Dynamic Behaviors of Solvent Molecules Restricted in Poly (Acryl Amide) Gels Analyzed by Dielectric and Diffusion NMR Spectroscopy

用介电和扩散核磁共振光谱分析聚(丙烯酰胺)凝胶中溶剂分子的动态行为

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作者:Hironobu Saito, Shunpei Kato, Keisuke Matsumoto, Yuya Umino, Rio Kita, Naoki Shinyashiki, Shin Yagihara, Minoru Fukuzaki, Masayuki Tokita

Abstract

Dynamics of solvent molecules restricted in poly (acryl amide) gels immersed in solvent mixtures of acetone⁻, 1,4-dioxane⁻, and dimethyl sulfoxide⁻water were analyzed by the time domain reflectometry method of dielectric spectroscopy and the pulse field gradient method of nuclear magnetic resonance. Restrictions of dynamic behaviors of solvent molecules were evaluated from relaxation parameters such as the relaxation time, its distribution parameter, and the relaxation strength obtained by dielectric measurements, and similar behaviors with polymer concentration dependences for the solutions were obtained except for the high polymer concentration in collapsed gels. Scaling analyses for the relaxation time and diffusion coefficient respectively normalized by those for bulk solvent suggested that the scaling exponent determined from the scaling variable defined as a ratio of the size of solvent molecule to mesh size of polymer networks were three and unity, respectively, except for collapsed gels. The difference in these components reflects characteristic molecular interactions in the rotational and translational diffusions, and offered a physical picture of the restriction of solvent dynamics. A universal treatment of slow dynamics due to the restriction from polymer chains suggests a new methodology of characterization of water structures.

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