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If one type of monomer interacts favorably with a liquid, and another type of monomer interacts favorably with another, immiscible liquid, then polymeric surfactants adsorb at the interface between the two liquids and reduce the interfacial tension. The effects of polymer architecture on the structural and thermodynamic properties of the liquid\u2013liquid interface are studied using molecular simulations. The interface is modeled with a non-additive binary Lennard-Jones fluid in the two-phase region of the phase diagram. Block and gradient copolymer surfactants are represented with coarse-grained, bead-spring models, where each component of the polymer favors one or the other liquid. Gradient copolymers have a greater concentration at the interface than do block copolymers because the gradient copolymers adopt conformations partially aligned with the interface. The interfacial tension is determined as a function of the surface excess of polymeric surfactant. Gradient copolymers are more potent surfactants than block copolymers because the gradient copolymers cross the dividing surface multiple times, effectively acting as multiple individual surfactants. For a given surface excess, the interfacial tension decreases monotonically when changing from a block to a gradient architecture. The coarse-grained simulations are complemented by all-atom simulations of acrylic-acid\/styrene copolymers at the chloroform-water interface, which have been studied in experiments. The agreement between the simulations (both coarse-grained and atomistic) and experiments is shown to be excellent, and the molecular-scale structures identified in the simulations help explain the variation of surfactancy with copolymer architecture.<\/jats:p>","DOI":"10.1063\/5.0189156","type":"journal-article","created":{"date-parts":[[2024,2,11]],"date-time":"2024-02-11T12:55:37Z","timestamp":1707656137000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":6,"title":["Polymeric surfactants at liquid\u2013liquid interfaces: Dependence of structural and thermodynamic properties on copolymer architecture"],"prefix":"10.1063","volume":"160","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7648-377X","authenticated-orcid":false,"given":"Jonathan G.","family":"Coldstream","sequence":"first","affiliation":[{"name":"School of Chemistry, University of Edinburgh 1 , David Brewster Road, Edinburgh EH9 3FJ, Scotland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7901-1364","authenticated-orcid":false,"given":"Philip J.","family":"Camp","sequence":"additional","affiliation":[{"name":"School of Chemistry, University of Edinburgh 1 , David Brewster Road, Edinburgh EH9 3FJ, Scotland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8055-5089","authenticated-orcid":false,"given":"Daniel J.","family":"Phillips","sequence":"additional","affiliation":[{"name":"Infineum UK Ltd. 2 , P.O. 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