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Title: Kinetically controlled morphology in copolymer-based hydrogels crosslinked by crystalline nanodomains determines efficacy of ice inhibition

Abstract

Nature uses protein structure to manipulate the properties of water by altering its local environment, but subtle changes in these structures can dramatically influence function. Here, a simple synthetic analog is demonstrated, a statistical copolymer of hydroxyethyl acrylate and n-octadecyl acrylate (HEA–ODA) with 21.3 mol% ODA, that generates a hydrogel in water. The crystallization of the ODA, whose nanodomains act as effective crosslinks, provides a simple route to manipulate the nanostructure through zone annealing without significantly altering the swelling ratio (1.38 to 1.22) of the hydrogel. Despite the identical average composition, changes in the nanostructure induced by zone annealing leads to significant differences in the inhibition of water crystallization within the hydrogels under supercooled conditions with the unfrozen water fraction varying between nearly 18 and 99%. Decreasing the average spacing between crystalline nanodomains leads to increased efficacy of the ice inhibition. However, the morphological details appear to be important as the average number of water molecules confined in a hypothetical square lattice based on the average interdomain spacing and average ODA nanodomain size does not appear to directly scale with the antifreeze capabilities. Furthermore, these results demonstrate control of water crystallization at supercooled temperatures within hydrogels without fluorinated hydrophobic moietiesmore » through manipulation of the nanostructure to confine the water.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [3];  [1]; ORCiD logo [4]
+ Show Author Affiliations
  1. Univ. of Akron, OH (United States)
  2. Univ. of Akron, OH (United States); Univ. of Delaware, Newark, DE (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Univ. of Akron, OH (United States); Pennsylvania State Univ., University Park, PA (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1614695
Alternate Identifier(s):
OSTI ID: 1569295
Report Number(s):
BNL-213821-2020-JAAM
Journal ID: ISSN 2058-9689; MSDEBG
Grant/Contract Number:  
SC0012704; CBET-1606685; DMR-1508249
Resource Type:
Accepted Manuscript
Journal Name:
Molecular Systems Design & Engineering
Additional Journal Information:
Journal Volume: 5; Journal Issue: 3; Journal ID: ISSN 2058-9689
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Sepulveda-Medina, Pablo I., Wang, Chao, Li, Ruipeng, Fukuto, Masafumi, Weiss, R. A., and Vogt, Bryan D. Kinetically controlled morphology in copolymer-based hydrogels crosslinked by crystalline nanodomains determines efficacy of ice inhibition. United States: N. p., 2019. Web. doi:10.1039/C9ME00101H.
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Sepulveda-Medina, Pablo I., Wang, Chao, Li, Ruipeng, Fukuto, Masafumi, Weiss, R. A., & Vogt, Bryan D. Kinetically controlled morphology in copolymer-based hydrogels crosslinked by crystalline nanodomains determines efficacy of ice inhibition. United States. https://doi.org/10.1039/C9ME00101H
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Sepulveda-Medina, Pablo I., Wang, Chao, Li, Ruipeng, Fukuto, Masafumi, Weiss, R. A., and Vogt, Bryan D. Tue . "Kinetically controlled morphology in copolymer-based hydrogels crosslinked by crystalline nanodomains determines efficacy of ice inhibition". United States. https://doi.org/10.1039/C9ME00101H. https://www.osti.gov/servlets/purl/1614695.
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@article{osti_1614695,
title = {Kinetically controlled morphology in copolymer-based hydrogels crosslinked by crystalline nanodomains determines efficacy of ice inhibition},
author = {Sepulveda-Medina, Pablo I. and Wang, Chao and Li, Ruipeng and Fukuto, Masafumi and Weiss, R. A. and Vogt, Bryan D.},
abstractNote = {Nature uses protein structure to manipulate the properties of water by altering its local environment, but subtle changes in these structures can dramatically influence function. Here, a simple synthetic analog is demonstrated, a statistical copolymer of hydroxyethyl acrylate and n-octadecyl acrylate (HEA–ODA) with 21.3 mol% ODA, that generates a hydrogel in water. The crystallization of the ODA, whose nanodomains act as effective crosslinks, provides a simple route to manipulate the nanostructure through zone annealing without significantly altering the swelling ratio (1.38 to 1.22) of the hydrogel. Despite the identical average composition, changes in the nanostructure induced by zone annealing leads to significant differences in the inhibition of water crystallization within the hydrogels under supercooled conditions with the unfrozen water fraction varying between nearly 18 and 99%. Decreasing the average spacing between crystalline nanodomains leads to increased efficacy of the ice inhibition. However, the morphological details appear to be important as the average number of water molecules confined in a hypothetical square lattice based on the average interdomain spacing and average ODA nanodomain size does not appear to directly scale with the antifreeze capabilities. Furthermore, these results demonstrate control of water crystallization at supercooled temperatures within hydrogels without fluorinated hydrophobic moieties through manipulation of the nanostructure to confine the water.},
doi = {10.1039/C9ME00101H},
journal = {Molecular Systems Design & Engineering},
number = 3,
volume = 5,
place = {United States},
year = {Tue Sep 24 00:00:00 EDT 2019},
month = {Tue Sep 24 00:00:00 EDT 2019}
}
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https://doi.org/10.1039/C9ME00101H
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Works referenced in this record:

