{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,23]],"date-time":"2026-03-23T11:04:06Z","timestamp":1774263846805,"version":"3.50.1"},"reference-count":38,"publisher":"MDPI AG","issue":"3","license":[{"start":{"date-parts":[[2026,3,21]],"date-time":"2026-03-21T00:00:00Z","timestamp":1774051200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"CONVOCATORIA DEL PROGRAMA PROPIO DEL CENTRO DE GASTRONOM\u00cdA DEL MEDITERR\u00c1NEO","award":["Gasterra 2024\u201325"],"award-info":[{"award-number":["Gasterra 2024\u201325"]}]},{"name":"UA_DENIA PARA EL FOMENTO DE LA I+D+i EN EL \u00c1MBITO DE LA GASTRONOM\u00cdA","award":["GASTERRA 2025"],"award-info":[{"award-number":["GASTERRA 2025"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Metabolites"],"abstract":"<jats:p>Background\/Objectives: Sea urchin gonads (\u201croe\u201d) are a valuable seafood product and a chemically complex matrix whose composition varies with physiology and environment. We present a biphasic extraction and 1H NMR workflow to build a reusable reference inventory of polar metabolites and apolar lipid features in Paracentrotus lividus. Methods: Gonads from 37 adults (23 males, 14 females) collected at two sites (Alicante and J\u00e1vea\u2013D\u00e9nia, Spain; October 2024) were lyophilized, extracted with methanol\/chloroform\/water, and analyzed by 400 MHz 1H NMR in buffered aqueous solution (polar) and CDCl3 (apolar). Polar metabolite identification combined 1D patterns with database matching and 1H\u201313C HSQC confirmation on representative samples, yielding 71 annotated resonances corresponding to 37 metabolites spanning amino acids, osmolytes\/quaternary amines, carbohydrates\/aminosugars, and nucleoside\/purine-related compounds. Results: Polar fingerprints enabled supervised modelling: PLS-LDA separated sexes with low cross-validated error, and SPA\/COSS ranking highlighted glycine, alanine, creatine and osmolyte-associated signals as key discriminants; pathway mapping supported the enrichment of amino-acid and one-carbon\/purine networks. Apolar spectra were annotated at the motif level and used for lipid-index estimation, indicating substantial unsaturation but low docosahexaenoic acid (DHA) and modest sex effects. Conclusions: The curated peak lists and reporting framework facilitate reproducible NMR annotation and future comparative studies of P. lividus gonads.<\/jats:p>","DOI":"10.3390\/metabo16030211","type":"journal-article","created":{"date-parts":[[2026,3,23]],"date-time":"2026-03-23T09:48:42Z","timestamp":1774259322000},"page":"211","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Sex-Driven Variation in Polar Metabolites and Lipid Motifs of Paracentrotus lividus Gonads Profiled by 1H NMR"],"prefix":"10.3390","volume":"16","author":[{"given":"Ricardo","family":"Ibanco-Ca\u00f1ete","sequence":"first","affiliation":[{"name":"Department of Marine Sciences and Applied Biology, University of Alicante, Carretera San Vicente del Raspeig s\/n, 03690 Alicante, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Estela","family":"Carbonell-Garz\u00f3n","sequence":"additional","affiliation":[{"name":"Department of Marine Sciences and Applied Biology, University of Alicante, Carretera San Vicente del Raspeig s\/n, 03690 Alicante, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sergio","family":"Amor\u00f3s-Trujillo","sequence":"additional","affiliation":[{"name":"Department of Biochemistry and Molecular Biology and Agricultural Chemistry and Edafology, University of Alicante, Carretera San Vicente del Raspeig s\/n, 03690 Alicante, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4047-238X","authenticated-orcid":false,"given":"Pablo","family":"Sanchez-Jerez","sequence":"additional","affiliation":[{"name":"Department of Marine Sciences and Applied Biology, University of Alicante, Carretera San Vicente del Raspeig s\/n, 03690 Alicante, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0402-9770","authenticated-orcid":false,"given":"Frutos