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Title: Water Dynamics in Gyroid Phases of Self-Assembled Gemini Surfactants

Abstract

Water-mediated ion transport through functional nanoporous materials depends on the dynamics of water confined within a given nanostructured morphology. In this study, we investigate hydrogen-bonding dynamics of interfacial water within a ‘normal’ (Type I) lyotropic gyroid phase formed by a gemini dicarboxylate surfactant self-assembly using a combina- tion of 2DIR spectroscopy and molecular dynamics simulations. Experiments and simulations demonstrate that water dynamics in the normal gyroid phase is one order of magnitude slower than that in bulk water, due to specific interactions between water, the ionic surfactant headgroups, and counterions. However, the dynamics of water in the normal gyroid phase are faster than those of water confined in a reverse spherical micelle of a sulfonate surfactant, given that the water pool in the reverse micelle and the water pore in the gyroid phase have roughly the same diameters. This difference in confined water dynamics likely arises from the significantly reduced curvature- induced frustration at the convex interfaces of the normal gyroid, as compared to the concave interfaces of a reverse spherical micelle. These detailed insights into confined water dynamics may guide the future design of artificial membranes that rapidly transport protons and other ions.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
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  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1341619
Report Number(s):
DOE-UWMadison-46938-1st product
Journal ID: ISSN 0002-7863; FG02-13ER46938
Grant/Contract Number:  
SC0010328; FG02-09ER16110; CHE-0840494
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 8; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; gyroid; Water dynamics; nanoconfinement

Citation Formats

Roy, Santanu, Skoff, David, Perroni, Dominic V., Mondal, Jagannath, Yethiraj, Arun, Mahanthappa, Mahesh K., Zanni, Martin T., and Skinner, James L. Water Dynamics in Gyroid Phases of Self-Assembled Gemini Surfactants. United States: N. p., 2016. Web. doi:10.1021/jacs.5b12370.
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Roy, Santanu, Skoff, David, Perroni, Dominic V., Mondal, Jagannath, Yethiraj, Arun, Mahanthappa, Mahesh K., Zanni, Martin T., & Skinner, James L. Water Dynamics in Gyroid Phases of Self-Assembled Gemini Surfactants. United States. https://doi.org/10.1021/jacs.5b12370
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Roy, Santanu, Skoff, David, Perroni, Dominic V., Mondal, Jagannath, Yethiraj, Arun, Mahanthappa, Mahesh K., Zanni, Martin T., and Skinner, James L. Sun . "Water Dynamics in Gyroid Phases of Self-Assembled Gemini Surfactants". United States. https://doi.org/10.1021/jacs.5b12370. https://www.osti.gov/servlets/purl/1341619.
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@article{osti_1341619,
title = {Water Dynamics in Gyroid Phases of Self-Assembled Gemini Surfactants},
author = {Roy, Santanu and Skoff, David and Perroni, Dominic V. and Mondal, Jagannath and Yethiraj, Arun and Mahanthappa, Mahesh K. and Zanni, Martin T. and Skinner, James L.},
abstractNote = {Water-mediated ion transport through functional nanoporous materials depends on the dynamics of water confined within a given nanostructured morphology. In this study, we investigate hydrogen-bonding dynamics of interfacial water within a ‘normal’ (Type I) lyotropic gyroid phase formed by a gemini dicarboxylate surfactant self-assembly using a combina- tion of 2DIR spectroscopy and molecular dynamics simulations. Experiments and simulations demonstrate that water dynamics in the normal gyroid phase is one order of magnitude slower than that in bulk water, due to specific interactions between water, the ionic surfactant headgroups, and counterions. However, the dynamics of water in the normal gyroid phase are faster than those of water confined in a reverse spherical micelle of a sulfonate surfactant, given that the water pool in the reverse micelle and the water pore in the gyroid phase have roughly the same diameters. This difference in confined water dynamics likely arises from the significantly reduced curvature- induced frustration at the convex interfaces of the normal gyroid, as compared to the concave interfaces of a reverse spherical micelle. These detailed insights into confined water dynamics may guide the future design of artificial membranes that rapidly transport protons and other ions.},
doi = {10.1021/jacs.5b12370},
journal = {Journal of the American Chemical Society},
number = 8,
volume = 138,
place = {United States},
year = {Sun Feb 14 00:00:00 EST 2016},
month = {Sun Feb 14 00:00:00 EST 2016}
}
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https://doi.org/10.1021/jacs.5b12370
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