The relationship between liquid, supercooled and glassy water
journal, November 1998

  • Mishima, Osamu; Stanley, H. Eugene
  • Nature, Vol. 396, Issue 6709
  • DOI: 10.1038/24540

Water as an Active Constituent in Cell Biology
journal, January 2008

Comparison of simple potential functions for simulating liquid water
journal, July 1983

  • Jorgensen, William L.; Chandrasekhar, Jayaraman; Madura, Jeffry D.
  • The Journal of Chemical Physics, Vol. 79, Issue 2
  • DOI: 10.1063/1.445869

The IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use
journal, June 2002

  • Wagner, W.; Pruß, A.
  • Journal of Physical and Chemical Reference Data, Vol. 31, Issue 2
  • DOI: 10.1063/1.1461829

Theory of amorphous ices
journal, May 2014

  • Limmer, David T.; Chandler, David
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 26
  • DOI: 10.1073/pnas.1407277111

Nature of Amorphous Polymorphism of Water
journal, April 2005

Experimental evidence of a liquid-liquid transition in interfacial water
journal, July 2005

  • Zanotti, J. -M; Bellissent-Funel, M. -C; Chen, S. -H
  • Europhysics Letters (EPL), Vol. 71, Issue 1
  • DOI: 10.1209/epl/i2004-10529-2

The structure of a new phase of ice
journal, January 1998

  • Lobban, C.; Finney, J. L.; Kuhs, W. F.
  • Nature, Vol. 391, Issue 6664
  • DOI: 10.1038/34622

Thermodynamic functions of water and ice confined to 2nm radius pores
journal, March 2005

  • Tombari, E.; Salvetti, G.; Ferrari, C.
  • The Journal of Chemical Physics, Vol. 122, Issue 10
  • DOI: 10.1063/1.1862244

First-order transition in confined water between high-density liquid and low-density amorphous phases
journal, November 2000

  • Koga, Kenichiro; Tanaka, Hideki; Zeng, X. C.
  • Nature, Vol. 408, Issue 6812
  • DOI: 10.1038/35046035

Phase diagram of water in carbon nanotubes
journal, December 2007

  • Takaiwa, D.; Hatano, I.; Koga, K.
  • Proceedings of the National Academy of Sciences, Vol. 105, Issue 1
  • DOI: 10.1073/pnas.0707917105

A Fully Size-Resolved Perspective on the Crystallization of Water Clusters
journal, September 2012

