{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,29]],"date-time":"2026-04-29T01:09:35Z","timestamp":1777424975154,"version":"3.51.4"},"reference-count":42,"publisher":"Wiley","issue":"12","license":[{"start":{"date-parts":[[2018,7,27]],"date-time":"2018-07-27T00:00:00Z","timestamp":1532649600000},"content-version":"am","delay-in-days":316,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#am"},{"start":{"date-parts":[[2017,9,14]],"date-time":"2017-09-14T00:00:00Z","timestamp":1505347200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100003074","name":"Agencia Nacional de Promoci\u00f3n Cient\u00edfica y Tecnol\u00f3gica","doi-asserted-by":"publisher","award":["CTQ2006\u201013969\u2010BQU"],"award-info":[{"award-number":["CTQ2006\u201013969\u2010BQU"]}],"id":[{"id":"10.13039\/501100003074","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["CHE 0411990"],"award-info":[{"award-number":["CHE 0411990"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["UID\/QUI\/50006\/2013 \u2013 POCI\u201001\u20100145\u2010FEDER\u2010007265"],"award-info":[{"award-number":["UID\/QUI\/50006\/2013 \u2013 POCI\u201001\u20100145\u2010FEDER\u2010007265"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100008425","name":"Conseller\u00eda de Cultura, Educaci\u00f3n e Ordenaci\u00f3n Universitaria, Xunta de Galicia","doi-asserted-by":"publisher","award":["10TAL314003PR"],"award-info":[{"award-number":["10TAL314003PR"]}],"id":[{"id":"10.13039\/501100008425","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Euro J Lipid Sci &amp;amp; Tech"],"published-print":{"date-parts":[[2017,12]]},"abstract":"<jats:sec><jats:label\/><jats:p>For decades, explorations with ground state, thermal reactions combined with pseudophase kinetic models and methods for interpreting the results have provided insights into the properties of the different regions of homogeneous association colloids. More recent successful determination of antioxidant (AO) distributions by this approach is providing new insights into AO efficiency in opaque, well\u2010mixed two\u2010phase intact emulsions and eliminating the need to separate the phases. The chemical probe reacts with AOs exclusively in the interfacial region of the emulsion, permitting simplification of the kinetic treatment, and determining its distribution between the oil, interfacial, and aqueous regions. AO distributions are obtained from the two partition constants, <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/ejlt201600277-math-0005.png\" xlink:title=\"urn:x-wiley:14381656:media:ejlt201600277:ejlt201600277-math-0005\"\/> and <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/ejlt201600277-math-0006.png\" xlink:title=\"urn:x-wiley:14381656:media:ejlt201600277:ejlt201600277-math-0006\"\/>, of the AOs between the oil\u2010interfacial and aqueous\u2010interfacial regions, respectively. <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/ejlt201600277-math-0007.png\" xlink:title=\"urn:x-wiley:14381656:media:ejlt201600277:ejlt201600277-math-0007\"\/> and <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/ejlt201600277-math-0008.png\" xlink:title=\"urn:x-wiley:14381656:media:ejlt201600277:ejlt201600277-math-0008\"\/> values are obtained by fitting the observed rate constant, <jats:italic>k<\/jats:italic><jats:sub>obs<\/jats:sub>, versus surfactant concentration profiles with an overall kinetic approach or model we call the \u201cpseudophase chemical kinetic method.\u201d However, because emulsions break up and reform, and reactants and other components diffuse at various time scales within and between the oil, interfacial, and water regions, <jats:italic>k<\/jats:italic><jats:sub>obs<\/jats:sub> could also depend on reactant diffusion coefficients. Here we demonstrate that reactant diffusion is generally orders of magnitude faster than most thermal reactions and reactant distributions between the multiple oil, aqueous, and interfacial droplets and regions of emulsions are in dynamic equilibrium throughout the multiphase systems during the time course of the reaction. Thus, kinetic probes are powerful tools for determining structure\u2010reactivity, for example, the HLB, relationships governing AO distributions and efficiencies in emulsions.