Carlos","family":"Marhuenda Egea","sequence":"additional","affiliation":[{"name":"Department of Biochemistry and Molecular Biology and Agricultural Chemistry and Edafology, University of Alicante, Carretera San Vicente del Raspeig s\/n, 03690 Alicante, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2026,3,21]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"100438","DOI":"10.1016\/j.ijgfs.2021.100438","article-title":"Dimensions for the valorisation of sea urchin (Paracentrotus lividus) gonads production through the eyes of experienced chefs","volume":"26","author":"Moura","year":"2021","journal-title":"Int. J. Gastron. Food Sci."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"134505","DOI":"10.1016\/j.foodchem.2022.134505","article-title":"Nucleotides and free amino acids in sea urchin Paracentrotus lividus gonads: Contributions for freshness and overall taste","volume":"404","author":"Camacho","year":"2023","journal-title":"Food Chem."},{"key":"ref_3","first-page":"2994","article-title":"The effect of sex, season and gametogenic cycle on gonad yield, biochemical composition and quality traits of Paracentrotus lividus along the North Atlantic coast of Portugal","volume":"9","author":"Rocha","year":"2019","journal-title":"PeerJ"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"117478","DOI":"10.1016\/j.trac.2023.117478","article-title":"Best Practices in NMR Metabolomics: Current State","volume":"171","author":"Powers","year":"2024","journal-title":"Trends Anal. Chem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"211","DOI":"10.1007\/s11306-007-0082-2","article-title":"Proposed minimum reporting standards for chemical analysis","volume":"3","author":"Sumner","year":"2007","journal-title":"Metabolomics"},{"key":"ref_6","first-page":"143","article-title":"Quantitative NMR Methods in Metabolomics","volume":"277","author":"Raftery","year":"2023","journal-title":"Handb. Exp. Pharmacol."},{"key":"ref_7","doi-asserted-by":"crossref","unstructured":"Carbonell-Garz\u00f3n, E., Ibanco-Ca\u00f1ete, R., Sanchez-Jerez, P., and Egea, F.C.M. (2025). Osmolytes vs. Anabolic Reserves: Contrasting Gonadal Metabolomes in Two Sympatric Mediterranean Sea Urchins. Metabolites, 15.","DOI":"10.20944\/preprints202511.0142.v1"},{"key":"ref_8","first-page":"100900","article-title":"Comparative lipidomics profiling of the sea urchin, Strongylocentrotus intermedius","volume":"40","author":"Wang","year":"2021","journal-title":"Comp. Biochem. Physiol. Part D Genom. Proteom."},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Amai, S., Yuki, K., Gowda, S.G.B., Gowda, D., and Hui, S.-P. (2025). Lipidomic Profiling of Edible Japanese Sea Urchins by LC\u2013MS. Foods, 14.","DOI":"10.3390\/foods14132268"},{"key":"ref_10","first-page":"D440","article-title":"MetaboLights: A resource evolving in response to the needs of its scientific community","volume":"48","author":"Haug","year":"2020","journal-title":"Nucleic Acids Res."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"12411","DOI":"10.1021\/acs.analchem.6b03724","article-title":"Comprehensive Metabolite Identification Strategy Using Multiple Two-Dimensional NMR Spectra of a Complex Mixture Implemented in the COLMARm Web Server","volume":"88","author":"Bingol","year":"2016","journal-title":"Anal. Chem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"871","DOI":"10.1021\/acsfoodscitech.3c00589","article-title":"Metabolomic and Lipidomic Tools for Tracing Fish Escapes from Aquaculture Facilities","volume":"4","author":"Badaoui","year":"2024","journal-title":"ACS Food Sci. Technol."},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Webb, G. (2018). Omega-3 fatty acid content of intact muscle of farmed Atlantic salmon (Salmo salar) examined by 1H MAS NMR spectroscopy. Modern Magnetic Resonance, Springer.","DOI":"10.1007\/978-3-319-28275-6_80-1"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"1341","DOI":"10.1093\/jaoac\/85.6.1341","article-title":"Determination of docosahexaenoic acid and n-3 fatty acids in refined fish oils by H-1-NMR spectroscopy: IUPAC interlaboratory study","volume":"85","author":"Igarashi","year":"2002","journal-title":"J. AOAC Int."