{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,19]],"date-time":"2026-10-19T23:56:00Z","timestamp":1792454160746,"version":"4.5.0"},"reference-count":56,"publisher":"MDPI AG","issue":"12","license":[{"start":{"date-parts":[[2025,6,14]],"date-time":"2025-06-14T00:00:00Z","timestamp":1749859200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"National Natural Science Foundation of China","award":["22208373"],"award-info":[{"award-number":["22208373"]}]},{"name":"National Natural Science Foundation of China","award":["22376217"],"award-info":[{"award-number":["22376217"]}]},{"name":"National Natural Science Foundation of China","award":["2022YFB3504100"],"award-info":[{"award-number":["2022YFB3504100"]}]},{"name":"National Natural Science Foundation of China","award":["2022YFB3506200"],"award-info":[{"award-number":["2022YFB3506200"]}]},{"name":"National Natural Science Foundation of China","award":["20220484215"],"award-info":[{"award-number":["20220484215"]}]},{"name":"National Natural Science Foundation of China","award":["2462023YJRC030"],"award-info":[{"award-number":["2462023YJRC030"]}]},{"name":"National Key Research and Development Program of China","award":["22208373"],"award-info":[{"award-number":["22208373"]}]},{"name":"National Key Research and Development Program of China","award":["22376217"],"award-info":[{"award-number":["22376217"]}]},{"name":"National Key Research and Development Program of China","award":["2022YFB3504100"],"award-info":[{"award-number":["2022YFB3504100"]}]},{"name":"National Key Research and Development Program of China","award":["2022YFB3506200"],"award-info":[{"award-number":["2022YFB3506200"]}]},{"name":"National Key Research and Development Program of China","award":["20220484215"],"award-info":[{"award-number":["20220484215"]}]},{"name":"National Key Research and Development Program of China","award":["2462023YJRC030"],"award-info":[{"award-number":["2462023YJRC030"]}]},{"name":"Beijing Nova Program","award":["22208373"],"award-info":[{"award-number":["22208373"]}]},{"name":"Beijing Nova Program","award":["22376217"],"award-info":[{"award-number":["22376217"]}]},{"name":"Beijing Nova Program","award":["2022YFB3504100"],"award-info":[{"award-number":["2022YFB3504100"]}]},{"name":"Beijing Nova Program","award":["2022YFB3506200"],"award-info":[{"award-number":["2022YFB3506200"]}]},{"name":"Beijing Nova Program","award":["20220484215"],"award-info":[{"award-number":["20220484215"]}]},{"name":"Beijing Nova Program","award":["2462023YJRC030"],"award-info":[{"award-number":["2462023YJRC030"]}]},{"name":"Science Foundation of China University of Petroleum, Beijing","award":["22208373"],"award-info":[{"award-number":["22208373"]}]},{"name":"Science Foundation of China University of Petroleum, Beijing","award":["22376217"],"award-info":[{"award-number":["22376217"]}]},{"name":"Science Foundation of China University of Petroleum, Beijing","award":["2022YFB3504100"],"award-info":[{"award-number":["2022YFB3504100"]}]},{"name":"Science Foundation of China University of Petroleum, Beijing","award":["2022YFB3506200"],"award-info":[{"award-number":["2022YFB3506200"]}]},{"name":"Science Foundation of China University of Petroleum, Beijing","award":["20220484215"],"award-info":[{"award-number":["20220484215"]}]},{"name":"Science Foundation of China University of Petroleum, Beijing","award":["2462023YJRC030"],"award-info":[{"award-number":["2462023YJRC030"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>This study employs molecular dynamics simulations to investigate counterion effects (Li+, Na+, K+) on the interfacial aggregation of mixed short-chain fluorocarbon, Perfluorohexanoic acid (PFHXA), and Sodium dodecyl sulfate (SDS) surfactants. Motivated by the need for greener surfactant alternatives and a fundamental understanding of molecular interactions governing their behavior, we demonstrate that counterion hydration radius critically modulates system organization. K+ ions induce superior monolayer condensation and interfacial performance compared to Li+ and Na+ counterparts, as evidenced by threefold analysis: (1) RMSD\/MSD-confirmed equilibrium attainment ensures data reliability; (2) 1D\/2D density profiles and surface tension measurements reveal K+-enhanced packing density (lower solvent-accessible surface area versus Na+ and Li+ systems); (3) Electrostatic potential analysis identifies synergistic complementarity between SDS\u2019s hydrophobic stabilization via dodecyl chain interactions and PFHXA\u2019s charge uniformity, optimizing molecular-level charge screening. Radial distribution function analysis demonstrates K+\u2019s stronger affinity for SDS head groups, with preferential sulfate coordination reducing surfactant-water hydration interactions. This behavior correlates with hydrogen-bond population reduction, attributed to SDS groups functioning as multidentate ligands\u2014their tetrahedral oxygen arrangement facilitates cooperative hydrogen-bond networks, while counterion-specific charge screening competitively modulates bond formation. The resultant interfacial restructuring enables ordered molecular arrangements with lower system curvature than those observed in Li+ and Na+-containing systems. These findings elucidate counterion-mediated interfacial modulation mechanisms and establish K+ as an optimal candidate for enhancing PFHXA\/SDS mixture performance through hydration-radius screening. The work provides molecular-level guidelines for designing eco-friendly surfactant systems with tailored interfacial properties.<\/jats:p>","DOI":"10.3390\/molecules30122592","type":"journal-article","created":{"date-parts":[[2025,6,16]],"date-time":"2025-06-16T05:28:33Z","timestamp":1750051713000},"page":"2592","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Counterion-Mediated Assembly of Fluorocarbon\u2013Hydrocarbon Surfactant Mixtures at the Air\u2013Liquid Interface: A Molecular Dynamics Study"],"prefix":"10.3390","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0009-0004-8067-2639","authenticated-orcid":false,"given":"Xiaolong","family":"Quan","sequence":"first","affiliation":[{"name":"State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tong","family":"Tong","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tao","family":"Li","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dawei","family":"Han","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Baolong","family":"Cui","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jing","family":"Xiong","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zekai","family":"Cui","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hao","family":"Guo","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jinqing","family":"Jiao","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1516-5778","authenticated-orcid":false,"given":"Yuechang","family":"Wei","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2025,6,14]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1777","DOI":"10.1007\/s11696-019-00730-z","article-title":"Synthesis and characterization of a novel surfactant used for aqueous film-forming foam extinguishing agent","volume":"73","author":"Jia","year":"2019","journal-title":"Chem. 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