<\/jats:p><jats:p><jats:bold>Practical applications:<\/jats:bold> The analysis presented here demonstrates that one of the basic assumptions of the pseudophase chemical kinetic model that we have developed has a solid foundation in the properties of emulsions. That is, we can determine the distributions of reactants between oil (O), interfacial (I), and aqueous (W) regions of the emulsions because the diffusivity coefficients of reactants within emulsions are orders of magnitude greater than the rate of the reaction between the antioxidant and the 4\u2010hexadecylbenzenediazonium probe. Consequently, we can use the same kinetic model in emulsions as we have used in homogeneous microemulsions. The method permits determination of the partition constants of many antioxidants between the O\u2010I and W\u2010I regions of the emulsions and from them their distributions. The method provides new insights into the relationships between antioxidant hydrophobic\u2010lipophilic balance (HLB) and its efficiency in emulsions and a natural explanation for the cut\u2010off effect observed with increasing antioxidant HLB.<\/jats:p><jats:p><jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/ejlt201600277-gra-0001.png\" xlink:title=\"ejlt201600277-gra-0001\"\/><\/jats:p><jats:p>Interpreting chemical reactivity in emulsions requires that reactive components <jats:bold>A<\/jats:bold> and <jats:bold>B<\/jats:bold> be in dynamic equilibrium, that separate second order rate constants, <jats:italic>k<\/jats:italic> defined for the oil, interfacial, and aqueous regions, subscripts O, I, and W, and for simplicity, the volume of each region depends on the added volumes of oil, surfactant, and water.<\/jats:p><\/jats:sec>","DOI":"10.1002\/ejlt.201600277","type":"journal-article","created":{"date-parts":[[2017,7,27]],"date-time":"2017-07-27T12:08:37Z","timestamp":1501157317000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["Using a pseudophase model to determine AO distributions in emulsions: Why dynamic equilibrium matters"],"prefix":"10.1002","volume":"119","author":[{"given":"Carlos","family":"Bravo\u2010D\u00edaz","sequence":"first","affiliation":[{"name":"Facultad de Qu\u00edmica, Dpto. Qu\u00edmica\u2010F\u00edsica Universidad de Vigo Vigo Spain"}]},{"given":"Laurence S.","family":"Romsted","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology Rutgers, the State University of New Jersey New Jersey New Jersey"}]},{"given":"Sonia","family":"Losada\u2010Barreiro","sequence":"additional","affiliation":[{"name":"Facultad de Qu\u00edmica, Dpto. Qu\u00edmica\u2010F\u00edsica Universidad de Vigo Vigo Spain"},{"name":"REQUIMTE\u2010LAQV, Departamento de Qu\u00edmica e Bioqu\u00edmica, Faculdade de Ci\u00eancias Universidade do Porto Porto Portugal"}]},{"given":"F\u00e1tima","family":"Paiva\u2010Martins","sequence":"additional","affiliation":[{"name":"REQUIMTE\u2010LAQV, Departamento de Qu\u00edmica e Bioqu\u00edmica, Faculdade de Ci\u00eancias Universidade do Porto Porto Portugal"}]}],"member":"311","published-online":{"date-parts":[[2017,9,14]]},"reference":[{"key":"e_1_2_6_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/B978-0-12-384947-2.00508-0"},{"key":"e_1_2_6_3_1","volume-title":"Handbook of Antioxidants for Food Preservation","author":"Shahidi F.","year":"2015"},{"key":"e_1_2_6_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/B978-0-08-091809-9.00011-X"},{"key":"e_1_2_6_5_1","doi-asserted-by":"publisher","DOI":"10.1111\/1541-4337.12097"},{"key":"e_1_2_6_6_1","doi-asserted-by":"publisher","DOI":"10.1533\/9780857097927"},{"key":"e_1_2_6_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jafc.6b01468"},{"key":"e_1_2_6_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejlt.201400507"},{"key":"e_1_2_6_9_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.foodchem.2014.10.016"},{"key":"e_1_2_6_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.langmuir.5b00112"},{"key":"e_1_2_6_11_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cocis.2012.11.001"},{"key":"e_1_2_6_12_1","first-page":"181","volume-title":"Supramolecular Chemistry: From Molecules to Nanomaterials","author":"Romsted L. S.","year":"2012"},{"key":"e_1_2_6_13_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cocis.2012.12.005"},{"key":"e_1_2_6_14_1","doi-asserted-by":"publisher","DOI":"10.1016\/S1359-0294(97)80055-6"},{"key":"e_1_2_6_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar00012a001"},{"key":"e_1_2_6_16_1","doi-asserted-by":"publisher","DOI":"10.1201\/9780203908662.ch8"},{"key":"e_1_2_6_17_1","volume-title":"\u201cSurfactants in Solution\u201d","author":"Romsted