Ice crystallization in water’s “no-man’s land”
journal, June 2010

  • Moore, Emily B.; Molinero, Valeria
  • The Journal of Chemical Physics, Vol. 132, Issue 24
  • DOI: 10.1063/1.3451112

Water motion in reverse micelles studied by quasielastic neutron scattering and molecular dynamics simulations
journal, January 2004

  • Harpham, Michael R.; Ladanyi, Branka M.; Levinger, Nancy E.
  • The Journal of Chemical Physics, Vol. 121, Issue 16
  • DOI: 10.1063/1.1792592

Water nanodroplets confined in zeolite pores
journal, January 2009

  • Coudert, François-Xavier; Cailliez, Fabien; Vuilleumier, Rodolphe
  • Faraday Discuss., Vol. 141
  • DOI: 10.1039/B804992K

Structural and mechanical properties of glassy water in nanoscale confinement
journal, January 2009

  • Lombardo, Thomas G.; Giovambattista, Nicolás; Debenedetti, Pablo G.
  • Faraday Discuss., Vol. 141
  • DOI: 10.1039/B805361H

X-ray Structure of Snow Flea Antifreeze Protein Determined by Racemic Crystallization of Synthetic Protein Enantiomers
journal, July 2008

  • Pentelute, Brad L.; Gates, Zachary P.; Tereshko, Valentina
  • Journal of the American Chemical Society, Vol. 130, Issue 30
  • DOI: 10.1021/ja8013538

Ice-binding structure and mechanism of an antifreeze protein from winter flounder
journal, June 1995

  • Sicheri, F.; Yang, D. S. C.
  • Nature, Vol. 375, Issue 6530
  • DOI: 10.1038/375427a0

Antifreeze Proteins:  Structures and Mechanisms of Function
journal, January 1996

  • Yeh, Yin; Feeney, Robert E.
  • Chemical Reviews, Vol. 96, Issue 2
  • DOI: 10.1021/cr950260c

Convergent evolution of antifreeze glycoproteins in Antarctic notothenioid fish and Arctic cod
journal, April 1997

  • Chen, L.; DeVries, A. L.; Cheng, C. -H. C.
  • Proceedings of the National Academy of Sciences, Vol. 94, Issue 8
  • DOI: 10.1073/pnas.94.8.3817

Facially Amphipathic Glycopolymers Inhibit Ice Recrystallization
journal, April 2018

  • Graham, Ben; Fayter, Alice E. R.; Houston, Judith E.
  • Journal of the American Chemical Society, Vol. 140, Issue 17
  • DOI: 10.1021/jacs.8b02066

Potent inhibition of ice recrystallization by low molecular weight carbohydrate-based surfactants and hydrogelators
journal, January 2012

  • Capicciotti, Chantelle J.; Leclère, Mathieu; Perras, Frédéric A.
  • Chemical Science, Vol. 3, Issue 5
  • DOI: 10.1039/c2sc00885h

Synthetic polymers enable non-vitreous cellular cryopreservation by reducing ice crystal growth during thawing
journal, February 2014

  • Deller, Robert C.; Vatish, Manu; Mitchell, Daniel A.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4244

Polyproline as a Minimal Antifreeze Protein Mimic That Enhances the Cryopreservation of Cell Monolayers
journal, November 2017

  • Graham, Ben; Bailey, Trisha L.; Healey, Joseph R. J.
  • Angewandte Chemie International Edition, Vol. 56, Issue 50
  • DOI: 10.1002/anie.201706703

Structure and reactivity of water at biomaterial surfaces
journal, February 1998

Origin of hydrophobicity and enhanced water hydrogen bond strength near purely hydrophobic solutes
journal, December 2016

  • Grdadolnik, Joze; Merzel, Franci; Avbelj, Franc
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 2
  • DOI: 10.1073/pnas.1612480114

Absence of the Density Minimum of Supercooled Water in Hydrophobic Confinement
journal, April 2009

  • Zhang, Yang; Liu, Kao-Hsiang; Lagi, Marco
  • The Journal of Physical Chemistry B, Vol. 113, Issue 15
  • DOI: 10.1021/jp900641y

