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Interfacial H-Bond Dynamics in Reverse Micelles: The Role of Surfactant Heterogeneity

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    Interfacial H-Bond Dynamics in Reverse Micelles: The Role of Surfactant Heterogeneity
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    Langmuir

    Cite this: Langmuir 2019, 35, 35, 11463–11470
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    https://doi.org/10.1021/acs.langmuir.9b01693
    Published August 13, 2019
    Copyright © 2019 American Chemical Society
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    Abstract

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    Characterizing the hydrogen bond structure and dynamics at surfactant interfaces is essential for understanding how microscopic interactions translate to bulk microemulsion properties. Heterogeneous blends containing tens or hundreds of surfactants are common in the industry, but the most fundamental studies have been carried out on micelles composed of a single surfactant species. Therefore, the effect of surfactant heterogeneity on the interfacial structure and dynamics remains poorly understood. Here, we use ultrafast two-dimensional infrared spectroscopy and molecular dynamics simulations to characterize sub-picosecond solvation dynamics as a function of the surfactant composition in ∼120 nm water-in-oil reverse micelles. We probe the ester carbonyl vibrations of nonionic sorbitan surfactants, which are located precisely at the interface between the polar and nonpolar regions, and as such, report on the interfacial water dynamics. We show a 7% increase in hydrogen bond populations together with a 37% slowdown of interfacial hydrogen bond dynamics in heterogeneous mixtures containing hundreds of species, compared to more uniform compositions. Simulations, which are in semiquantitative agreement with experiments, indicate that structural diversity leads to decreased packing efficiency, which in turn drives water further into the otherwise hydrophobic region. Interestingly, this increase in hydration is accompanied by a slowdown of dynamics, indicating that water molecules solvating surfactants are conformationally constrained. These studies demonstrate that the composition and heterogeneity are key factors in determining interfacial properties.

    Copyright © 2019 American Chemical Society

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.langmuir.9b01693.

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    Langmuir

    Cite this: Langmuir 2019, 35, 35, 11463–11470
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.langmuir.9b01693
    Published August 13, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

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