L. S.","year":"1984"},{"key":"e_1_2_6_18_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cocis.2004.05.029"},{"key":"e_1_2_6_19_1","doi-asserted-by":"publisher","DOI":"10.1016\/S1359-0294(00)00044-3"},{"key":"e_1_2_6_20_1","doi-asserted-by":"publisher","DOI":"10.3184\/146867807X273173"},{"key":"e_1_2_6_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/cphc.201500882"},{"key":"e_1_2_6_22_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcis.2012.07.036"},{"key":"e_1_2_6_23_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4OB02058H"},{"key":"e_1_2_6_24_1","doi-asserted-by":"publisher","DOI":"10.1007\/s11483-014-9332-9"},{"key":"e_1_2_6_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/jf400981x"},{"key":"e_1_2_6_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/jf301998s"},{"key":"e_1_2_6_27_1","volume-title":"Chemical Kinetics and Reaction Mechanisms","author":"Espenson J. H.","year":"1995"},{"key":"e_1_2_6_28_1","volume-title":"The Physical Basis of Organic Chemistry","author":"Maskill H.","year":"1995"},{"key":"e_1_2_6_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00070a004"},{"key":"e_1_2_6_30_1","first-page":"170","article-title":"He contributions of solomon F. acree (1875\u20131957) and the centennial anniversary of the discovery of the Acree\u2013","volume":"13","author":"Andraos J.","year":"2008","journal-title":"Chem. Educator"},{"key":"e_1_2_6_31_1","volume-title":"Modern Physical Organic Chemistry","author":"Anslyn E. V.","year":"2006"},{"key":"e_1_2_6_32_1","first-page":"129","article-title":"Versuch einer mathematischen theorie der koagulationskinetik kolloider losungen","author":"Smoluchowski M. V.","year":"1917","journal-title":"Zeitschrift f. Physik. Chemie"},{"key":"e_1_2_6_33_1","volume-title":"Chemical Kinetics","author":"Laidler K. J.","year":"1987"},{"key":"e_1_2_6_34_1","volume-title":"Kinetic Modeling of Reactions in Foods","author":"Van Boekel M. A. J. S.","year":"2009"},{"key":"e_1_2_6_35_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-1-4757-1592-7"},{"key":"e_1_2_6_36_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)70691-5"},{"key":"e_1_2_6_37_1","unstructured":"Refina (http:\/\/www.refina.co.uk\/webpdfs\/Info_docs\/Viscosity_guide_chart.pdf) Basco\u2010USA (http:\/\/bascousa.com\/images\/advisors\/407%20condensed.pdf) B\u00fcrkle\u2010GmbH (https:\/\/www.buerkle.de\/media\/files\/Downloads\/Viscosity_EN_2014.pdf) CRC handbook of Chemistry 84th Ed)."},{"key":"e_1_2_6_38_1","volume-title":"Fundamentals of food reaction technology: Understanding and controlling changes in foods during processing and storage","author":"Earle R. L.","year":"2008"},{"key":"e_1_2_6_39_1","doi-asserted-by":"publisher","DOI":"10.1351\/pac200779061111"},{"key":"e_1_2_6_40_1","doi-asserted-by":"publisher","DOI":"10.1002\/poc.2949"},{"key":"e_1_2_6_41_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0001-8686(98)00086-4"},{"key":"e_1_2_6_42_1","doi-asserted-by":"publisher","DOI":"10.1016\/S1359-0294(03)00022-0"},{"key":"e_1_2_6_43_1","doi-asserted-by":"publisher","DOI":"10.1002\/9781444305524.ch5"}],"container-title":["European Journal of Lipid Science and Technology"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fejlt.201600277","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/ejlt.201600277","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/ejlt.201600277","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/am-pdf\/10.1002\/ejlt.201600277","content-type":"application\/pdf","content-version":"am","intended-application":"syndication"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/ejlt.201600277","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,9,12]],"date-time":"2023-09-12T10:37:35Z","timestamp":1694515055000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/ejlt.201600277"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2017,9,14]]},"references-count":42,"journal-issue":{"issue":"12","published-print":{"date-parts":[[2017,12]]}},"alternative-id":["10.1002\/ejlt.201600277"],"URL":"https:\/\/doi.org\/10.1002\/ejlt.201600277","archive":["Portico"],"relation":{},"ISSN":["1438-7697","1438-9312"],"issn-type":[{"value":"1438-7697","type":"print"},{"value":"1438-9312","type":"electronic"}],"subject":[],"published":{"date-parts":[[2017,9,14]]},"assertion":[{"value":"2016-09-22","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2017-07-19","order":1,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2017-09-14","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"1600277"}}