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Article

Confinement Effects on Glass-Forming Aqueous Dimethyl Sulfoxide Solutions

Institute of Condensed Matter Physics, Technische Universität Darmstadt, 64289 Darmstadt, Germany
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Author to whom correspondence should be addressed.
These authors contributed equally to this work.
Molecules 2020, 25(18), 4127; https://doi.org/10.3390/molecules25184127
Received: 11 August 2020 / Revised: 4 September 2020 / Accepted: 5 September 2020 / Published: 9 September 2020
(This article belongs to the Special Issue Physical Chemistry of Aqueous Solutions and Glass Forming Systems)
Combining broadband dielectric spectroscopy and nuclear magnetic resonance studies, we analyze the reorientation dynamics and the translational diffusion associated with the glassy slowdown of the eutectic aqueous dimethyl sulfoxide solution in nano-sized confinements, explicitly, in silica pores with different diameters and in ficoll and lysozyme matrices at different concentrations. We observe that both rotational and diffusive dynamics are slower and more heterogeneous in the confinements than in the bulk but the degree of these effects depends on the properties of the confinement and differs for the components of the solution. For the hard and the soft matrices, the slowdown and the heterogeneity become more prominent when the size of the confinement is reduced. In addition, the dynamics are more retarded for dimethyl sulfoxide than for water, implying specific guest-host interactions. Moreover, we find that the temperature dependence of the reorientation dynamics and of the translational diffusion differs in severe confinements, indicating a breakdown of the Stokes–Einstein–Debye relation. It is discussed to what extent these confinement effects can be rationalized in the framework of core-shell models, which assume bulk-like and slowed-down motions in central and interfacial confinement regions, respectively. View Full-Text
Keywords: confinement; aqueous solutions; glass transition; molecular dynamics; broadband dielectric spectroscopy; nuclear magnetic resonance confinement; aqueous solutions; glass transition; molecular dynamics; broadband dielectric spectroscopy; nuclear magnetic resonance
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MDPI and ACS Style

Demuth, D.; Reuhl, M.; Hopfenmüller, M.; Karabas, N.; Schoner, S.; Vogel, M. Confinement Effects on Glass-Forming Aqueous Dimethyl Sulfoxide Solutions. Molecules 2020, 25, 4127. https://doi.org/10.3390/molecules25184127

AMA Style

Demuth D, Reuhl M, Hopfenmüller M, Karabas N, Schoner S, Vogel M. Confinement Effects on Glass-Forming Aqueous Dimethyl Sulfoxide Solutions. Molecules. 2020; 25(18):4127. https://doi.org/10.3390/molecules25184127

Chicago/Turabian Style

Demuth, Dominik, Melanie Reuhl, Moritz Hopfenmüller, Nail Karabas, Simon Schoner, and Michael Vogel. 2020. "Confinement Effects on Glass-Forming Aqueous Dimethyl Sulfoxide Solutions" Molecules 25, no. 18: 4127. https://doi.org/10.3390/molecules25184127

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