RATIONALE Glycosphingolipids are important lipid molecules namely as constituents of the plasma membrane organized in lipid rafts, in signal transduction, and cell‐cell communication. Although many human diseases are associated with oxidative stress and lipid oxidation, a link between oxidative stress and modification of glycosphingolipids has never been addressed. METHODS In this study, the structural changes caused by UVA‐induced photooxidation of galactosyl‐ (GalCer) and lactosylceramide (LacCer) molecular species were studied by electrospray ionization mass spectrometry (ESI‐MS and MS/MS), using a quadrupole time‐of‐flight (QTOF) mass spectrometer and high‐performance liquid chromatography/tandem mass spectrometry with a C5 stationary phase (C5 HPLC/MS/MS) using a linear ion trap. RESULTS ESI‐MS spectra of GalCer and LacCer after photooxidation showed new ions with a mass shift of +32 Da when compared with the ions of the non‐modified glycosphingolipids. These new species were assigned as hydroperoxyl derivatives, confirmed by HPLC/MS/MS and through FOX 2 assay. In the ESI‐MS and LC/MS of lactosylceramide a new ion with lower m/z value, assigned as glucosylceramide (GlcCer) + 32 Da, was also detected and proposed to be formed due to oxidative cleavage of lactosyl moieties. ESI‐MS/MS of the oxidized species allowed us to infer the presence of isomeric hydroperoxyl derivatives, with the hydroperoxyl moiety either linked to the sphingosine backbone or in the unsaturated acyl chain. Oxidation in the sugar moieties was observed in the case of LacCer, suggesting an oxidation via radical reactive oxygen species that can induce the oxidative cleavage of the lactosyl moiety. CONCLUSIONS This study shows that glycosphingolipids are prone to oxidation and the identified mass spectrometry fingerprint of oxidized galactosyl‐ and lactosylceramide species will support their future identification in lipidomic studies of biological samples under oxidative conditions. Copyright © 2014 John Wiley & Sons, Ltd.

Lactosylceramide

Hydroperoxyl

10.1002/rcm.7020

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Citations (9)

New Insights on the Impact of Statin Therapy in the Susceptibility to Hypovitaminosis D Through Serum Lipidome Profiling.

Central Nervous System Agents in Medicinal Chemistry (2016)

Santos Estrela Ar Frederico Cerveira Correia Br Ana Reis Margarida Fardilha

Lipidome

Profiling (computer programming)

Hypovitaminosis

Source

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Discovering oxidized polar lipids in microalgae lipidome using liquid chromatography mass spectrometry approaches

Algal Research (2024)

Tiago Conde Diana Lopes Rita Pais Joana Batista Tatiana Maurício

Lipidome

10.1016/j.algal.2024.103764

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Citations (1)

Positive and negative electrospray ionisation tandem mass spectrometry as a tool for structural characterisation of acid released oligosaccharides from olive pulp glucuronoxylans

Carbohydrate Research (2003)

Ana Reis M. Rosário M. Domingues Pedro Domíngues A. J. Ferrer‐Correia Manuel A. Coimbra

Glycosidic bond

Fragmentation

10.1016/s0008-6215(03)00196-4

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Lipidomics of common octopus' (Octopus vulgaris) arm muscle using untargeted high-resolution liquid chromatography-mass spectrometry

Journal of Food Composition and Analysis (2022)

Luís Gaspar Fernando Ricardo Tânia Melo Pedro Domíngues M. Rosário M. Domingues

The common octopus, Octopus vulgaris, is one of the most important cephalopod fisheries in the world. In Mediterranean cuisine, the common octopus is perceived as an ingredient highly valued for its palatability and nutritional value (source of omega-3 fatty acids). However, the polar lipids of this species are still poorly understood. The present study performed the first fingerprinting of the polar lipidome of the arm muscle of O. vulgaris using a high-resolution mass spectrometry HILIC-LC-MS lipidomics approach. Samples of common octopus were sourced from specimens landed in Santa Luzia (Tavira, Algarve, Portugal), the most important octopus mono-specific fishing harbour in mainland Portugal. Nearly 400 lipid species have been identified from 13 classes of polar lipids. Phosphatidylcholine and phosphatidylethanolamine were the main phospholipids recorded, while the phosphonolipid CAEP and ceramides were the main sphingolipids identified. The structural characterization recognised a high proportion of essential fatty acids, such as EPA, DHA and several other very-long-chain fatty acids (24:5, 24:6) esterified in the polar lipids. The present study provides an unprecedented elucidation of the polar lipidome of O. vulgaris that can be used as a reference for future studies on nutritional value, ecology and traceability of geographic origin.

