Journal
FREE RADICAL BIOLOGY AND MEDICINE
Volume 144, Issue -, Pages 144-155Publisher
ELSEVIER SCIENCE INC
DOI: 10.1016/j.freeradbiomed.2019.05.025
Keywords
Phosphatidylethanolamine; Phosphatidylserine; Oxidation; Glycation; Mass spectrometry; Lipidomics
Funding
- European Commission [675132]
- University of Aveiro
- Thermo Fisher Scientific Bremen
- Marine Lipidomics Laboratory
- Fundacao para a Ciencia e a Tecnologia (FCT, MECPortugal)
- QREN
- European Union
- Programa Operacional Factores de Competitividade (COMPETE)
- FEDER [FCT UID/QUI/00062/2019, UID/AMB/50017/2019, LISBOA-01-0145-FEDER-402-022125]
- German Federal Ministry of Education and Research (BMBF)
- FEDER, within the PT2020 Partnership Agreement
- Compete 2020
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The aminophospholipids (APL), phosphatidylethanolamine (PE) and phosphatidylserine (PS) are widely present in cell membranes and lipoproteins. Glucose and reactive oxygen species (ROS), such as the hydroxyl radical ((OH)-O-center dot), can react with APL leading to an array of oxidised, glycated and glycoxidised derivatives. Modified APL have been implicated in inflammatory diseases and diabetes, and were identified as signalling molecules regulating cell death. However, the biological relevance of these molecules has not been completely established, since they are present in very low amounts, and new sensitive methodologies are needed to detect them in biological systems. Few studies have focused on the characterisation of APL modifications using liquid chromatography-tandem mass spectrometry (LC-MS/MS), mainly using C5 or C18 reversed phase (RP) columns. In the present study, we propose a new analytical approach for the characterisation of complex mixtures of oxidised, glycated and glycoxidised PE and PS. This LC approach was based on a reversed-phase C30 column combined with high-resolution MS, and higher energy C-trap dissociation (HCD) MS/MS. C30 RP-LC separated short and long fatty acyl oxidation products, along with glycoxidised APL bearing oxidative modifications on the glucose moiety and the fatty acyl chains. Functional isomers (e.g. hydroxy-hydroperoxy-APL and tri-hydroxy-APL) and positional isomers (e.g. 9-hydroxy-APL and 13-hydroxy-APL) were also discriminated by the method. HCD fragmentation patterns allowed unequivocal structural characterisation of the modified APL, and are translatable into targeted MS/MS fingerprinting of the modified derivatives in biological samples.
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