{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,2]],"date-time":"2026-03-02T04:36:59Z","timestamp":1772426219332,"version":"3.50.1"},"reference-count":45,"publisher":"MDPI AG","issue":"3","license":[{"start":{"date-parts":[[2022,1,27]],"date-time":"2022-01-27T00:00:00Z","timestamp":1643241600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e Tecnologia","doi-asserted-by":"publisher","award":["UIDB\/QUI\/50006\/2020"],"award-info":[{"award-number":["UIDB\/QUI\/50006\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e Tecnologia","doi-asserted-by":"publisher","award":["SFRH\/BD\/100889\/2014"],"award-info":[{"award-number":["SFRH\/BD\/100889\/2014"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100010801","name":"Xunta de Galicia","doi-asserted-by":"publisher","award":["10TAL314003PR"],"award-info":[{"award-number":["10TAL314003PR"]}],"id":[{"id":"10.13039\/501100010801","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100006761","name":"Universidade de Vigo","doi-asserted-by":"publisher","award":["Sabatical leave"],"award-info":[{"award-number":["Sabatical leave"]}],"id":[{"id":"10.13039\/501100006761","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100006761","name":"Universidade de Vigo","doi-asserted-by":"publisher","award":["Postdoctoral grant\u2014Talent Recruitment Program 2018"],"award-info":[{"award-number":["Postdoctoral grant\u2014Talent Recruitment Program 2018"]}],"id":[{"id":"10.13039\/501100006761","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Selecting effective antioxidants is challenging since their efficiency in inhibiting lipid oxidation depends on the rate constants of the chemical reactions involved and their concentration at the reaction site, i.e., at the interfacial region. Accumulation of antioxidants at the interface of emulsions is key to modulate their efficiency in inhibiting lipid oxidation but its control was not well understood, especially in emulsions. It can be optimized by modifying the physicochemical properties of antioxidants or the environmental conditions. In this work, we analyze the effects of surfactant concentration, droplet size, and oil to water ratio on the effective interfacial concentration of a set of chlorogenic acid (CGA) esters in fish oil-in-water (O\/W) emulsions and nanoemulsions and on their antioxidant efficiency. A well-established pseudophase kinetic model is used to determine in the intact emulsified systems the effective concentrations of the antioxidants (AOs). The relative oxidative stability of the emulsions is assessed by monitoring the formation of primary oxidation products with time. Results show that the concentration of all AOs at the interfacial region is much higher (20\u201390 fold) than the stoichiometric one but is much lower than those of other phenolipid series such as caffeic or hydroxytyrosol derivatives. The main parameter controlling the interfacial concentration of antioxidants is the surfactant volume fraction, \u03a6I, followed by the O\/W ratio. Changes in the droplet sizes (emulsions and nanoemulsions) have no influence on the interfacial concentrations. Despite the high radical scavenging capacity of CGA derivatives and their being concentrated at the interfacial region, the investigated AOs do not show a significant effect in inhibiting lipid oxidation in contrast with what is observed using other series of homologous antioxidants with similar reactivity. Results are tentatively interpreted in terms of the relatively low interfacial concentrations of the antioxidants, which may not be high enough to make the rate of the inhibition reaction faster than the rate of radical propagation.<\/jats:p>","DOI":"10.3390\/molecules27030861","type":"journal-article","created":{"date-parts":[[2022,1,27]],"date-time":"2022-01-27T22:00:56Z","timestamp":1643320856000},"page":"861","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Unexpected Antioxidant Efficiency of Chlorogenic Acid Phenolipids in Fish Oil-in-Water Nanoemulsions: An Example of How Relatively Low Interfacial Concentrations Can Make Antioxidants to Be Inefficient"],"prefix":"10.3390","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9614-409X","authenticated-orcid":false,"given":"Marlene","family":"Costa","sequence":"first","affiliation":[{"name":"REQUIMTE-LAQV, Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9447-5626","authenticated-orcid":false,"given":"Sonia","family":"Losada-Barreiro","sequence":"additional","affiliation":[{"name":"REQUIMTE-LAQV, Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal"},{"name":"Department of Physical Chemistry, Faculty of Chemistry, Universidade de Vigo, 36200 Vigo, Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3593-8878","authenticated-orcid":false,"given":"Ant\u00f3nio","family":"Vicente","sequence":"additional","affiliation":[{"name":"Centre