Dioctyl sodium sulfosuccinate surfactant self-assembly dependency of solvent hydrophilicity: a modelling study

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

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en

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14

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Physical Chemistry Chemical Physics, Volume 25, issue 40, pp. 27250-27263

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The self-assembly of dioctyl sodium sulfosuccinate (AOT) model surfactant in solvent environments of differing polarity is examined by means of dissipative particle dynamics (DPD) bead model parametrized against Hildebrand solubility parameters from atomistic molecular dynamics (MD) simulations. The model predicts that in hydrophobic solvents (e.g. dodecane) the surfactant forms small (Nagg ∼ 8) reverse micellar aggregates, while in a solvent corresponding to water lamellar assembly takes place, in good agreement with literature structural parameters. Interestingly, solvents of intermediate polarity lead to formation of large, internally structured aggregates. In these, the surfactant headgroups cluster within the aggregate, surrounded by a continuous phase formed by the hydrocarbon tails. We show that the partitioning of the headgroups between the aggregate surface layer and the inner clustered phase depends primarily on solvent polarity, and can be controlled by the solvent, but also system composition. Finally, we compare the DPD assembly response to simplified effective interaction potentials derived at dilute concentration limit for the interactions. The comparison reveals that the simplified effective potential descriptions provide good level of insight on the assembly morphologies, despite drastic, isotropic interactions simplification involved.

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Funding Information: This work was supported by the Academy of Finland through its Centres of Excellence Programme (2022-2029, LIBER) under project no. 346111 (M. S.), Novo Nordisk Foundation under project no. NNF22OC0074060 (M. S.) and the Project HPC-EUROPA3 (INFRAIA-2016-1-730897) (A. S.), with the support of the EC Research Innovation Action under the H2020 Programme. M. S. thanks Prof. Jaakko Timonen for asking the questions that motivated examining AOT aggregation response via modelling approaches and the ensuing discussions. A. S. gratefully acknowledges Prof. Uwe Thiele for scientific discussions and hosting of his research visit at the Institute of Theoretical Physics, WWU Münster, as well as the computer resources and technical support provided by HLSR Stuttgart. Computational resources by CSC IT Centre for Finland, RAMI – RawMatters Finland Infrastructure, and Aalto Science-IT project are also gratefully acknowledged. We are grateful for the support by FinnCERES Materials Bioeconomy Ecosystem. Publisher Copyright: © 2023 The Royal Society of Chemistry.

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Vuorte, M, Lokka, A, Scacchi, A & Sammalkorpi, M 2023, 'Dioctyl sodium sulfosuccinate surfactant self-assembly dependency of solvent hydrophilicity: a modelling study', Physical Chemistry Chemical Physics, vol. 25, no. 40, pp. 27250-27263. https://doi.org/10.1039/d3cp02173d