Identification of new, very long-chain polyunsaturated fatty acids in fish by gas chromatography coupled to quadrupole/t
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RESEARCH PAPER
Identification of new, very long-chain polyunsaturated fatty acids in fish by gas chromatography coupled to quadrupole/time-of-flight mass spectrometry with atmospheric pressure chemical ionization Roque Serrano 1,2 & Juan Carlos Navarro 2,3 & Tania Portolés 1 & Carlos Sales 1 & Joaquín Beltrán 1 & Óscar Monroig 2,3 & Félix Hernández 1,2 Received: 9 September 2020 / Revised: 2 November 2020 / Accepted: 11 November 2020 # Springer-Verlag GmbH Germany, part of Springer Nature 2020
Abstract The characterization of very long-chain (>C24) polyunsaturated fatty acids (VLC-PUFAs), which are essential in the vision, neural function, and reproduction of vertebrates, is challenging because of the lack of reference standards and their very low concentrations in certain lipid classes. In this research, we have developed a new methodology for VLC-PUFA identification based on gas chromatography coupled to quadrupole/time-of-flight mass spectrometry with an atmospheric pressure chemical ionization source (GC-APCI-QTOF MS). The mass accuracy attainable with the innovative QTOF instrument, together with the soft ionization of the APCI source, provides valuable information on the intact molecule, traditionally lost with electron ionization sources due to the extensive fragmentation suffered. We have identified, for the first time, VLC-PUFAs with chains up to 44 carbons in eyes, brain, and gonads of gilthead sea bream, a commercially important fish in the Mediterranean. The added value of ion mobility-mass spectrometry (IMS), recently developed in combination with GC-QTOF MS, and the contribution of the collisional cross section (CCS) parameter in the characterization of novel VLC-PUFAs (for which reference standards are not available) have been also evaluated. The methodology developed has allowed assessing qualitative differences between farmed and wild fish, and opens new perspectives in a still scarcely known field of research. Keywords Gas chromatography . Quadrupole/time-of-flight mass spectrometer . Very long-chain polyunsaturated fatty acids . Fish
Introduction The existence of very long-chain polyunsaturated fatty acids (VLC-PUFAs) ranging from 26 to 36 carbons in length in mammal spermatozoa and vertebrate retina was reported in 1986–1987 by Poulos et al. [1, 2] and Aveldaño and Sprecher [3]. Since then, low concentrations of up to C38 VLC-PUFAs have been reported in
* Roque Serrano [email protected] 1
Research Institute for Pesticides and Water (IUPA), University Jaume I, Av. Sos Baynat S/N, 12071 Castellón, Spain
2
Research Unit of Marine Ecotoxicology (IATS-IUPA), Ribera de Cabanes, S/N, 12595 Cabanes, Castellón, Spain
3
Instituto de Acuicultura de Torre de la Sal (IATS-CSIC), Ribera de Cabanes, S/N, 12595 Cabanes, Castellón, Spain
phosphatidylcholine (PC) of human brain [4]; triacylglycerides (TG) and cholesterol esters (CHE) of mammalian testis [5]; sperm and brain of mammals; PC, sphingomyelin (SM), and cerebrosides (CE) of human retina [6–9]; and PC of fish retina [10, 11]. VLC-PUFAs have been a
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