of Biological Engineering, Campus de Gualtar, University of Minho, 4710-057 Braga, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9468-0881","authenticated-orcid":false,"given":"Carlos","family":"Bravo-D\u00edaz","sequence":"additional","affiliation":[{"name":"Department of Physical Chemistry, Faculty of Chemistry, Universidade de Vigo, 36200 Vigo, Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1149-6876","authenticated-orcid":false,"given":"F\u00e1tima","family":"Paiva-Martins","sequence":"additional","affiliation":[{"name":"REQUIMTE-LAQV, Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2022,1,27]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Jacobsen, C., Nielsen, N.S., Horn, A.F., and S\u00f8rensen, A.-D.M. (2013). Food Enrichment with Omega-3 Fatty Acids, Elsevier.","DOI":"10.1533\/9780857098863"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"600","DOI":"10.3945\/an.115.009084","article-title":"Intravenous lipid emulsions in parenteral nutrition","volume":"6","author":"Fell","year":"2015","journal-title":"Adv. Nutr."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"577","DOI":"10.1080\/10408390902841529","article-title":"Structural Design Principles for Delivery of Bioactive Components in Nutraceuticals and Functional Foods","volume":"49","author":"McClements","year":"2009","journal-title":"Crit. Rev. Food Sci. Nutr."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"24","DOI":"10.1016\/j.tifs.2011.12.002","article-title":"Beneficial effects and oxidative stability of omega-3 long-chain polyunsaturated fatty acids","volume":"25","author":"Jacquot","year":"2012","journal-title":"Trends Food Sci. Technol."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"425","DOI":"10.1016\/j.bbrc.2016.12.127","article-title":"Omega-3 fatty acid fish oil dietary supplements contain saturated fats and oxidized lipids that may interfere with their intended biological benefits","volume":"483","author":"Mason","year":"2017","journal-title":"Biochem. Biophys. Res. Commun."},{"key":"ref_6","doi-asserted-by":"crossref","unstructured":"Catala, A. (2017). Fatty Acids in Fish. Fatty Acids, IntechOpen. Chapter 8.","DOI":"10.5772\/65211"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"842","DOI":"10.1111\/j.1440-1681.2006.04451.x","article-title":"Omega-3 fatty acids and hypertension in humans","volume":"33","author":"Mori","year":"2006","journal-title":"Clin. Exp. Pharmacol. Physiol."},{"key":"ref_8","unstructured":"Jacobsen, C., Nielsen, N.S., Horn, A.F., and Moltke Sorensen, A.-D. (2013). 1-Nutritional benefits of omega-3 fatty acids. Woodhead Publishing Series in Food Science, Technology and Nutrition, Woodhead Publishing."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"124","DOI":"10.1080\/1828051X.2015.1128687","article-title":"From farm to fork: Lipid oxidation in fish products. A review","volume":"15","author":"Secci","year":"2016","journal-title":"Ital. J. Anim. Sci."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"930","DOI":"10.1002\/ejlt.201000044","article-title":"Novel antioxidants in food quality preservation and health promotion","volume":"112","author":"Shahidi","year":"2010","journal-title":"Eur. J. Lipid Sci. Technol."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"874","DOI":"10.1016\/j.jnutbio.2010.08.004","article-title":"Docosahexaenoic acid reverts resistance to UV-induced apoptosis in human keratinocytes: Involvement of COX-2 and HuR","volume":"22","author":"Serini","year":"2011","journal-title":"J. Nutr. Biochem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1415","DOI":"10.1007\/s00217-017-2852-z","article-title":"Influence of droplet size on the antioxidant efficacy of oil-in-water emulsions loaded with rosemary in raw fermented sausages","volume":"243","author":"Erdmann","year":"2017","journal-title":"Eur. Food Res. Technol."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1094","DOI":"10.1002\/mnfr.200600303","article-title":"Dietary advanced lipid oxidation endproducts are risk factors to human health","volume":"51","author":"Kanner","year":"2007","journal-title":"Mol. Nutr. Food Res."},{"key":"ref_14","doi-asserted-by":"crossref","unstructured":"Shahidi, F. (2005). Lipid oxidation: Measurement methods. Bailey\u2019s Industrial Oil and Fat Products, John Wiley & Sons Inc.. [6th ed.].","DOI":"10.1002\/047167849X.bio050"},{"key":"ref_15","unstructured":"Barclay, L.R.C., and Vinqvist, M.R. (2003). The Chemistry of Phenols, John Wiley & Sons."