Effects of wavelength, fluence, and dose on fragmentation pathways and photoproduct ion yield in 213 nm and 266 nm ultraviolet photodissociation experiments

Becher, Simon; Spengler, Bernhard; Heiles, Sven

doi:10.1177/1469066717741747

Cited by 8 publications

(12 citation statements)

References 40 publications

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“…HCD was performed on the Q Exactive instrument, whereas the LTQ FT Ultra was used for ion trap CID and UVPD at 213 nm as described previously. 54 Normalized collision energy (NCE) were tested for CID and HCD (Figure S-1) and best results (highest sn-2 selectivity) were obtained for NCE 12 for LTQ-FT Ultra and NCE 10 for Q Exactive experiments. UVPD with 213 nm laser light was performed with 40 laser pulses but the fragment ion identity does not depend on the number of laser pulses.…”

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confidence: 99%

Relative Quantification of Phosphatidylcholine sn-Isomers Using Positive Doubly Charged Lipid–Metal Ion Complexes

2018

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Phosphatidylcholines are the major phospholipid component of most eukaryotic cell membranes. Phosphatidylcholines have been shown to actively participate in regulatory and metabolic processes. Dysfunctional metabolic processes have been linked to human disease and can result in altered phosphatidylcholine structural features, such as permutation of fatty acid connectivity. Assignment and relative quantitation of structural isomers that arise from fatty acid permutation on the phosphatidylcholine backbone, so-called sn-isomers, is difficult with routine tandem mass spectrometry or with liquid chromatography without authentic standards. In this work, we report on the observation that phosphatidylcholines form abundant doubly charged metal ion complexes during electrospray ionization (ESI) and show that these complexes can be used to assign fatty acid moieties, relatively quantify sn-isomers in MS experiments, and mass spectrometrically separate phosphatidylcholines from other phospholipid classes in positive ion mode. Addition of Fe salts (20 mol %) to ESI spray solutions affords highly abundant doubly charged metal ion phosphatidylcholine complexes (∼110% of protonated compounds) and allows sensitive fragment ion detection (limit of detection = 100 pM). Higher energy collisional dissociation, collision-induced dissociation, and ultraviolet photodissociation of doubly charged complexes yield two fragment ions for every fatty acid moiety. The latter two tandem MS methods preferentially yield sn-2 associated product ions enabling relative sn-isomer quantification. The analytical utility of doubly charged phosphatidylcholine-metal ion complexes is demonstrated for polar lipid extracts, including extracts from diabetes type 1 and type 2 mouse models, and sn-isomer abundances are derived.

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confidence: 99%

Relative Quantification of Phosphatidylcholine sn-Isomers Using Positive Doubly Charged Lipid–Metal Ion Complexes

2018

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“…In addition to product ions from the saccharide moieties of these compounds, diagnostic ions for FA side chains and the sphingoid base helped to extensively characterize the structure of these complex lipids. Follow-up studies showed that optimized experimental settings enable identification of DB positions [77,78], sn-isomers [77,79,80], hydroxylation sites as well as linkages [81], and FA branching/ cylclopropanation [82] sites in glycerophospholipids and sphingolipids when using 193 nm or 213 nm UVPD. All these studies showed that UVPD results in extensive metabolite and lipid fragmentation, thereby enabling annotation of structural details not accessible with CID methodologies.…”

Section: Photon-based Fragmentationmentioning

confidence: 99%

Advanced tandem mass spectrometry in metabolomics and lipidomics—methods and applications

