Ion-specific Confined Water Dynamics in Convex Nanopores of Gemini Surfactant Lyotropic Liquid Crystals

Jackson, Grayson L.; Mantha, Sriteja; Kim, Sung A.; Diallo, Souleymane O.; Herwig, Kenneth W.; Yethiraj, Arun; Mahanthappa, Mahesh K.

doi:10.1021/acs.jpcb.8b05942

Title: Ion-specific Confined Water Dynamics in Convex Nanopores of Gemini Surfactant Lyotropic Liquid Crystals

Abstract

The impact of pore geometry and functionality on the dynamics of water nanoconfined in porous media are the subject of some debate. Here, we report the synthesis and small-angle X-ray scattering (SAXS) characterization of a series of perdeuterated gemini surfactant lyotropic liquid crystals (LLCs), in which convex, water-filled nanopores of well-defined dimensions are lined with carboxylate functionalities. Quasielastic neutron scattering (QENS) measurements of the translational water dynamics in these dicarboxylate LLC nanopores as functions of the surfactant hydration state and the charge compensating counterion (Na⁺, K⁺, NMe₄⁺) reveal that the measured dynamics depend primarily on surfactant hydration, with an unexpected counterion dependence that varies with hydration number. We rationalize these trends in terms of a balance between counterion-water attractions and the nanopore volume excluded by the counterions. On the basis of electron density maps derived from SAXS analyses of these LLCs, we directly show that the volume excluded by the counterions depends on both their size and spatial distribution in the water-filled channels. The translational water dynamics in the convex pores of these LLCs are also slower than those reported in the concave pores of AOT reverse micelles, implying that water dynamics also depend on the nanopore curvature.

Authors:

Jackson, Grayson L. ^[1]; Mantha, Sriteja ^[1]; Kim, Sung A. ^[2]; Diallo, Souleymane O. ^[3]; Herwig, Kenneth W. ^[4]; Yethiraj, Arun ^[1]; Mahanthappa, Mahesh K. ^[5]

Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry
Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemical Engineering and Materials Science
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Science Division
Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry; Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemical Engineering and Materials Science

Publication Date:: Tue Sep 25 00:00:00 EDT 2018

Research Org.:: Univ. of Minnesota, Minneapolis, MN (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Dept. of Defense (DOD); National Science Foundation (NSF); National Institutes of Health (NIH)

OSTI Identifier:: 1473701

Grant/Contract Number:: SC0010328; AC02-06CH11357; CHE-9974839; CHE-1048642; DMR-0832760; DMR-1121288; DMR-1420013; S10OD011952

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Additional Journal Information:: Journal Volume: 122; Journal Issue: 43; Journal ID: ISSN 1520-6106

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats


                    Jackson, Grayson L., Mantha, Sriteja, Kim, Sung A., Diallo, Souleymane O., Herwig, Kenneth W., Yethiraj, Arun, and Mahanthappa, Mahesh K. Ion-specific Confined Water Dynamics in Convex Nanopores of Gemini Surfactant Lyotropic Liquid Crystals.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpcb.8b05942.

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                    Jackson, Grayson L., Mantha, Sriteja, Kim, Sung A., Diallo, Souleymane O., Herwig, Kenneth W., Yethiraj, Arun, & Mahanthappa, Mahesh K. Ion-specific Confined Water Dynamics in Convex Nanopores of Gemini Surfactant Lyotropic Liquid Crystals.  United States.  https://doi.org/10.1021/acs.jpcb.8b05942

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                    Jackson, Grayson L., Mantha, Sriteja, Kim, Sung A., Diallo, Souleymane O., Herwig, Kenneth W., Yethiraj, Arun, and Mahanthappa, Mahesh K. Tue .  
"Ion-specific Confined Water Dynamics in Convex Nanopores of Gemini Surfactant Lyotropic Liquid Crystals".  United States.  https://doi.org/10.1021/acs.jpcb.8b05942.  https://www.osti.gov/servlets/purl/1473701.

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@article{osti_1473701,

  title        = {Ion-specific Confined Water Dynamics in Convex Nanopores of Gemini Surfactant Lyotropic Liquid Crystals},

  author       = {Jackson, Grayson L. and Mantha, Sriteja and Kim, Sung A. and Diallo, Souleymane O. and Herwig, Kenneth W. and Yethiraj, Arun and Mahanthappa, Mahesh K.},

  abstractNote = {The impact of pore geometry and functionality on the dynamics of water nanoconfined in porous media are the subject of some debate. Here, we report the synthesis and small-angle X-ray scattering (SAXS) characterization of a series of perdeuterated gemini surfactant lyotropic liquid crystals (LLCs), in which convex, water-filled nanopores of well-defined dimensions are lined with carboxylate functionalities. Quasielastic neutron scattering (QENS) measurements of the translational water dynamics in these dicarboxylate LLC nanopores as functions of the surfactant hydration state and the charge compensating counterion (Na+, K+, NMe4+) reveal that the measured dynamics depend primarily on surfactant hydration, with an unexpected counterion dependence that varies with hydration number. We rationalize these trends in terms of a balance between counterion-water attractions and the nanopore volume excluded by the counterions. On the basis of electron density maps derived from SAXS analyses of these LLCs, we directly show that the volume excluded by the counterions depends on both their size and spatial distribution in the water-filled channels. The translational water dynamics in the convex pores of these LLCs are also slower than those reported in the concave pores of AOT reverse micelles, implying that water dynamics also depend on the nanopore curvature.},

  doi          = {10.1021/acs.jpcb.8b05942},

  journal      = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},

  number       = 43,

  volume       = 122,

  place        = {United States},

  year         = {Tue Sep 25 00:00:00 EDT 2018},

  month        = {Tue Sep 25 00:00:00 EDT 2018}

}

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https://doi.org/10.1021/acs.jpcb.8b05942

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Figure 1: Water-driven self-assembly of gemini dicarboxylate amphiphiles affords well-defined convex nanochannels lined with carboxylate functionalities and filled with hydrated surfactant counterions. Gemini amphiphiles form bicontinuous double gyroid network (G_I) phases at low hydrations and hexagonallypacked cylinders (H_I) at higher hydrations.

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