Enhanced Characterization of Cardiolipins via Hybrid 193 nm Ultraviolet Photodissociation Mass Spectrometry

Macias, Luis A.; Brodbelt, Jennifer S.

doi:10.1021/acs.analchem.1c05071

Cited by 3 publications

(2 citation statements)

References 89 publications

(200 reference statements)

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“…Fragments diagnostic for sn ‐positions, however, could only be generated in positive ion mode. Therefore, an improved procedure for cardiolipin analysis was developed, which relies on methylation of the phosphates to increase the ionization efficiency in positive polarity [47b] . Hybrid HCD/UVPD of metal‐cationized methylated cardiolipins afforded both double bond and sn ‐position specific fragmentation.…”

Section: Photodissociation Of Lipids In Tandem Mass Spectrometrymentioning

confidence: 99%

Lipid Analysis by Mass Spectrometry coupled with Laser Light

Kirschbaum

Pagel

2022

Analysis & Sensing

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Lipids are small but complex biomolecules that feature an immense structural and functional diversity. The molecular structure and biological functions of lipids are intricately linked. Therefore, modern lipid analysis strives for complete structural elucidation and spatial mapping of individual species in tissues. Mass spectrometry is the uncontested key technology in lipidomics but cannot achieve this goal as a standalone technique. In particular, the distinction between frequently occurring isomers constitutes a major challenge. A promising step towards complete structural analysis of lipids consists in the coupling of mass spectrometry with laser light. Here we review recent advances in lipidomics applications employing laser‐induced ultraviolet and infrared photodissociation and ion spectroscopy, which substantially increase the gain in structural information. Fundamental concepts, instrumentation and promises of these powerful emerging techniques for future lipid analysis are outlined.

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Section: Photodissociation Of Lipids In Tandem Mass Spectrometrymentioning

confidence: 99%

Lipid Analysis by Mass Spectrometry coupled with Laser Light

Kirschbaum

Pagel

2022

Analysis & Sensing

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“…Isomer discrimination is of significant importance and well-acknowledged to be a challenging problem. Direct mass spectrometry (MS)-based methods, albeit with the merits of sensitivity and efficiency, are generally not suitable for this purpose because of the identical mass of the isomers, but it is possible to overcome such obstacles with the aid of liquid and gas chromatography, − ion mobility spectrometry, − and ultraviolet as well as infrared spectroscopy. − Additionally, tandem MS has evolved as another crucial means for isomer discrimination on the basis of the diagnostic ratio of fragment ions. − …”

Section: Introductionmentioning

confidence: 99%

Influence of Metal Coordination on the Gas-Phase Chemistry of the Positional Isomers of Fluorobenzoate Complexes

Xiong

Yang

Chen

et al. 2022

J. Am. Soc. Mass Spectrom.

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The fragmentation behaviors of the o-, m-, and p-fluorobenzoate complexes of La 3+ , Ce 3+ , Fe 3+ , Cu 2+ , and UO 2 2+ were investigated by electrospray ionization mass spectrometry, and the corresponding reaction mechanisms were explored by density functional theory (DFT) calculations. Fluoride transfer product La III FCl 3 − /Ce III FCl 3 − and decarboxylation product La III Cl 3 (C 6 H 4 F) − /Ce III Cl 3 (C 6 H 4 F) − were observed when the carboxylate precursors La III Cl 3 (C 6 H 4 FCO 2 ) − /Ce III Cl 3 (C 6 H 4 FCO 2 ) − were subjected to collision-induced dissociation. The variation in product ratios, which is not obvious in the meta and para cases, qualitatively follows the increasing overall energy barrier and reaction endothermicity of the two-step CO 2 /C 6 H 4 elimination mechanism, and this aligns with the increase in U−F distance in the ortho, meta, and para decarboxylation product isomers. In contrast, the mass spectra of Fe III Cl 3 (C 6 H 4 FCO 2 ) − /Cu II Cl 2 (C 6 H 4 FCO 2 ) − are dominated by the reduction product FeCl 3 − /CuCl 2 − regardless of the fluorobenzoate isomer. DFT/B3LYP calculations show that the two-step CO 2 /C 6 H 4 F elimination pathways are comparable in energy for all three positional isomers. It is energetically more favorable to give the reduction product than the fluoride transfer product, which is opposite to the lanthanum cases. Although the decarboxylation product was observed for all three U VI O 2 Cl 2 (C 6 H 4 FCO 2 ) − isomers, the ortho isomer behaves more similarly to La III Cl 3 (C 6 H 4 FCO 2 ) − /Ce III Cl 3 (C 6 H 4 FCO 2 ) − as evidenced by the formation of U VI O 2 FCl 2 − , and the appearance of U V O 2 Cl 2 − in the cases of the meta and para isomers indicates the similarity with Fe III Cl 3 (C 6 H 4 FCO 2 ) − /Cu II Cl 2 (C 6 H 4 FCO 2 ) − . The shorter U−F distance in U VI O 2 Cl 2 (o-C 6 H 4 F) − causes the decrease in the fluoride transfer barrier and thus makes this process more favorable over o-C 6 H 4 F radical loss to give U V O 2 Cl 2 − .

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