Nanoporous Polymer Networks Templated by Gemini Surfactant Lyotropic Liquid Crystals
Abstract
Nanoporous polymers with periodic, ordered structures have attracted significant interest for their potential applications as drug delivery vehicles, biomaterials, separations membranes, and materials for energy storage. Inducing polymer nanostructure through lyotropic liquid crystal-templated (LLC-templated) cross-linking photopolymerizations offers a promising means for morphological control at smaller length scales, which are difficult to access by other established strategies. In this paper we report the synthesis of a gemini dicarboxylate surfactant that self-assembles in water to form various aqueous LLC mesophases over a broad range of amphiphile concentrations, with an especially strong propensity to form the coveted bicontinuous double gyroid (GI) network mesophase. Aqueous GI LLCs surprisingly persist upon incorporation of as much as 10–37 wt % hexane-1,6-diol dimethacrylate (HDDMA) into the hydrophobic domains of these supramolecular surfactant assemblies, and cross-linking photopolymerization of the HDDMA unexpectedly proceeds with retention of this intricate LLC nanostructure. The nanoporous nature of the resulting templated polymers remains after surfactant removal by solvent extraction, as manifested by increased swelling ratios in water and 2-propanol as compared to isotropic materials of similar compositions. The exquisite level of control over polymer network porosity provided by templating within GI phases furnishes a promising new route toward nanostructured hydrophobic polymers.
- Authors:
-
[2];
[4]
- Univ. of Wisconsin, Madison, WI (United States)
- Univ. of Iowa, Iowa City, IA (United States)
- Univ. of Minnesota, Minneapolis, MN (United States)
- Univ. of Wisconsin, Madison, WI (United States); Univ. of Minnesota, Minneapolis, MN (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- National Science Foundation (NSF); Wisconsin Alumni Research Foundation
- OSTI Identifier:
- 1417385
- Grant/Contract Number:
- CHE-9974839; DMR-0832760; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 30; Journal Issue: 1; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- ENGLISH
- Subject:
- 36 MATERIALS SCIENCE; Hydrophobicity; Genetics; Polymerization; Surfactants; Polymers
Citation Formats
Jennings, James, Green, Brian, Mann, Tyler J., Guymon, C. Allan, and Mahanthappa, Mahesh K. Nanoporous Polymer Networks Templated by Gemini Surfactant Lyotropic Liquid Crystals. United States: N. p., 2017.
Web. doi:10.1021/acs.chemmater.7b04183.
Jennings, James, Green, Brian, Mann, Tyler J., Guymon, C. Allan, & Mahanthappa, Mahesh K. Nanoporous Polymer Networks Templated by Gemini Surfactant Lyotropic Liquid Crystals. United States. https://doi.org/10.1021/acs.chemmater.7b04183
Jennings, James, Green, Brian, Mann, Tyler J., Guymon, C. Allan, and Mahanthappa, Mahesh K. Fri .
"Nanoporous Polymer Networks Templated by Gemini Surfactant Lyotropic Liquid Crystals". United States. https://doi.org/10.1021/acs.chemmater.7b04183. https://www.osti.gov/servlets/purl/1417385.
@article{osti_1417385,
title = {Nanoporous Polymer Networks Templated by Gemini Surfactant Lyotropic Liquid Crystals},
author = {Jennings, James and Green, Brian and Mann, Tyler J. and Guymon, C. Allan and Mahanthappa, Mahesh K.},
abstractNote = {Nanoporous polymers with periodic, ordered structures have attracted significant interest for their potential applications as drug delivery vehicles, biomaterials, separations membranes, and materials for energy storage. Inducing polymer nanostructure through lyotropic liquid crystal-templated (LLC-templated) cross-linking photopolymerizations offers a promising means for morphological control at smaller length scales, which are difficult to access by other established strategies. In this paper we report the synthesis of a gemini dicarboxylate surfactant that self-assembles in water to form various aqueous LLC mesophases over a broad range of amphiphile concentrations, with an especially strong propensity to form the coveted bicontinuous double gyroid (GI) network mesophase. Aqueous GI LLCs surprisingly persist upon incorporation of as much as 10–37 wt % hexane-1,6-diol dimethacrylate (HDDMA) into the hydrophobic domains of these supramolecular surfactant assemblies, and cross-linking photopolymerization of the HDDMA unexpectedly proceeds with retention of this intricate LLC nanostructure. The nanoporous nature of the resulting templated polymers remains after surfactant removal by solvent extraction, as manifested by increased swelling ratios in water and 2-propanol as compared to isotropic materials of similar compositions. The exquisite level of control over polymer network porosity provided by templating within GI phases furnishes a promising new route toward nanostructured hydrophobic polymers.},
doi = {10.1021/acs.chemmater.7b04183},
journal = {Chemistry of Materials},
number = 1,
volume = 30,
place = {United States},
year = {Fri Dec 22 00:00:00 EST 2017},
month = {Fri Dec 22 00:00:00 EST 2017}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 20 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Zeolite membranes – a review and comparison with MOFs
journal, January 2015
- Rangnekar, N.; Mittal, N.; Elyassi, B.