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"100618","DOI":"10.1016\/j.jlr.2024.100618","article-title":"A high-resolution 13C NMR approach for profiling fatty acid unsaturation in lipid extracts and in live Caenorhabditis elegans","volume":"65","author":"Cravero","year":"2024","journal-title":"J. Lipid Res."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"182","DOI":"10.1016\/j.foodchem.2015.01.104","article-title":"Usefulness of 1H NMR in assessing the extent of lipid digestion","volume":"179","author":"Goicoechea","year":"2015","journal-title":"Food Chem."},{"key":"ref_17","doi-asserted-by":"crossref","unstructured":"Ibanco-Ca\u00f1ete, R., Carbonell-Garz\u00f3n, E., Sanchez-Jerez, P., and Marhuenda Egea, F.C. (2025). Identification of Sex-Dependent Aroma Compounds in Gonads of Commercially Valuable Sea Urchins: Implications for Gastronomical Use of Paracentrotus lividus. J. Mar. Sci. Eng., 13.","DOI":"10.20944\/preprints202510.1229.v1"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"911","DOI":"10.1139\/y59-099","article-title":"A Rapid Method of Total Lipid Extraction and Purification","volume":"37","author":"Bligh","year":"1959","journal-title":"Can. J. Biochem. Physiol."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"34","DOI":"10.1016\/j.chemolab.2018.03.003","article-title":"libPLS: An integrated library for partial least squares regression and linear discriminant analysis","volume":"176","author":"Li","year":"2018","journal-title":"Chemom. Intell. Lab. Syst."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"353","DOI":"10.1007\/s11306-010-0213-z","article-title":"Recipe for revealing informative metabolites based on model population analysis","volume":"6","author":"Li","year":"2010","journal-title":"Metabolomics"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"1456","DOI":"10.1039\/c0an00667j","article-title":"Noise incorporated subwindow permutation analysis for informative gene selection using support vector machines","volume":"136","author":"Wang","year":"2011","journal-title":"Analyst"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"W398","DOI":"10.1093\/nar\/gkae253","article-title":"MetaboAnalyst 6.0: Towards a unified platform for metabolomics data processing, analysis and interpretation","volume":"52","author":"Pang","year":"2024","journal-title":"Nucleic Acids Res."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"27","DOI":"10.1093\/nar\/28.1.27","article-title":"KEGG: Kyoto Encyclopedia of Genes and Genomes","volume":"28","author":"Kanehisa","year":"2000","journal-title":"Nucleic Acids Res."},{"key":"ref_24","first-page":"23","article-title":"Quantitative determination of fatty acids from fish oils using GC-MS method and 1H-NMR spectroscopy","volume":"75","author":"Bratu","year":"2013","journal-title":"UPB Sci. Bull. Ser. B Chem. Mater. Sci."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1007\/s11306-011-0330-3","article-title":"Double-check: Validation of diagnostic statistics for PLS-DA models in metabolomics studies","volume":"8","author":"Saccenti","year":"2012","journal-title":"Metabolomics"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"171","DOI":"10.1007\/s11306-006-0037-z","article-title":"Statistical strategies for avoiding false discoveries in metabolomics and related experiments","volume":"2","author":"Broadhurst","year":"2006","journal-title":"Metabolomics"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"81","DOI":"10.1007\/s11306-007-0099-6","article-title":"Assessment of PLSDA cross validation","volume":"4","author":"Westerhuis","year":"2008","journal-title":"Metabolomics"},{"key":"ref_28","doi-asserted-by":"crossref","unstructured":"Podbielski, I., Schmittmann, L., Sanders, T., and Melzner, F. (2022). Acclimation of marine invertebrate osmolyte systems to low salinity: A systematic review & meta-analysis. Front. Mar. Sci., 9.","DOI":"10.3389\/fmars.2022.934378"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"2819","DOI":"10.1242\/jeb.01730","article-title":"Organic osmolytes as compatible, metabolic and counteracting cytoprotectants in high osmolarity and other stresses","volume":"208","author":"Yancey","year":"2005","journal-title":"J. Exp. Biol."