{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,16]],"date-time":"2026-10-16T17:42:58Z","timestamp":1792172578146,"version":"4.4.0"},"reference-count":47,"publisher":"MDPI AG","issue":"14","license":[{"start":{"date-parts":[[2020,7,11]],"date-time":"2020-07-11T00:00:00Z","timestamp":1594425600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Peru is one of the main areas where there are large cocoa crops with special relevance to the economy of this country. In fact, cocoa is a major, economically important, international crop which has been linked to several benefits, such as anti-allergenic, anti-atherogenic, anti-inflammatory, anti-microbial, anti-oxidant, anti-thrombotic, cardioprotective and vasodilatory properties, relating to its bioactive compound content. However, in cocoa industrial processing, several residues or wastes, which are commonly discarded generating a negative impact on the environment, are produced in large amounts. Some of the cocoa by-products, which go underutilized, could be a good source of bioactive compounds with high utility for the development of innovative products in nutraceutical, medical or pharmaceutical industries. For this reason, the aim of this study is to qualitatively determine the phytochemical composition of husk and bean extracts from different cocoa-growing areas and processes from Peru by high performance liquid chromatography coupled to mass spectrometry. Furthermore, we aim to evaluate their phenolic and flavan-3-ol contents and antioxidant capacities for the purpose of highlighting the potential of cocoa by-products from these cultivars as functional ingredients. In total, 49 chemical compounds were detected in the analyzed extracts. Comparing both husks and beans, bean extracts were characterized by high content in flavonoids whereas husk extracts had a higher content of phenolic acids. The presence of these compounds together with the bioactivity results suggest that these matrices may be further studied for their revaluation in the development of high added-value products in nutraceutical, medical, and pharmaceutical industries.<\/jats:p>","DOI":"10.3390\/molecules25143177","type":"journal-article","created":{"date-parts":[[2020,7,22]],"date-time":"2020-07-22T05:10:30Z","timestamp":1595394630000},"page":"3177","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":45,"title":["LC-MS and Spectrophotometric Approaches for Evaluation of Bioactive Compounds from Peru Cocoa By-Products for Commercial Applications"],"prefix":"10.3390","volume":"25","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2613-4889","authenticated-orcid":false,"given":"Mar\u00eda de la Luz","family":"C\u00e1diz-Gurrea","sequence":"first","affiliation":[{"name":"Department of Analytical Chemistry, Faculty of Sciences, University of Granada, Av. Fuentenueva s\/n, E-18071 Granada, Spain"},{"name":"Functional Food Research and Development Center, Health Science Technological Park, Av. del Conocimiento s\/n, E-18016 Granada, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5547-3209","authenticated-orcid":false,"given":"\u00c1lvaro","family":"Fern\u00e1ndez-Ochoa","sequence":"additional","affiliation":[{"name":"Department of Analytical Chemistry, Faculty of Sciences, University of Granada, Av. Fuentenueva s\/n, E-18071 Granada, Spain"},{"name":"Functional Food Research and Development Center, Health Science Technological Park, Av. del Conocimiento s\/n, E-18016 Granada, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Francisco Javier","family":"Leyva-Jim\u00e9nez","sequence":"additional","affiliation":[{"name":"Functional Food Research and Development Center, Health Science Technological Park, Av. del Conocimiento s\/n, E-18016 Granada, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Noelia","family":"Guerrero-Mu\u00f1oz","sequence":"additional","affiliation":[{"name":"Department of Analytical Chemistry, Faculty of Sciences, University of Granada, Av. Fuentenueva s\/n, E-18071 Granada, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2067-1365","authenticated-orcid":false,"given":"Mar\u00eda del Carmen","family":"Villegas-Aguilar","sequence":"additional","affiliation":[{"name":"Department of Analytical Chemistry, Faculty of Sciences, University of Granada, Av. Fuentenueva s\/n, E-18071 Granada, Spain"},{"name":"Functional Food Research and Development Center, Health Science Technological Park, Av. del Conocimiento s\/n, E-18016 Granada, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sandra","family":"Pimentel-Moral","sequence":"additional","affiliation":[{"name":"Department of Analytical Chemistry, Faculty of Sciences, University of Granada, Av. Fuentenueva s\/n, E-18071 Granada, Spain"},{"name":"Functional Food Research and Development Center, Health Science Technological Park, Av. del Conocimiento s\/n, E-18016 