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Title: Antifreeze Hydrogels from Amphiphilic Statistical Copolymers

Abstract

Prevention of ice formation is a critical issue for many applications, but routes to overcome the large thermodynamic driving force for crystallization of water at significant supercooling are limited. Here, we demonstrate that supramolecular hydrogels formed from statistical copolymers of 2-hydroxyethyl acrylate (HEA) and 2-(N-ethylperfluorooctane sulfonamido)ethyl methacrylate (FOSM) exhibit a degree of ice formation suppression unprecedented in a synthetic material. The mechanisms of ice prevention by these hydrogels mimic two methods used by nature: (1) hydrogen bonding of water to highly hydrophilic macromolecular chains and (2) nanoconfinement of water between hydrophobic moieties. From systematic variation in the copolymer composition to control the nanoscale (<4 nm) separation of the self-assembled hydrophobic nanodomains, the main mechanism by which these supramolecular hydrogels inhibit large amounts of water from freezing appears to be soft nanoconfinement. Nearly complete ice inhibition was achieved in hydrogels when the nanodomain separation was <3 nm (i.e., confinement volume ~15 nm3) where <290 water molecules are present. Dielectric spectroscopy is consistent with two primary populations of water: a population of water with a bulk-like dynamics as well as Tg (136 K) and a minority population of water with suppressed dynamics and an enhanced Tg near 151 K that is attributedmore » to interfacial water. The nanostructured design of these supramolecular hydrogels provides a blueprint concept for controlling and manipulating ice formation in concentrated soft matter using the length scale between hydrophobic domains and the hydrophilicity of the network water-soluble component. Furthermore, these insights have the potential to provide solutions to challenges with ice in engineering applications where confinement of water to nanoscale dimensions is possible.« less

Authors:
ORCiD logo [1];  [2];  [1];  [1]; ORCiD logo [3];  [4];  [4]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Akron, Akron, OH (United States)
  2. Univ. of Akron, Akron, OH (United States); 3M Center St., St. Paul, MN (United States)
  3. Univ. of South Florida, Tampa, FL (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1493571
Report Number(s):
BNL-211245-2019-JAAM
Journal ID: ISSN 0897-4756
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 1; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Wang, Chao, Wiener, Clinton G., Sepulveda-Medina, Pablo I., Ye, Changhuai, Simmons, David S., Li, Ruipeng, Fukuto, Masafumi, Weiss, R. A., and Vogt, Bryan D. Antifreeze Hydrogels from Amphiphilic Statistical Copolymers. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.8b03650.
Wang, Chao, Wiener, Clinton G., Sepulveda-Medina, Pablo I., Ye, Changhuai, Simmons, David S., Li, Ruipeng, Fukuto, Masafumi, Weiss, R. A., & Vogt, Bryan D. Antifreeze Hydrogels from Amphiphilic Statistical Copolymers. United States. doi:10.1021/acs.chemmater.8b03650.
Wang, Chao, Wiener, Clinton G., Sepulveda-Medina, Pablo I., Ye, Changhuai, Simmons, David S., Li, Ruipeng, Fukuto, Masafumi, Weiss, R. A., and Vogt, Bryan D. Thu . "Antifreeze Hydrogels from Amphiphilic Statistical Copolymers". United States. doi:10.1021/acs.chemmater.8b03650. https://www.osti.gov/servlets/purl/1493571.
@article{osti_1493571,
title = {Antifreeze Hydrogels from Amphiphilic Statistical Copolymers},
author = {Wang, Chao and Wiener, Clinton G. and Sepulveda-Medina, Pablo I. and Ye, Changhuai and Simmons, David S. and Li, Ruipeng and Fukuto, Masafumi and Weiss, R. A. and Vogt, Bryan D.},
abstractNote = {Prevention of ice formation is a critical issue for many applications, but routes to overcome the large thermodynamic driving force for crystallization of water at significant supercooling are limited. Here, we demonstrate that supramolecular hydrogels formed from statistical copolymers of 2-hydroxyethyl acrylate (HEA) and 2-(N-ethylperfluorooctane sulfonamido)ethyl methacrylate (FOSM) exhibit a degree of ice formation suppression unprecedented in a synthetic material. The mechanisms of ice prevention by these hydrogels mimic two methods used by nature: (1) hydrogen bonding of water to highly hydrophilic macromolecular chains and (2) nanoconfinement of water between hydrophobic moieties. From systematic variation in the copolymer composition to control the nanoscale (<4 nm) separation of the self-assembled hydrophobic nanodomains, the main mechanism by which these supramolecular hydrogels inhibit large amounts of water from freezing appears to be soft nanoconfinement. Nearly complete ice inhibition was achieved in hydrogels when the nanodomain separation was <3 nm (i.e., confinement volume ~15 nm3) where <290 water molecules are present. Dielectric spectroscopy is consistent with two primary populations of water: a population of water with a bulk-like dynamics as well as Tg (136 K) and a minority population of water with suppressed dynamics and an enhanced Tg near 151 K that is attributed to interfacial water. The nanostructured design of these supramolecular hydrogels provides a blueprint concept for controlling and manipulating ice formation in concentrated soft matter using the length scale between hydrophobic domains and the hydrophilicity of the network water-soluble component. Furthermore, these insights have the potential to provide solutions to challenges with ice in engineering applications where confinement of water to nanoscale dimensions is possible.},
doi = {10.1021/acs.chemmater.8b03650},
journal = {Chemistry of Materials},
number = 1,
volume = 31,
place = {United States},
year = {2018},
month = {12}
}

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Biomimetic Extreme‐Temperature‐ and Environment‐Adaptable Hydrogels
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