-dependent fragment ions. In common for all lipid classes is the liberation of fatty acid-metal adducts that yield fragment ions from the fatty acid hydrocarbon chain upon activation. This ability is used to pinpoint sites of branching in saturated fatty acids and is showcased for free fatty acids as well as glycerophospholipids. The analytical utility of doubly charged phospholipid-metal ion complexes is demonstrated by distinguishing fatty acid branching-site isomers in phospholipid mixtures and relatively quantifying the corresponding isomeric compounds.

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Section: Methodssupporting

confidence: 89%

Section: Proposed Fragmentation Pathways Of [L + M] 2+mentioning

confidence: 99%

Formation and Tandem Mass Spectrometry of Doubly Charged Lipid-Metal Ion Complexes

Hormann,

Sommer,

Heiles

2023

J. Am. Soc. Mass Spectrom.

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“…Along with other method advancements for isomeric lipid characterization, − a few methodologies have been developed to target sn -positional isomer identification. These include charge inversion ion–ion reactions, anion/cation adduction of lipids, ,− radical-induced dissociation of bicarbonate-adducted lipids, CID fragmentation coupled with ozone-induced fragmentation, electron-induced dissociation of lipids, and coupling MS with ion mobility …”

mentioning

confidence: 99%

Lipid Isobaric Mass Tagging for Enhanced Relative Quantification of Unsaturated sn-Positional Isomers

Yang,

Tang,

Feng

et al. 2024

ACS Meas. Sci. Au

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Changes in the levels of lipid sn-positional isomers are associated with perturbation of the physiological environment within the biological system. Consequently, knowing the concentrations of these lipids holds significant importance for unraveling their involvement in disease diagnosis and pathological mechanisms. However, existing methods for lipid quantification often fall short in accuracy due to the structural diversity and isomeric forms of lipids. To address this challenge, we have developed an aziridine-based isobaric tag labeling strategy that allows (i) differentiation and (ii) enhanced relative quantification of lipid snpositional isomers from distinct samples in a single run. The methodology enabled by aziridination, isobaric tag labeling, and lithiation has been applied to various phospholipids, enabling the determination of the sn-positions of fatty acyl chains and enhanced relative quantification. The analysis of Escherichia coli lipid extracts demonstrated the enhanced determination of the concentration ratios of lipid isomers by measuring the intensity ratios of mass reporters released from sn-positional diagnostic ions. Moreover, we applied the method to the analysis of human colon cancer plasma. Intriguingly, 17 PC lipid sn-positional isomers were identified and quantified simultaneously, and among them, 7 showed significant abundance changes in the colon cancer plasma, which can be used as potential plasma markers for diagnosis of human colon cancer.

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In situ droplet-based on-tissue chemical derivatization for lipid isomer characterization using LESA

et al. 2023

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Characterization of glycerophospholipids at multiple isomer levels via Mn(ii)-catalyzed epoxidation

Abstract: Characterization of glycerophospholipid isomers is of significant importance as they play different roles in physiological and pathological processes. In this work, we present a novel and bifunctional derivatization method utilizing...

Cited by 5 publications

References 59 publications

Formation and Tandem Mass Spectrometry of Doubly Charged Lipid-Metal Ion Complexes

Formation and Tandem Mass Spectrometry of Doubly Charged Lipid-Metal Ion Complexes

Lipid Isobaric Mass Tagging for Enhanced Relative Quantification of Unsaturated sn-Positional Isomers

In situ droplet-based on-tissue chemical derivatization for lipid isomer characterization using LESA

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