Granada, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6907-3166","authenticated-orcid":false,"given":"Fernando","family":"Ramos-Escudero","sequence":"additional","affiliation":[{"name":"Unidad de Investigaci\u00f3n en Nutrici\u00f3n, Salud, Alimentos Funcionales y Nutrace\u00faticos, Universidad San Ignacio de Loyola (UNUSAN-USIL), Calle Toulon 310, Lima 15024, Peru"},{"name":"Facultad de Ciencias de la Salud, Universidad San Ignacio de Loyola, Av. La Fontana 750, Lima 15024, Peru"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Antonio","family":"Segura-Carretero","sequence":"additional","affiliation":[{"name":"Department of Analytical Chemistry, Faculty of Sciences, University of Granada, Av. Fuentenueva s\/n, E-18071 Granada, Spain"},{"name":"Functional Food Research and Development Center, Health Science Technological Park, Av. del Conocimiento s\/n, E-18016 Granada, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2020,7,11]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"39","DOI":"10.1016\/j.foodres.2012.08.005","article-title":"Chemical, technological and in vitro antioxidant properties of cocoa (Theobroma cacao L.) co-products","volume":"49","author":"Martinez","year":"2012","journal-title":"Food Res. Int."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"214","DOI":"10.1016\/j.foodchem.2014.11.004","article-title":"Effects of bioactive constituents in functional cocoa products on cardiovascular health in humans","volume":"174","author":"Goya","year":"2015","journal-title":"Food Chem."},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"C\u00e1diz-Gurrea, M.D.L.L., Borr\u00e1s-Linares, I., Lozano-S\u00e1nchez, J., Joven, J., Fern\u00e1ndez-Arroyo, S., and Segura-Carretero, A. (2017). Cocoa and Grape Seed Byproducts as a Source of Antioxidant and Anti-Inflammatory Proanthocyanidins. Int. J. Mol. Sci., 18.","DOI":"10.3390\/ijms18020376"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"e12767","DOI":"10.1111\/jfbc.12767","article-title":"Hydro-ethanol seed extract of Theobroma cacao exhibits antioxidant activities and potential anticancer property","volume":"43","author":"Ebuehi","year":"2019","journal-title":"J. Food Biochem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1150","DOI":"10.1002\/jsfa.7197","article-title":"Anti-influenza virus effects of cocoa","volume":"96","author":"Kamei","year":"2015","journal-title":"J. Sci. Food Agric."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"7725","DOI":"10.4238\/2014.September.26.10","article-title":"Antimicrobial activity of fermented Theobroma cacao pod husk extract","volume":"13","author":"Santos","year":"2014","journal-title":"Genet. Mol. Res."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"2209","DOI":"10.1002\/jcb.24548","article-title":"Cocoa powder triggers neuroprotective and preventive effects in a human Alzheimer\u2019s disease model by modulating BDNF signaling pathway","volume":"114","author":"Cimini","year":"2013","journal-title":"J. Cell. Biochem."},{"key":"ref_8","first-page":"831","article-title":"Bioactive compounds in Mexican genotypes of cocoa cotyledon and husk","volume":"240","author":"Sillero","year":"2017","journal-title":"Food Chem."},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Felice, F., Fabiano, A., De Leo, M., Piras, A.M., Beconcini, D., Cesare, M.M., Braca, A., Zambito, Y., and Di Stefano, R. (2020). Antioxidant Effect of Cocoa By-Product and Cherry Polyphenol Extracts: A Comparative Study. Antioxidants, 9.","DOI":"10.3390\/antiox9020132"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"480","DOI":"10.1016\/j.jff.2018.04.031","article-title":"Design cocoa processing towards healthy cocoa products: The role of phenolics and melanoidins","volume":"45","author":"Reyes","year":"2018","journal-title":"J. Funct. Foods"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"103","DOI":"10.1016\/j.tifs.2017.03.007","article-title":"Cocoa shell and its compounds: Applications in the food industry","volume":"63","author":"Okiyama","year":"2017","journal-title":"Trends Food Sci. Technol."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"897","DOI":"10.1007\/s11947-010-0363-z","article-title":"Recovery of Phenolic Antioxidants and Functional Compounds from Coffee Industry By-Products","volume":"5","author":"Murthy","year":"2010","journal-title":"Food Bioprocess Technol."},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Balenti\u0107, J.P., A\u010dkar, \u0110., Joki\u0107, S., Jozinovi\u0107, A., Babi\u0107, J., Mili\u010devi\u0107, B., \u0160ubari\u0107, D., and Pavlovi\u0107, N. (2018). Cocoa Shell: A By-Product with Great Potential for Wide Application. Molecules, 23.","DOI":"10.3390\/molecules23061404"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"200","DOI":"10.1016\/j.foodres.2018.08.057","article-title":"Cocoa bean shell waste valorisation; extraction from lab to pilot-scale cavitational reactors","volume":"115","author":"Grillo","year":"2019","journal-title":"Food Res. Int."