Grayson L Jackson1, Sung A Kim2, Ashish Jayaraman2, Souleymane O Diallo3, Mahesh K Mahanthappa1,2. 1. Department of Chemistry , University of Wisconsin-Madison , 1101 University Avenue , Madison , Wisconsin 53706 , United States. 2. Department of Chemical Engineering & Materials Science , University of Minnesota , 421 Washington Avenue, S.E. , Minneapolis , Minnesota 55455 , United States. 3. Chemical and Engineering Materials Division , Oak Ridge National Laboratory , Oak Ridge , Tennessee 37831 United States.
Abstract
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+, NMe4+). The consistency of the observed counterion-dependent water dynamics trends 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-SO3- 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.
A fundamental understanding of confined water is crucial for developing selective ion transport and n class="Chemical">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+, NMe4+). The consistency of the observed counterion-dependent water dynamics trends 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-SO3- 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.
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Authors: N C Osti; T N Etampawala; U M Shrestha; D Aryal; M Tyagi; S O Diallo; E Mamontov; C J Cornelius; D Perahia Journal: J Chem Phys Date: 2016-12-14 Impact factor: 3.488
Authors: Grayson L Jackson; Sriteja Mantha; Sung A Kim; Souleymane O Diallo; Kenneth W Herwig; Arun Yethiraj; Mahesh K Mahanthappa Journal: J Phys Chem B Date: 2018-10-18 Impact factor: 2.991