Influence of Pore Wall Hydrophobicity on Freezing and Melting of Confined Water
journal, January 2018

Impact of surface wettability on dynamics of supercooled water confined in nitrogen-doped ordered mesoporous carbon
journal, January 2018

  • Wiener, Clinton G.; Qiang, Zhe; Xia, Yanfeng
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 44
  • DOI: 10.1039/C8CP05670F

Water crystallization and its importance to freezing of foods: A review
journal, August 2011

Anti-icing and de-icing techniques for wind turbines: Critical review
journal, January 2011

Quantitative study on the antifreeze protein mimetic ice growth inhibition properties of poly(ampholytes) derived from vinyl-based polymers
journal, January 2014

  • Mitchell, Daniel E.; Lilliman, Mary; Spain, Sebastian G.
  • Biomater. Sci., Vol. 2, Issue 12
  • DOI: 10.1039/C4BM00153B

Dynamics of supercooled water in confined geometry
journal, January 2000

X-ray diffraction study of water confined in activated carbon pores over a temperature range of 228–298 K
journal, October 2006

Supercooled Water in PVA Matrixes:  I. An Incoherent Quasi-Elastic Neutron Scattering (QENS) Study
journal, August 2003

  • Paradossi, Gaio; Cavalieri, Francesca; Chiessi, Ester
  • The Journal of Physical Chemistry B, Vol. 107, Issue 33
  • DOI: 10.1021/jp034542p

Supercooled Water in PVA Matrixes. II. A Molecular Dynamics Simulation Study and Comparison with QENS Results
journal, April 2005

  • Chiessi, Ester; Cavalieri, Francesca; Paradossi, Gaio
  • The Journal of Physical Chemistry B, Vol. 109, Issue 16
  • DOI: 10.1021/jp044807f

Neutron Diffraction of Ice in Hydrogels
journal, September 2014

  • Sekine, Yurina; Ikeda-Fukazawa, Tomoko; Aizawa, Mamoru
  • The Journal of Physical Chemistry B, Vol. 118, Issue 47
  • DOI: 10.1021/jp508269b

Nonfreezing Water Structuration in Heteroprotein Coacervates
journal, April 2015

Non-freezing water in protein solutions
journal, May 1985

  • Ali, S.; Bettelheim, F. A.
  • Colloid and Polymer Science, Vol. 263, Issue 5
  • DOI: 10.1007/BF01410387

Porous Gelatin Hydrogels:  1. Cryogenic Formation and Structure Analysis
journal, February 2007

  • Van Vlierberghe, Sandra; Cnudde, Veerle; Dubruel, Peter
  • Biomacromolecules, Vol. 8, Issue 2
  • DOI: 10.1021/bm060684o

Thermoresponsive Composite Hydrogels with Aligned Macroporous Structure by Ice-Templated Assembly
journal, November 2013

  • Bai, Hao; Polini, Alessandro; Delattre, Benjamin
  • Chemistry of Materials, Vol. 25, Issue 22
  • DOI: 10.1021/cm4025827

Evaluation of the impact of freezing preparation techniques on the characterisation of alginate hydrogels by cryo-SEM
journal, September 2016

Hydrogel with Aligned and Tunable Pore Via “Hot Ice” Template Applies as Bioscaffold
journal, February 2016

  • He, Hongjian; Liu, Mingyu; Wei, Junjie
  • Advanced Healthcare Materials, Vol. 5, Issue 6
  • DOI: 10.1002/adhm.201500707

States of water in partially swollen poly(vinyl alcohol) hydrogels
journal, November 2005

Properties of Water Bound in Hydrogels
journal, October 2017

  • Gun’ko, Vladimir; Savina, Irina; Mikhalovsky, Sergey
  • Gels, Vol. 3, Issue 4
  • DOI: 10.3390/gels3040037