},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Nguyen, V.T. (2017). Potential of Agricultural Wastes: Uses and Future Perspectives. Recovering Bioactive Compounds from Agricultural Wastes, John Wiley & Sons.","DOI":"10.1002\/9781119168850"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"9948","DOI":"10.1021\/acs.jafc.5b01062","article-title":"Effect of Fermentation and Drying on Cocoa Polyphenols","volume":"63","author":"Albertini","year":"2015","journal-title":"J. Agric. Food Chem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"108834","DOI":"10.1016\/j.foodres.2019.108834","article-title":"Analysis of volatile compounds of five varieties of Maya cocoa during fermentation and drying processes by Venn diagram and PCA","volume":"129","author":"Gschaedler","year":"2020","journal-title":"Food Res. Int."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"576","DOI":"10.1016\/j.foodchem.2015.05.040","article-title":"Multi-element, multi-compound isotope profiling as a means to distinguish the geographical and varietal origin of fermented cocoa (Theobroma cacao L.) beans","volume":"188","author":"Diomande","year":"2015","journal-title":"Food Chem."},{"key":"ref_19","doi-asserted-by":"crossref","unstructured":"Rojo-Poveda, O., Barbosa-Pereira, L., Zeppa, G., and St\u00e9vigny, C. (2020). Cocoa Bean Shell\u2014A By-Product with Nutritional Properties and Biofunctional Potential. Nutrients, 12.","DOI":"10.3390\/nu12041123"},{"key":"ref_20","first-page":"1","article-title":"UHPLC-DAD-ESI-MS\/MS Analysis of Flavonoids from Ethanolic Extracts of Theobroma cacao Husk in Cuba","volume":"6","author":"Salgado","year":"2019","journal-title":"OALib"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"41","DOI":"10.1016\/j.chroma.2016.12.022","article-title":"Targeted and untargeted characterisation of free and glycosylated simple phenols in cocoa beans using high resolution-tandem mass spectrometry (Q-Orbitrap)","volume":"1480","author":"Barnaba","year":"2017","journal-title":"J. Chromatogr. A"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"204","DOI":"10.1016\/j.aca.2018.06.068","article-title":"Characterization of secondary metabolites from green cocoa beans using focusing-modulated comprehensive two-dimensional liquid chromatography coupled to tandem mass spectrometry","volume":"1036","author":"Montero","year":"2018","journal-title":"Anal. Chim. Acta"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"485","DOI":"10.1016\/j.jff.2014.07.016","article-title":"Isolation, comprehensive characterization and antioxidant activities of Theobroma cacao extract","volume":"10","author":"Contreras","year":"2014","journal-title":"J. Funct. Foods"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"1676","DOI":"10.1016\/j.foodchem.2012.06.006","article-title":"Fast determination of N-phenylpropenoyl-l-amino acids (NPA) in cocoa samples from different origins by ultra-performance liquid chromatography and capillary electrophoresis","volume":"135","author":"Lechtenberg","year":"2012","journal-title":"Food Chem."},{"key":"ref_25","doi-asserted-by":"crossref","unstructured":"Li, Y., and Chemat, F. (2019). Green Extracts from Chinese Medicinal Plants as Bio-source of Drugs. Plant Based \u201cGreen Chemistry 2.0\u201d, Springer Nature Singapore Pte Ltd.","DOI":"10.1007\/978-981-13-3810-6"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"915","DOI":"10.1016\/j.foodchem.2018.09.072","article-title":"Aroma formation and dynamic changes during white tea processing","volume":"274","author":"Chen","year":"2018","journal-title":"Food Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"21","DOI":"10.1016\/j.scienta.2015.05.017","article-title":"Influence of the site altitude on strawberry phenolic composition and quality","volume":"192","author":"Scampicchio","year":"2015","journal-title":"Sci. Hortic."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"20382","DOI":"10.3390\/ijms151120382","article-title":"Pine bark and green tea concentrated extracts: Antioxidant activity and comprehensive characterization of bioactive compounds by HPLC-ESI-QTOF-MS","volume":"15","year":"2014","journal-title":"Int. J. Mol. Sci."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"550","DOI":"10.1016\/j.foodres.2017.06.007","article-title":"Origin-based polyphenolic fingerprinting of Theobroma cacao in unfermented and fermented beans","volume":"99","author":"Grimbs","year":"2017","journal-title":"Food Res. Int."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1242","DOI":"10.1080\/10942912.2015.1071840","article-title":"Antioxidant Properties of Cocoa Beans (Theobroma cacao L.): Influence of Cultivar and Roasting Conditions","volume":"19","author":"Oracz","year":"2015","journal-title":"Int. J. Food Prop."