Heiles

2021

Anal Bioanal Chem

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Metabolomics and lipidomics are new drivers of the omics era as molecular signatures and selected analytes allow phenotypic characterization and serve as biomarkers, respectively. The growing capabilities of untargeted and targeted workflows, which primarily rely on mass spectrometric platforms, enable extensive charting or identification of bioactive metabolites and lipids. Structural annotation of these compounds is key in order to link specific molecular entities to defined biochemical functions or phenotypes. Tandem mass spectrometry (MS), first and foremost collision-induced dissociation (CID), is the method of choice to unveil structural details of metabolites and lipids. But CID fragment ions are often not sufficient to fully characterize analytes. Therefore, recent years have seen a surge in alternative tandem MS methodologies that aim to offer full structural characterization of metabolites and lipids. In this article, principles, capabilities, drawbacks, and first applications of these “advanced tandem mass spectrometry” strategies will be critically reviewed. This includes tandem MS methods that are based on electrons, photons, and ion/molecule, as well as ion/ion reactions, combining tandem MS with concepts from optical spectroscopy and making use of derivatization strategies. In the final sections of this review, the first applications of these methodologies in combination with liquid chromatography or mass spectrometry imaging are highlighted and future perspectives for research in metabolomics and lipidomics are discussed. Graphical abstract

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“…For the latter case mentioned above, the methods of gas‐phase photon action spectroscopy in the IR or UV regions provide unique and valuable information about their structures and relative dynamics 38–50 . However, the collection of spectra usually needs longer time and higher requirements for researchers.…”

Section: Introductionmentioning

confidence: 99%

“…Typically, infrared multiphoton dissociation (IRMPD) induces glycosidic bond cleavages and generates B/Y‐ and C/Z‐type ions, according to the Domon–Costello nomenclature of carbohydrate fragmentation 53 . For UVPD and radical‐related dissociation methods, complementary fragment ions to those observed in CID, higher‐energy collisional dissociation (HCD) and IRMPD, relative to cross‐ring cleavages, could also be observed, allowing elucidation of the glycan moiety 49 . Thus, the combination of the two different fragmentation methods can provide richer fragmentation patterns and structural information, making isomer differentiation easier.…”

Section: Introductionmentioning

confidence: 99%

Differentiation of disaccharide isomers via a combination of IR and UV photodissociation mass spectrometry

Zhang

Jiao

et al. 2021

Rapid Comm Mass Spectrometry

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Rationale The challenge of glycan identification due to their structural complexity and diversity has profited enormously from recent developments in mass spectrometry (MS)‐related methods. For photodissociation MS, infrared (IR) and ultraviolet (UV) lasers can generate complementary fragment ions, so an effective combination of the two methods may provide rich and valuable fragmentation patterns for glycan analysis. Methods A 7.0 T Fourier transform ion cyclotron resonance (FTICR) mass spectrometer equipped with a double‐beam laser system was applied for the experiments. 3,5‐Diiodo‐L‐tyrosine was selected as the assistant molecule to form complex ions with ten isomeric disaccharides through electrospray ionization. The complex ions were further isolated and irradiated by IR and UV lasers separately or continuously in the FTICR cell. Results By combining the two complementary fragment spectra generated from the IR and UV lasers, a clear identification of all the ten isomers was achieved using their binary codes based on their fragmentation patterns. The double‐beam method simplifies the experiment by introducing the two lasers sequentially in one experiment, providing richer fragmentation patterns and making the full discrimination easier. Conclusions This study demonstrates the capabilities of the combination of IR and UV photodissociation MS in the identification of diverse glycan isomers. The double‐beam photodissociation method described here distinguished compositional, configurational and connectivity disaccharide isomers successfully. Compared with the data accumulation method based on separate IR and UV experiments, this method is simpler, faster, more flexible and also characterized by richer fragmentation patterns.

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Effects of wavelength, fluence, and dose on fragmentation pathways and photoproduct ion yield in 213 nm and 266 nm ultraviolet photodissociation experiments

Cited by 8 publications

References 40 publications

Relative Quantification of Phosphatidylcholine sn-Isomers Using Positive Doubly Charged Lipid–Metal Ion Complexes

Relative Quantification of Phosphatidylcholine sn-Isomers Using Positive Doubly Charged Lipid–Metal Ion Complexes

Advanced tandem mass spectrometry in metabolomics and lipidomics—methods and applications

Differentiation of disaccharide isomers via a combination of IR and UV photodissociation mass spectrometry

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