Consequences of Convex Nanopore Chemistry on Confined Water Dynamics

Jackson, Grayson L.; Kim, Sung A.; Jayaraman, Ashish; Diallo, Souleymane O.; Mahanthappa, Mahesh K.

doi:10.1021/acs.jpcb.9b10176

Title: Consequences of Convex Nanopore Chemistry on Confined Water Dynamics

Journal Article · Mon Feb 17 00:00:00 EST 2020 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.9b10176· OSTI ID:1601776

^[1]; Kim, Sung A. ^[2];

^[2]; Diallo, Souleymane O. ^[3];

^[4]

Univ. of Wisconsin, Madison, WI (United States)
Univ. of Minnesota, Minneapolis, MN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Wisconsin, Madison, WI (United States); Univ. of Minnesota, Minneapolis, MN (United States)

A basic 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 discuss 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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Research Organization:: Univ. of Wisconsin, Madison, WI (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0010328; AC02-06CH11357; NSF-1608115; DMR-1420013

OSTI ID:: 1601776

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 124, Issue 8; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 3 works

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