},{"key":"ref_31","doi-asserted-by":"crossref","unstructured":"Shalaby, E. (2019). Antioxidant Compounds from Agro-Industrial Residue. Antioxidants, IntechOpen.","DOI":"10.5772\/intechopen.77838"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"8813","DOI":"10.3390\/molecules15128813","article-title":"Phenolic-Compound-Extraction Systems for Fruit and Vegetable Samples","volume":"15","year":"2010","journal-title":"Molecules"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"259","DOI":"10.1016\/j.foodres.2018.08.084","article-title":"Effect of the solar drying process on the sensory and chemical quality of cocoa (Theobroma cacao L.) cultivated in Antioquia, Colombia","volume":"115","author":"Barrientos","year":"2019","journal-title":"Food Res. Int."},{"key":"ref_34","doi-asserted-by":"crossref","unstructured":"Nollet, L.M.L., and Toldra, F. (2012). Vitamin D. Handbook of Analysis of Active Compounds in Functional Foods, CRC Press.","DOI":"10.1201\/b11653"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"21138","DOI":"10.3390\/molecules201219753","article-title":"Antioxidant Phytochemicals for the Prevention and Treatment of Chronic Diseases","volume":"20","author":"Zhang","year":"2015","journal-title":"Molecules"},{"key":"ref_36","first-page":"325","article-title":"Cocoa bean husk: Industrial source of antioxidant phenolic extract","volume":"99","author":"Sillero","year":"2018","journal-title":"J. Sci. Food Agric."},{"key":"ref_37","first-page":"6697","article-title":"Flavonoids and phenolic acids: Role and biochemical activity in plants and human","volume":"5","author":"Ghasemzadeh","year":"2011","journal-title":"J. Med. Plants Res."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"9342","DOI":"10.3390\/ijms12129342","article-title":"The Relationships Between Biological Activities and Structure of Flavan-3-Ols","volume":"12","author":"Braicu","year":"2011","journal-title":"Int. J. Mol. Sci."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"1514","DOI":"10.1021\/jf0350111","article-title":"Relationship between Antibacterial Activity of (+)-Catechin Derivatives and Their Interaction with a Model Membrane","volume":"52","author":"Kajiya","year":"2004","journal-title":"J. Agric. Food Chem."},{"key":"ref_40","doi-asserted-by":"crossref","unstructured":"Monteiro, J.P., Alves, M.G., Oliveira, P.F., and Silva, B.M. (2016). Structure-Bioactivity Relationships of Methylxanthines: Trying to Make Sense of All the Promises and the Drawbacks. Molecules, 21.","DOI":"10.3390\/molecules21080974"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"100","DOI":"10.1016\/j.jphotobiol.2016.06.027","article-title":"Bioactive properties and potentials cosmeceutical applications of phlorotannins isolated from brown seaweeds: A review","volume":"162","author":"Sanjeewa","year":"2016","journal-title":"J. Photochem. Photobiol. B: Boil."},{"key":"ref_42","doi-asserted-by":"crossref","unstructured":"Mavarro, M., Zamora, W., Quesada, S., Azofeifa, G., Alvarado, D., and Monagas, M. (2017). Fractioning of Proanthocyanidins of Uncaria tomentosa. Composition and Structure-Bioactivity Relationship. Antioxidants, 6.","DOI":"10.3390\/antiox6030060"},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"933","DOI":"10.1016\/0891-5849(95)02227-9","article-title":"Structure-antioxidant activity relationships of flavonoids and phenolic acids","volume":"20","author":"Miller","year":"1996","journal-title":"Free. Radic. Biol. Med."},{"key":"ref_44","doi-asserted-by":"crossref","unstructured":"Dong, Y., Hou, Q., Sun, M., Sun, J., and Zhang, B. (2020). Targeted Isolation of Antioxidant Constituents from Plantago asiatica L. and In Vitro Activity Assay. Molecules, 25.","DOI":"10.3390\/molecules25081825"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"600","DOI":"10.1021\/np050447r","article-title":"Vanillic Acid Glycoside and Quinic Acid Derivatives from Gardeniae Fructus","volume":"69","author":"Kim","year":"2006","journal-title":"J. Nat. Prod."},{"key":"ref_46","first-page":"40","article-title":"Bioactive Compounds from Theobroma cacao: Effect of Isolation and Safety Evaluation","volume":"74","author":"Nieves","year":"2018","journal-title":"Plant. Foods Hum. Nutr."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"W486","DOI":"10.1093\/nar\/gky310","article-title":"MetaboAnalyst 4.0: Towards more transparent and integrative metabolomics analysis","volume":"46","author":"Chong","year":"2018","journal-title":"Nucleic Acids Res."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/25\/14\/3177\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T09:50:26Z","timestamp":1760176226000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/25\/14\/3177"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,7,11]]},"references-count":47,"journal-issue":{"issue":"14","published-online":{"date-parts":[[2020,7]]}},"alternative-id":["molecules25143177"],"URL":"https:\/\/doi.org\/10.3390\/molecules25143177","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,7,11]]}}}