Lipidome

octopus (software)

Cephalopod

Sepia

Cuttlefish

Glycerophospholipids

Domoic Acid

10.1016/j.jfca.2022.104871

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Citations (9)

Identification of oxidation products and free radicals of tryptophan by mass spectrometry

Journal of the American Society for Mass Spectrometry (2003)

M. Rosário M. Domingues Pedro Domíngues Ana Reis Conceição Fonseca Francisco Amado

New oxidation products and free radicals derived from tryptophan (Trp) oxidation under Fenton reaction conditions were identified using mass spectrometry. After the oxidation of tryptophan using hydrogen peroxide and iron (II) system (Fenton reaction), mono- and dihydoxy tryptophans and N-formylkynurenine were identified using electrospray mass spectrometry (ES-MS) and ES-MS/MS. Besides these products, new products resulting from the reaction of tryptophan and oxidized tryptophan and 3-methyl indole derivatives were also identified. The 3-methyl indole derivatives resulted, most probably, from the oxidation process and not from in-source processes. A dimer formed by cross-linking between two Trp radicals (Trp-Trp), similar to the previously described tyrosine dimer was observed, as well as the corresponding monohydroxy-dimer (Trp-Trp-OH). Tandem mass spectrometry was used to identify the structures of these new oxidation products. Free radicals derived from tryptophan oxidation under Fenton reaction were detected using as spin trap the DMPO. The free radical species originated during the oxidation reaction formed stable adducts with the spin trap, and these adducts were identified by ES-MS. New adducts of oxidized tryptophan radicals, namely monohydroxy-tryptophan and dihydroxy-Trp dimer radicals, with one and two DMPO spin trap molecules where identified. Tandem mass spectrometry was used to confirm the proposed structure of the observed adducts.

10.1016/s1044-0305(03)00127-2

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Citations (95)

A lipidomic approach towards identifying the effects of fragrance hydroperoxides on keratinocytes

Contact Dermatitis (2024)

A. T. Moore Ana S. P. Moreira Inês M. S. Guerra Laura Goracci Pedro Domíngues

Abstract Background Limonene and linalool are used in cosmetic products for their floral scents, but their oxidation products are strong contact allergens whose mechanisms of action are still not fully understood. Objectives The effects of limonene hydroperoxide (Lim‐2‐OOH) and linalool hydroperoxides (Lin‐6/7‐OOH) on the lipid profile of a human keratinocyte cell line (HaCaT) were evaluated. 2,4‐Dinitrofluorobenzene (DNFB) was also included. Methods Lim‐2‐OOH and Lin‐6/7‐OOH were synthesised according to previous methods. HaCaT cells were treated with allergens (10 μM) for 24 h and the cellular lipid extracts were analysed by C18 liquid chromatography with tandem mass spectrometry (LC–MS/MS). Data analysis was performed using Lipostar software. Statistical analysis was carried out using Metaboanalyst and R software. Results All three sensitisers used caused significant changes in the lipidome of HaCaT cells in a similar trend. There was an upregulation in several plasmanyl/plasmenyl phospholipids (O‐/P‐phosphatidylcholines [PC] and O‐/P‐phosphatidylethanolamines [PE]), sphingolipids (HexCer) and triacylglycerol lipid species, and a decrease in some polyunsaturated fatty acids‐containing phospholipid (PE and PC) species suggesting oxidative stress and inflammation. Conclusions This study is the first to evaluate the plasticity of the HaCaT cell lipidome in response to allylic hydroperoxide allergens Lim‐2‐OOH and Lin‐6/7‐OOH, together with the experimental contact allergen DNFB. These allergens are able to upregulate and downregulate certain lipid classes to a varying degree.

Lipidome

HaCaT

Honokiol

10.1111/cod.14711

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