Consequences of Convex Nanopore Chemistry on Confined Water Dynamics
| Autor: | Grayson L. Jackson, Souleymane Diallo, Sung A Kim, Mahesh K. Mahanthappa, Ashish Jayaraman |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
Alkanesulfonates
chemistry.chemical_classification Molecular Structure Scattering Small-angle X-ray scattering Water Ionic bonding Molecular Dynamics Simulation Article Liquid Crystals Surfaces Coatings and Films Nanopores Neutron Diffraction Nanopore Membrane chemistry Lyotropic liquid crystal Chemical physics Scattering Small Angle Quasielastic neutron scattering Materials Chemistry Physical and Theoretical Chemistry Counterion Hydrophobic and Hydrophilic Interactions |
| Zdroj: | J Phys Chem B |
| ISSN: | 1520-5207 1520-6106 |
| DOI: | 10.1021/acs.jpcb.9b10176 |
| Popis: | A fundamental understanding of confined water is crucial for developing selective ion transport and water purification membranes, yet the roles of nanopore geometry and functionality on confined water dynamics remain unresolved. We report the synthesis of perdeuterated ionic alkylsulfonate amphiphiles and their water-induced self-assembly into lyotropic liquid crystal (LLC) mesophases with well-defined, convex sulfonate-lined nanopores. Quasielastic neutron scattering (QENS) measurements demonstrate that the water self-diffusion coefficients within these sulfonate-lined convex nanopores depend on the hydration level and amphiphile counterion identity (H(+), K(+), NMe(4)(+)). The consistency of the observed counterion-dependent water dynamics with those of carboxylate LLCs is rationalized on the basis of similarities in the counterion spatial distributions in the water-filled channels, which we deduce from electron density maps derived from small-angle X-ray scattering (SAXS) analyses. These findings indicate that water diffusion is systematically faster in sulfonate-lined nanopores as compared to carboxylate-lined pores due to weaker water interactions with the softer and more hydrophobic–SO(3)(−) functionalities. These molecular-level insights into the relationships between convex pore wall chemical functionalities, hydrated counterions, and confined water diffusion may inform future development of new nanoporous media. |
| Databáze: | OpenAIRE |
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