Understanding the nitrolipidome: From chemistry to mass spectrometry and biological significance of modified complex lipids


Complex lipids, phospholipids (PLs) and triacylglycerides (TAGs), are prone to modifications induced by reactive nitrated species and reactive oxygen species, generating a range of nitrated, nitrosated or nitroxidized derivatives, as nitro PLs and nitro TAGs. These modified lipids (epilipids) have been reported in vitro and in vivo using lipidomics approaches. However, their detection in living systems remains a challenge hampered by its complexity, high structural diversity, and low abundance. The advances in high-resolution mass spectrometry combined with the higher sensitivity of the instruments like Orbitrap-based mass spectrometers opened new opportunities for the detection of these modified complex lipids. This review summarizes the challenges and findings behind the identification of nitrated, nitrosated and nitroxidized PLs and TAGs fragmentation fingerprints based on collision-induced dissociation (CID) and higher energy CID (HCD) MS/MS approaches. Following what has already been reported for nitrated fatty acids, these complex lipids are found to act as endogenous mediators with potential electmphilic properties and can express bioactivities such as anti-inflammatory and antioxidant actions. This information can be used to design untargeted and targeted lipidomics strategies for these modified complex lipids in biological samples as well as in pathological, food and industrial settings, further unveiling their biological and signalling roles.



subject category

Biochemistry & Molecular Biology; Nutrition & Dietetics


Neves, B; Perez-Sala, D; Ferreira, HB; Guerra, IMS; Moreira, ASP; Domingues, P; Domingues, MR; Melo, T

our authors


The authors would like to thanks to the University of Aveiro and FCT/MCT for the financial support to LAQV/REQUIMTE (UIDP/50006/2020 + UIDB/50006/2020), CESAM (UIDB/50017/2020 + UIDP/50017/2020 + LA/P/0094/2020), CICECO (UIDB/50011/2020+UIDP/50011/2020) and to RNEM, Portuguese Mass Spectrometry Network, (LISBOA-01-0145-FEDER-402-022125) through national founds and, where applicable, co-financed by the FEDER, within the PT2020 Partnership Agreement and Compete 2020. The authors are also thankful to the COST Action EpiLipidNET, CA19105 -Pan-European Network in Lipidomics and EpiLipidomics. Dolores Perez-Sala thanks to RTI2018-097624-B-I00 from Agencia Estatal de Investigacion, MICINN/FEDER, Spain, and Instituto de Salud Carlos III/FEDER, RETIC ARADyAL RD16/0006/0021. Ana Moreira thanks the research contract under the project Coccolitho4BioMat -Coccolithophore microalgae biorefinery: an approach for sustainable biomaterials (POCI-01-0145-FEDER-031032), funded by Centro2020, through FEDER and PT2020. Tania Melo thanks the Junior Researcher contract in the scope of the Individual Call to Scientific Employment Stimulus 2020 [CEECIND/01578/2020]. Bruna Neves (2021.04602.BD), Helena Beatriz Ferreira (2020.04611.BD) and In <^>es Guerra (2021.04754.BD) thanks FCT for the PhD grant.

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