Coagulation size of freezable water in poly(vinyl alcohol) hydrogels formed by different freeze/thaw cycle periods
journal, September 2011

  • Nakano, Tatsuro; Nakaoki, Takahiko
  • Polymer Journal, Vol. 43, Issue 11
  • DOI: 10.1038/pj.2011.92

Heterogeneous ice nucleation correlates with bulk-like interfacial water
journal, April 2019

Bioinspired Materials for Controlling Ice Nucleation, Growth, and Recrystallization
journal, April 2018

Physical hydrogels composed of polyampholytes demonstrate high toughness and viscoelasticity
journal, July 2013

  • Sun, Tao Lin; Kurokawa, Takayuki; Kuroda, Shinya
  • Nature Materials, Vol. 12, Issue 10
  • DOI: 10.1038/nmat3713

Tough and Self-Healing Hydrogels Formed via Hydrophobic Interactions
journal, June 2011

  • Tuncaboylu, Deniz C.; Sari, Murat; Oppermann, Wilhelm
  • Macromolecules, Vol. 44, Issue 12
  • DOI: 10.1021/ma200579v

Physically Cross-Linked Alkylacrylamide Hydrogels:  A SANS Analysis of the Microstructure
journal, December 2004

  • Tian, Jun; Seery, Thomas A. P.; Ho, Derek L.
  • Macromolecules, Vol. 37, Issue 26
  • DOI: 10.1021/ma049474z

Supramolecular Hydrophobic Aggregates in Hydrogels Partially Inhibit Ice Formation
journal, June 2016

  • Wiener, Clinton G.; Tyagi, Madhusudan; Liu, Yun
  • The Journal of Physical Chemistry B, Vol. 120, Issue 24
  • DOI: 10.1021/acs.jpcb.6b02863

Antifreeze Hydrogels from Amphiphilic Statistical Copolymers
journal, November 2018

Behaviour and fate of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in drinking water treatment: A review
journal, March 2014

Extending Dynamic Range of Block Copolymer Ordering with Rotational Cold Zone Annealing (RCZA) and Ionic Liquids
journal, October 2015

The crystal growth of δ-VN by floating zone and zone annealing techniques
journal, May 1977

Nika : software for two-dimensional data reduction
journal, March 2012

Small-Angle Scattering from Polymeric Mass Fractals of Arbitrary Mass-Fractal Dimension
journal, April 1996

Strain rate dependent nanostructure of hydrogels with reversible hydrophobic associations during uniaxial extension
journal, January 2019

  • Wang, Chao; Wiener, Clinton G.; Fukuto, Masafumi
  • Soft Matter, Vol. 15, Issue 2
  • DOI: 10.1039/C8SM02165A

Irena : tool suite for modeling and analysis of small-angle scattering
journal, February 2009

A new method for the determination of particle size distributions from small-angle neutron scattering measurements
journal, December 1988

  • Potton, J. A.; Daniell, G. J.; Rainford, B. D.
  • Journal of Applied Crystallography, Vol. 21, Issue 6
  • DOI: 10.1107/S0021889888004595

Order-Disorder Transition of a Hydrogel Containing an n-Alkyl Acrylate
journal, December 1994

  • Matsuda, Atsushi; Sato, Jun'ichi; Yasunaga, Hidekazu
  • Macromolecules, Vol. 27, Issue 26
  • DOI: 10.1021/ma00104a027

Polyproline as a Minimal Antifreeze Protein Mimic That Enhances the Cryopreservation of Cell Monolayers
journal, November 2017

  • Graham, Ben; Bailey, Trisha L.; Healey, Joseph R. J.
  • Angewandte Chemie, Vol. 129, Issue 50
  • DOI: 10.1002/ange.201706703

Facially Amphipathic Glycopolymers Inhibit Ice Recrystallization.
text, January 2018

  • Graham, Ben; Fayter, Alice ER; Houston, Judith E.
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.26776

Theory of amorphous ices
text, January 2013

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