Synthesis of New Cationic Dicephalic Surfactants and Their Nonequivalent Adsorption at the Air/Solution Interface

The interfacial behavior of aqueous solutions of newly synthesized 2-alkyl-N,N,N,N',N',N'-hexamethylpropan-1,3-ammonium dibromides with decyl, dodecyl, and tetradecyl alkyl chains was investigated both experimentally and theoretically. The results of the surface tension measurements w...

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Veröffentlicht in:Langmuir : the ACS journal of surfaces and colloids. - 1985. - 41(2025), 12 vom: 01. Apr., Seite 8125-8137
1. Verfasser: Lamch, Łukasz (VerfasserIn)
Weitere Verfasser: Leszczyńska, Izabella, Długowska, Daria, Szczęsna-Górniak, Weronika, Batys, Piotr, Jarek, Ewelina, Wilk, Kazimiera A, Warszyński, Piotr
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2025
Zugriff auf das übergeordnete Werk:Langmuir : the ACS journal of surfaces and colloids
Schlagworte:Journal Article
Beschreibung
Zusammenfassung:The interfacial behavior of aqueous solutions of newly synthesized 2-alkyl-N,N,N,N',N',N'-hexamethylpropan-1,3-ammonium dibromides with decyl, dodecyl, and tetradecyl alkyl chains was investigated both experimentally and theoretically. The results of the surface tension measurements were described using the modified surface quasi-two-dimensional electrolyte (mSTDE) model of ionic surfactant adsorption, which was supported by molecular dynamics simulations. Our contribution encompasses the design, synthesis, and characterization of a novel class of dicephalic-type cationic surfactants, branched on a methine motif, possessing two symmetric trimethylammonium groups, which constitute a double-head extension of the standard alkyltrimethylammonium salts of the single-head, single-tail structure. The convenient synthetic route and final purification steps allowed for the high-yield, high-purity production of the surfactants. Dicephalic-type surfactants demonstrated lower surface activity and higher critical micelle concentration values when compared with their single head-single tail counterparts. That can be attributed primarily to the presence of strong electrostatic repulsive forces within the bulky, double-charge headgroups and significant counterion condensation. Furthermore, molecular dynamics simulations demonstrated a propensity for the desorption of surfactants from the interface, even in diluted solutions, which constrained the attainable surface concentration and resulted in a lower reduction in surface tension. The mSTDE model of adsorption provided an excellent description of the experimental surface isotherms with a concise set of parameters. The model's predictive power was demonstrated by the studies of the effect of inorganic salts on the surface activity of investigated surfactants. Our unique approach enabled us to gain a theoretical explanation of the newly devised surfactants' behavior at the water/air interface
Beschreibung:Date Revised 05.04.2025
published: Print-Electronic
Citation Status PubMed-not-MEDLINE
ISSN:1520-5827
DOI:10.1021/acs.langmuir.4c04803