},{"key":"ref_16","doi-asserted-by":"crossref","unstructured":"Pokorny, J., Yanishlieva, N., and Gordon, M. (2001). Antioxidants in Food: Practical Applications, Elsevier.","DOI":"10.1201\/9781439823057"},{"key":"ref_17","doi-asserted-by":"crossref","unstructured":"Shahidi, F. (2015). Handbook of Antioxidants for Food Preservation, Woodhead Publishing.","DOI":"10.1016\/B978-1-78242-089-7.00001-4"},{"key":"ref_18","doi-asserted-by":"crossref","unstructured":"Wanasundara, P.K.J.P.D., and Shahidi, F. (2005). Antioxidants: Science, Technology, and Applications. Bailey\u2019s Industrial Oil and Fat Products, Wiley & Sons.","DOI":"10.1002\/047167849X.bio002"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"8961","DOI":"10.1021\/acs.langmuir.5b00112","article-title":"To Model Chemical Reactivity in Heterogeneous Emulsions, Think Homogeneous Microemulsions","volume":"31","author":"Romsted","year":"2015","journal-title":"Langmuir"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"233","DOI":"10.1016\/j.foodchem.2014.10.016","article-title":"A direct correlation between the antioxidant efficiencies of caffeic acid and its alkyl esters and their concentrations in the interfacial region of olive oil emulsions. The pseudophase model interpretation of the \u201ccut-off\u201d effect","volume":"175","author":"Costa","year":"2015","journal-title":"Food Chem."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"125716","DOI":"10.1016\/j.foodchem.2019.125716","article-title":"Influence of AO chain length, droplet size and oil to water ratio on the distribution and on the activity of gallates in fish oil-in-water emulsified systems: Emulsion and nanoemulsion comparison","volume":"310","author":"Costa","year":"2020","journal-title":"Food Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"3917","DOI":"10.1002\/jsfa.9615","article-title":"Control of antioxidant efficiency of chlorogenates in emulsions: Modulation of antioxidant interfacial concentrations","volume":"99","author":"Meireles","year":"2019","journal-title":"J. Sci. Food Agric."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"212","DOI":"10.3390\/antiox3020212","article-title":"Distribution and antioxidant efficiency of resveratrol in stripped corn oil emulsions","volume":"3","author":"Costa","year":"2014","journal-title":"Antioxidants"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"192","DOI":"10.1016\/j.foodres.2018.06.007","article-title":"Modulating the interfacial concentration of gallates to improve the oxidative stability of fish oil-in-water emulsions","volume":"112","author":"Ferreira","year":"2018","journal-title":"Food Res. Int."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"352","DOI":"10.1016\/j.jcis.2019.12.011","article-title":"Effects of droplet size on the interfacial concentrations of antioxidants in fish and olive oil-in-water emulsions and nanoemulsions and on their oxidative stability","volume":"562","author":"Costa","year":"2020","journal-title":"J. Colloid Interface Sci."},{"key":"ref_26","doi-asserted-by":"crossref","unstructured":"Costa, M., Losada-Barreiro, S., Paiva-Martins, F., and Bravo-D\u00edaz, C. (2021). Polyphenolic antioxidants in lipid emulsions: Partitioning effects and interfacial phenomena. Foods, 10.","DOI":"10.3390\/foods10030539"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"1600277","DOI":"10.1002\/ejlt.201600277","article-title":"Using a pseudophase model to determine AO distributions in emulsions: Why dynamic equilibrium matters","volume":"119","author":"Romsted","year":"2017","journal-title":"Eur. J. Lipid Sci. Technol."},{"key":"ref_28","doi-asserted-by":"crossref","unstructured":"Costa, M., Losada-Barreiro, S., Bravo-D\u00edaz, C., Monteiro, L.S., and Paiva-Martins, F. (2020). Interfacial Concentrations of Hydroxytyrosol Derivatives in Fish Oil-in-Water Emulsions and Nanoemulsions and Its Influence on Their Lipid Oxidation: Droplet Size Effects. Foods, 9.","DOI":"10.3390\/foods9121897"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"5274","DOI":"10.1021\/acs.jafc.6b01468","article-title":"Interfacial Concentrations of Hydroxytyrosol and Its Lipophilic Esters in Intact Olive Oil-in-Water Emulsions: Effects of Antioxidant Hydrophobicity, Surfactant Concentration, and the Oil-to-Water Ratio on the Oxidative Stability of the Emulsions","volume":"64","author":"Almeida","year":"2016","journal-title":"J. Agric. Food Chem."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"2999","DOI":"10.1021\/acs.jced.8b00258","article-title":"Differential partitioning of bioantioxidants in edible oil\u2013water and octanol\u2013water systems: Linear free energy relationships","volume":"63","year":"2018","journal-title":"J. Chem. Eng. Data"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"248","DOI":"10.1016\/j.jcis.2021.06.101","article-title":"Interfacial kinetics in olive oil-in-water nanoemulsions: Relationships between rates of initiation of lipid peroxidation, induction times and effective interfacial antioxidant concentrations","volume":"604","author":"Costa","year":"2021","journal-title":"J. Colloid Interface Sci."