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The Nature of the Low-Temperature Crossover of Water in Hard Confinement

[Image: see text] The dynamics of water confined in mesoporous MIP (2–3 nm pores in size) with silica gel (secondary silica; further, the abbreviation SG will be used) and MAP (10–35 nm pores in size) without SG borosilicate glasses have been studied by broadband dielectric spectroscopy (BDS), nucle...

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Autores principales: Beilinson, Yael, Schiller, Verena, Regentin, Julia, Melillo, Jorge H., Greenbaum, Anna, Antropova, Tatiana, Cerveny, Silvina, Vogel, Michael, Feldman, Yuri
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10258804/
https://www.ncbi.nlm.nih.gov/pubmed/37229523
http://dx.doi.org/10.1021/acs.jpcb.3c00747
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author Beilinson, Yael
Schiller, Verena
Regentin, Julia
Melillo, Jorge H.
Greenbaum, Anna
Antropova, Tatiana
Cerveny, Silvina
Vogel, Michael
Feldman, Yuri
author_facet Beilinson, Yael
Schiller, Verena
Regentin, Julia
Melillo, Jorge H.
Greenbaum, Anna
Antropova, Tatiana
Cerveny, Silvina
Vogel, Michael
Feldman, Yuri
author_sort Beilinson, Yael
collection PubMed
description [Image: see text] The dynamics of water confined in mesoporous MIP (2–3 nm pores in size) with silica gel (secondary silica; further, the abbreviation SG will be used) and MAP (10–35 nm pores in size) without SG borosilicate glasses have been studied by broadband dielectric spectroscopy (BDS), nuclear magnetic resonance (NMR), and differential scanning calorimetry (DSC). MIP samples contain secondary silica inside the pores and provide a confinement size of about 2–3 nm, whereas MAP samples are free of secondary silica and provide a confinement size of about 10–35 nm. It is shown by BDS and NMR techniques that water exhibits a dynamic crossover of around 180 K when it is confined in MIP samples. By contrast, water confined in larger pores (MAP) does not exhibit any changes in its relaxation behavior. It is also shown that the crossover temperature depends on the hydration level (the higher the hydration level, the lower the crossover temperature). Below the crossover temperature, we find that water reorientation is isotropic (NMR) and that the temperature-dependent dielectric relaxation strength (BDS) follows the tendency expected for a solid-like material. In contrast, water reorientation is related to long-range diffusion above the crossover temperature, and the dielectric relaxation strength follows the tendency expected for a liquid-like material. Furthermore, the calorimetric results are compatible with crossing a glass transition near 180 K. Finally, the results are discussed within the Gibbs–Thomson model. In this framework, the crossover could be related to ice crystals melting.
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spelling pubmed-102588042023-06-13 The Nature of the Low-Temperature Crossover of Water in Hard Confinement Beilinson, Yael Schiller, Verena Regentin, Julia Melillo, Jorge H. Greenbaum, Anna Antropova, Tatiana Cerveny, Silvina Vogel, Michael Feldman, Yuri J Phys Chem B [Image: see text] The dynamics of water confined in mesoporous MIP (2–3 nm pores in size) with silica gel (secondary silica; further, the abbreviation SG will be used) and MAP (10–35 nm pores in size) without SG borosilicate glasses have been studied by broadband dielectric spectroscopy (BDS), nuclear magnetic resonance (NMR), and differential scanning calorimetry (DSC). MIP samples contain secondary silica inside the pores and provide a confinement size of about 2–3 nm, whereas MAP samples are free of secondary silica and provide a confinement size of about 10–35 nm. It is shown by BDS and NMR techniques that water exhibits a dynamic crossover of around 180 K when it is confined in MIP samples. By contrast, water confined in larger pores (MAP) does not exhibit any changes in its relaxation behavior. It is also shown that the crossover temperature depends on the hydration level (the higher the hydration level, the lower the crossover temperature). Below the crossover temperature, we find that water reorientation is isotropic (NMR) and that the temperature-dependent dielectric relaxation strength (BDS) follows the tendency expected for a solid-like material. In contrast, water reorientation is related to long-range diffusion above the crossover temperature, and the dielectric relaxation strength follows the tendency expected for a liquid-like material. Furthermore, the calorimetric results are compatible with crossing a glass transition near 180 K. Finally, the results are discussed within the Gibbs–Thomson model. In this framework, the crossover could be related to ice crystals melting. American Chemical Society 2023-05-25 /pmc/articles/PMC10258804/ /pubmed/37229523 http://dx.doi.org/10.1021/acs.jpcb.3c00747 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Beilinson, Yael
Schiller, Verena
Regentin, Julia
Melillo, Jorge H.
Greenbaum, Anna
Antropova, Tatiana
Cerveny, Silvina
Vogel, Michael
Feldman, Yuri
The Nature of the Low-Temperature Crossover of Water in Hard Confinement
title The Nature of the Low-Temperature Crossover of Water in Hard Confinement
title_full The Nature of the Low-Temperature Crossover of Water in Hard Confinement
title_fullStr The Nature of the Low-Temperature Crossover of Water in Hard Confinement
title_full_unstemmed The Nature of the Low-Temperature Crossover of Water in Hard Confinement
title_short The Nature of the Low-Temperature Crossover of Water in Hard Confinement
title_sort nature of the low-temperature crossover of water in hard confinement
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10258804/
https://www.ncbi.nlm.nih.gov/pubmed/37229523
http://dx.doi.org/10.1021/acs.jpcb.3c00747
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