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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

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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.

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Acknowledgements

This work has been developed within the framework of the Research Unit of Marine Ecotoxicology (IATS-CSIC/IUPA-UJI). Tania Portolés acknowledges Ramon y Cajal Program from the Ministry of Economy and Competitiveness, Spain (RYC-2017-22525), for funding her research. Carlos Sales acknowledges the financial support from University Jaume I, Spain for his predoctoral grant. Funding: Pla 2018 de Promoció de la Investigació a l’UJI. Research Project: Identificación y cuantificación de ácidos grasos poliinsaturados de cadena muy larga mediante cromatografía de gases acoplada a espectrometría de masas de alta resolución en peces. Ref: UJI-B2018-08. Programa Estatal de Investigacion, Desarrollo e Innovacion orientada a los retos de la sociedad (Ministry of Economy and Competitiveness): Research Project “Acidos grasos poliinsaturados de cadena muy larga en peces: biosíntesis e implicaciones durante fases tempranas de desarrollo en especies cultivadas” (AGL2013-40986-R).

We are grateful with David Fabregat Safont for his help on the fragmentation routes proposal.

Funding

Pla 2018 de Promoció de la Investigació a l’UJI. Research Project: Identificación y cuantificación de ácidos grasos poliinsaturados de cadena muy larga mediante cromatografía de gases acoplada a espectrometría de masas de alta resolución en peces. Ref: UJI-B2018–08. Programa Estatal de Investigación, Desarrollo e Innovación orientada a los retos de la sociedad (Ministry of Economy and Competitiveness): Research Project “Ácidos grasos poliinsaturados de cadena muy larga en peces: biosíntesis e implicaciones durante fases tempranas de desarrollo en especies cultivadas” (AGL2013–40986-R). Ramon y Cajal Program from the Ministry of Economy and Competitiveness, Spain (RYC-2017-22525). The UJI authors acknowledge the financial support from Generalitat Valenciana (Group of Excellence Prometeo 2019/040).

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Authors and Affiliations

  1. Research Institute for Pesticides and Water (IUPA), University Jaume I, Av. Sos Baynat S/N, 12071, Castellón, Spain

    Roque Serrano, Tania Portolés, Carlos Sales, Joaquín Beltrán & Félix Hernández

  2. Research Unit of Marine Ecotoxicology (IATS-IUPA), Ribera de Cabanes, S/N, 12595, Cabanes, Castellón, Spain

    Roque Serrano, Juan Carlos Navarro, Óscar Monroig & Félix Hernández

  3. Instituto de Acuicultura de Torre de la Sal (IATS-CSIC), Ribera de Cabanes, S/N, 12595, Cabanes, Castellón, Spain

    Juan Carlos Navarro & Óscar Monroig

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  1. Roque Serrano
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  2. Juan Carlos Navarro
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  3. Tania Portolés
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  4. Carlos Sales
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  6. Óscar Monroig
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  7. Félix Hernández
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Correspondence to Roque Serrano.

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Serrano, R., Navarro, J.C., Portolés, T. et al. 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. Anal Bioanal Chem 413, 1039–1046 (2021). https://doi.org/10.1007/s00216-020-03062-0

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