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"1600274","DOI":"10.1002\/ejlt.201600274","article-title":"Partitioning and antioxidative effect of protocatechuates in soybean oil emulsions: Relevance of emulsifier concentration","volume":"119","author":"Silva","year":"2017","journal-title":"Eur. J. Lipid Sci. Technol."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"222","DOI":"10.1021\/ar0682029","article-title":"Solvent Effects on the Rates and Mechanisms of Reaction of Phenols with Free Radicals","volume":"40","author":"Litwinienko","year":"2007","journal-title":"Acc. Chem. Res."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"6533","DOI":"10.1021\/jf400981x","article-title":"A Maximum in Antioxidant Distributions and Efficiencies with Increasing Hydrophobicity of Gallic Acid and its Alkyl Esters. The Pseudophase Model Interpretation of the \u201cCut-Off\u201d Effect","volume":"61","author":"Romsted","year":"2013","journal-title":"J. Agric. Food. Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"11335","DOI":"10.1021\/jf9026266","article-title":"Chain Length Affects Antioxidant Properties of Chlorogenate Esters in Emulsion: The Cutoff Theory Behind the Polar Paradox","volume":"57","author":"Laguerre","year":"2009","journal-title":"J. Agric. Food Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"2869","DOI":"10.1021\/jf904119v","article-title":"Relationship between Hydrophobicity and Antioxidant Ability of \u201cPhenolipids\u201d in Emulsion: A Parabolic Effect of the Chain Length of Rosmarinate Esters","volume":"58","author":"Laguerre","year":"2010","journal-title":"J. Agric. Food Chem."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"489","DOI":"10.1007\/s11746-010-1696-5","article-title":"The efficacy of compounds with different polarities as antioxidants in emulsions with omega-3 lipids","volume":"88","author":"Nielsen","year":"2011","journal-title":"J. Am. Oil Chem. Soc."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"290","DOI":"10.1002\/poc.3196","article-title":"Distribution of catechol in emulsions","volume":"27","author":"Costa","year":"2014","journal-title":"J. Phys. Org. Chem."},{"key":"ref_39","doi-asserted-by":"crossref","unstructured":"Costa, M., Losada-Barreiro, S., Magalh\u00e3es, J., Monteiro, L.S., Bravo-D\u00edaz, C., and Paiva-Martins, F. (2021). Effects of the Reactive Moiety of Phenolipids on Their Antioxidant Efficiency in Model Emulsified Systems. Foods, 10.","DOI":"10.3390\/foods10051028"},{"key":"ref_40","doi-asserted-by":"crossref","unstructured":"Frankel, E.N. (2012). Preface. Lipid Oxidation, Woodhead Publishing. [2nd ed.].","DOI":"10.1016\/B978-0-9531949-8-8.50017-5"},{"key":"ref_41","doi-asserted-by":"crossref","unstructured":"Costa, M., Losada-Barreiro, S., Paiva-Martins, F., and Bravo-D\u00edaz, C. (2021). Effects of Surfactant Volume Fraction on the Antioxidant Efficiency and on The Interfacial Concentrations of Octyl and Tetradecyl p-Coumarates in Corn Oil-in-Water Emulsions. Molecules, 26.","DOI":"10.3390\/molecules26196058"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"76","DOI":"10.1016\/j.tifs.2007.08.001","article-title":"Antioxidant strategies for preventing oxidative flavour deterioration of foods enriched with n-3 polyunsaturated lipids: A comparative evaluation","volume":"19","author":"Jacobsen","year":"2008","journal-title":"Trends Food Sci. Technol."},{"key":"ref_43","doi-asserted-by":"crossref","unstructured":"Costa, M., Paiva-Martins, F., Losada-Barreiro, S., and Bravo-D\u00edaz, C. (2021). Modeling Chemical Reactivity at the Interfaces of Emulsions: Effects of Partitioning and Temperature. Molecules, 26.","DOI":"10.3390\/molecules26154703"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"1629","DOI":"10.1007\/s11746-013-2309-x","article-title":"Effects of acidity, temperature and emulsifier concentration on the distribution of caffeic acid in stripped corn and olive oil-in-water emulsions","volume":"90","author":"Costa","year":"2013","journal-title":"J. Am. Oil Chem. Soc."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"91483","DOI":"10.1039\/C6RA18282H","article-title":"Optimizing the efficiency of antioxidants in emulsions by lipophilization: Tuning interfacial concentrations","volume":"6","author":"Costa","year":"2016","journal-title":"RSC Adv."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/27\/3\/861\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T22:09:00Z","timestamp":1760134140000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/27\/3\/861"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,1,27]]},"references-count":45,"journal-issue":{"issue":"3","published-online":{"date-parts":[[2022,2]]}},"alternative-id":["molecules27030861"],"URL":"https:\/\/doi.org\/10.3390\/molecules27030861","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,1,27]]}}}