Voltage-Controlled Divergent Cascade of Electrochemical Reactions for Characterization of Lipids at Multiple Isomer Levels Using Mass Spectrometry

Tang, Shuli; Chen, Xi; Ke, Yuepeng; Wang, Fen; Yan, Xingru

doi:10.1021/acs.analchem.2c02375

Cited by 22 publications

(19 citation statements)

References 67 publications

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“…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%

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: 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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“…8 Tang et al identied the position of lipid C]C isomers and sn-isomers by combining two voltage-dependent electrochemical reactions, interfacial electro-epoxidation, and cobalt anodic corrosion in a single nano-ESI. 9,12 Double bonds are widely present in biomolecules, and are a signicant contributor to the spatial conformation of biomolecules. The efficient identication of the position and the number of double bonds in biomolecules is important in biochemistry as it helps reect the misexpression of cells and other related information of metabolic diseases.…”

Section: Introductionmentioning

confidence: 99%

“…The supposed "downside" of ESI oxidation has also been utilized for specialpurpose analyses. 3,[8][9][10][11][12] For example, Cheng et al used a Pd electrode to release the Pd cation to catalyze the Suzuki coupling reaction at room temperature during mass spectrometry analysis. 8 Tang et al identied the position of lipid C]C isomers and sn-isomers by combining two voltage-dependent electrochemical reactions, interfacial electro-epoxidation, and cobalt anodic corrosion in a single nano-ESI.…”

Section: Introductionmentioning

confidence: 99%

Tuning oxidative modification by a strong electric field using nanoESI of highly conductive solutions near the minimum flow rate

et al. 2023

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“…The chemical conversion of a CC into a functional group that can be readily dissociated by MS/MS is another successful strategy . Notable derivatization methods which have been applied to lipidomic analysis include the Paternò–Büchi (PB) reaction, − epoxidation, − singlet oxygen-ene reaction, and aziridination. , These derivatization methods enjoy the advantage of being instrument independent and the flexibility to be coupled with different lipidomic analysis settings, including shotgun, , liquid chromatography (LC), , and mass spectrometry imaging. ,− However, compared to the gas-phase dissociation methods, special care needs to be drawn to the derivatization step, which contributes to the overall performance of lipid identification and quantitation.…”

Section: Introductionmentioning

confidence: 99%

Visible-Light Paternò–Büchi Reaction for Lipidomic Profiling at Detailed Structure Levels

et al. 2023

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The Paternò–Büchi (PB) derivatization of carbon–carbon double bond (CC) has been increasingly employed with tandem mass spectrometry to analyze unsaturated lipids. It enables the discovery of altered or uncanonical lipid desaturation metabolism, which would be otherwise undetected by conventional methods. Although highly useful, the reported PB reactions only provide moderate yield (∼30%). Herein, we aim to determine the key factors that affect the PB reactions and develop a system with improved capabilities for lipidomic analysis. An Ir(III) photocatalyst is chosen as the triplet energy donor for the PB reagent under 405 nm light irradiation, while phenylglyoxalate and its charge-tagging version, pyridylglyoxalate, are developed as the most efficient PB reagents. The above visible-light PB reaction system provides higher PB conversions than all previously reported PB reactions. Around 90% conversion can be achieved at high concentrations (>0.5 mM) for different classes of lipids but drops as the lipid concentration decreases. The visible-light PB reaction has then been integrated with shotgun and liquid chromatography-based workflows. The limits of detection for locating CC in standard lipids of glycerophospholipids (GPLs) and triacylglycerides (TGs) are in the sub-nM to nM range. More than 600 distinct GPLs and TGs have been profiled at the CC location level or the sn-position level from the total lipid extract of bovine liver, demonstrating that the developed method is capable of large-scale lipidomic analysis.

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Voltage-Controlled Divergent Cascade of Electrochemical Reactions for Characterization of Lipids at Multiple Isomer Levels Using Mass Spectrometry

Cited by 22 publications

References 67 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

Tuning oxidative modification by a strong electric field using nanoESI of highly conductive solutions near the minimum flow rate

Visible-Light Paternò–Büchi Reaction for Lipidomic Profiling at Detailed Structure Levels

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