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"591","DOI":"10.1242\/jeb.158.1.591","article-title":"Arginine Kinase and Creatine Kinase Appear to be Present in the Same Cells of an Echinoderm Muscle","volume":"158","author":"Ellington","year":"1991","journal-title":"J. Exp. Biol."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"517","DOI":"10.2983\/035.029.0231","article-title":"The Effect of Seasonality on Gonad Fatty Acids of the Sea Urchins Paracentrotus lividus and Arbacia lixula (Echinodermata: Echinoidea)","volume":"29","author":"Pita","year":"2010","journal-title":"J. Shellfish Res."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"14174","DOI":"10.1038\/s41598-021-93669-9","article-title":"Lipid metabolism of sea urchin Paracentrotus lividus in two contrasting natural habitats","volume":"11","author":"Anedda","year":"2021","journal-title":"Sci. Rep."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"124","DOI":"10.1016\/j.marenvres.2015.12.001","article-title":"Influence of seasonal and environmental patterns on the lipid content and fatty acid profiles in gonads of the edible sea urchin Paracentrotus lividus from Sardinia","volume":"113","author":"Siliani","year":"2016","journal-title":"Mar. Environ. Res."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"113","DOI":"10.1016\/j.marenvres.2017.07.003","article-title":"The role of fatty acids and triglycerides in the gonads of Paracentrotus lividus from Sardinia: Growth, reproduction and cold acclimatization","volume":"130","author":"Sanna","year":"2017","journal-title":"Mar. Environ. Res."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"71","DOI":"10.1016\/S1570-0232(01)00628-6","article-title":"Separation of phospholipid classes in sea urchin, Paracentrotus lividus by high-performance liquid chromatography","volume":"770","year":"2002","journal-title":"J. Chromatogr. B"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"575","DOI":"10.1017\/S0025315403007501h","article-title":"Seasonal changes in the biochemical composition of body components of the sea urchin, Paracentrotus lividus, in Lorb\u00e9 (Galicia, north-western Spain)","volume":"83","year":"2003","journal-title":"J. Mar. Biol. Assoc. United Kingd."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"2023","DOI":"10.1111\/are.14051","article-title":"Effect of three diets on the gametogenic development and fatty acid profile of Paracentrotus lividus (Lamarck, 1816) gonads","volume":"50","author":"Raposo","year":"2019","journal-title":"Aquac. Res."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"127","DOI":"10.1016\/j.aquaculture.2019.03.005","article-title":"Effect of protein and lipid levels in diets for adult sea urchin Paracentrotus lividus (Lamarck, 1816)","volume":"506","author":"Rocha","year":"2019","journal-title":"Aquaculture"}],"container-title":["Metabolites"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2218-1989\/16\/3\/211\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,3,23]],"date-time":"2026-03-23T10:15:53Z","timestamp":1774260953000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2218-1989\/16\/3\/211"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,3,21]]},"references-count":38,"journal-issue":{"issue":"3","published-online":{"date-parts":[[2026,3]]}},"alternative-id":["metabo16030211"],"URL":"https:\/\/doi.org\/10.3390\/metabo16030211","relation":{},"ISSN":["2218-1989"],"issn-type":[{"value":"2218-1989","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,3,21]]}}}