Confinement Effects on Glass-Forming Aqueous Dimethyl Sulfoxide Solutions
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 wi...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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MDPI AG
2020-09-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/18/4127 |
| _version_ | 1797554169507217408 |
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| author | Dominik Demuth Melanie Reuhl Moritz Hopfenmüller Nail Karabas Simon Schoner Michael Vogel |
| author_facet | Dominik Demuth Melanie Reuhl Moritz Hopfenmüller Nail Karabas Simon Schoner Michael Vogel |
| author_sort | Dominik Demuth |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-03-10T16:28:01Z |
| format | Article |
| id | doaj.art-ddee83d529014534a187c0d382186409 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T16:28:01Z |
| publishDate | 2020-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-ddee83d529014534a187c0d3821864092023-11-20T13:08:11ZengMDPI AGMolecules1420-30492020-09-012518412710.3390/molecules25184127Confinement Effects on Glass-Forming Aqueous Dimethyl Sulfoxide SolutionsDominik Demuth0Melanie Reuhl1Moritz Hopfenmüller2Nail Karabas3Simon Schoner4Michael Vogel5Institute of Condensed Matter Physics, Technische Universität Darmstadt, 64289 Darmstadt, GermanyInstitute of Condensed Matter Physics, Technische Universität Darmstadt, 64289 Darmstadt, GermanyInstitute of Condensed Matter Physics, Technische Universität Darmstadt, 64289 Darmstadt, GermanyInstitute of Condensed Matter Physics, Technische Universität Darmstadt, 64289 Darmstadt, GermanyInstitute of Condensed Matter Physics, Technische Universität Darmstadt, 64289 Darmstadt, GermanyInstitute of Condensed Matter Physics, Technische Universität Darmstadt, 64289 Darmstadt, GermanyCombining 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.https://www.mdpi.com/1420-3049/25/18/4127confinementaqueous solutionsglass transitionmolecular dynamicsbroadband dielectric spectroscopynuclear magnetic resonance |
| spellingShingle | Dominik Demuth Melanie Reuhl Moritz Hopfenmüller Nail Karabas Simon Schoner Michael Vogel Confinement Effects on Glass-Forming Aqueous Dimethyl Sulfoxide Solutions Molecules confinement aqueous solutions glass transition molecular dynamics broadband dielectric spectroscopy nuclear magnetic resonance |
| title | Confinement Effects on Glass-Forming Aqueous Dimethyl Sulfoxide Solutions |
| title_full | Confinement Effects on Glass-Forming Aqueous Dimethyl Sulfoxide Solutions |
| title_fullStr | Confinement Effects on Glass-Forming Aqueous Dimethyl Sulfoxide Solutions |
| title_full_unstemmed | Confinement Effects on Glass-Forming Aqueous Dimethyl Sulfoxide Solutions |
| title_short | Confinement Effects on Glass-Forming Aqueous Dimethyl Sulfoxide Solutions |
| title_sort | confinement effects on glass forming aqueous dimethyl sulfoxide solutions |
| topic | confinement aqueous solutions glass transition molecular dynamics broadband dielectric spectroscopy nuclear magnetic resonance |
| url | https://www.mdpi.com/1420-3049/25/18/4127 |
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