- Chemical Society Reviews, Vol. 44, Issue 20
Spatiotemporal hydrogel biomaterials for regenerative medicine
journal, January 2017
- Brown, Tobin E.; Anseth, Kristi S.
- Chemical Society Reviews, Vol. 46, Issue 21
Ordered porous materials for emerging applications
journal, June 2002
- Davis, Mark E.
- Nature, Vol. 417, Issue 6891, p. 813-821
On the Controllable Soft-Templating Approach to Mesoporous Silicates
journal, July 2007
- Wan, Ying
- Chemical Reviews, Vol. 107, Issue 7
Maximizing the right stuff: The trade-off between membrane permeability and selectivity
journal, June 2017
- Park, Ho Bum; Kamcev, Jovan; Robeson, Lloyd M.
- Science, Vol. 356, Issue 6343
The Future of Seawater Desalination: Energy, Technology, and the Environment
journal, August 2011
- Elimelech, M.; Phillip, W. A.
- Science, Vol. 333, Issue 6043
50th Anniversary Perspective : Block Polymers—Pure Potential
journal, December 2016
- Bates, Christopher M.; Bates, Frank S.
- Macromolecules, Vol. 50, Issue 1
Templating Nanoporous Polymers with Ordered Block Copolymers †
journal, February 2008
- Olson, David A.; Chen, Liang; Hillmyer, Marc A.
- Chemistry of Materials, Vol. 20, Issue 3
Relationship between morphology and conductivity of block-copolymer based battery separators
journal, March 2012
- Wong, David T.; Mullin, Scott A.; Battaglia, Vincent S.
- Journal of Membrane Science, Vol. 394-395
Reticulated Nanoporous Polymers by Controlled Polymerization-Induced Microphase Separation
journal, June 2012
- Seo, M.; Hillmyer, M. A.
- Science, Vol. 336, Issue 6087
Block Copolymer Lithography: Periodic Arrays of 1011 Holes in 1 Square Centimeter
journal, May 1997
- Park, Miri; Harrison, Christopher; Chaikin, Paul M.
- Science, Vol. 276, Issue 5317, p. 1401-1404
Controlling Polymer-Surface Interactions with Random Copolymer Brushes
journal, March 1997
- Mansky, P.; Liu, Y.; Huang, E.
- Science, Vol. 275, Issue 5305, p. 1458-1460
Block Copolymer Nanolithography: Translation of Molecular Level Control to Nanoscale Patterns
journal, July 2009
- Bang, Joona; Jeong, Unyong; Ryu, Du Yeol
- Advanced Materials, Vol. 21, Issue 47, p. 4769-4792
Block Copolymer Lithography
journal, November 2013
- Bates, Christopher M.; Maher, Michael J.; Janes, Dustin W.
- Macromolecules, Vol. 47, Issue 1, p. 2-12
High χ–Low N Block Polymers: How Far Can We Go?
journal, September 2015
- Sinturel, Christophe; Bates, Frank S.; Hillmyer, Marc A.
- ACS Macro Letters, Vol. 4, Issue 9
Stability of the Gyroid Phase in Diblock Copolymers at Strong Segregation
journal, April 2006
- Cochran, Eric W.; Garcia-Cervera, Carlos J.; Fredrickson, Glenn H.
- Macromolecules, Vol. 39, Issue 7
Polymerization of Preformed Self-Organized Assemblies
journal, October 1998
- O'Brien, David F.; Armitage, Bruce; Benedicto, Alto
- Accounts of Chemical Research, Vol. 31, Issue 12
Polymerization of and within self-organized media
journal, June 2003
- Hentze, Hans-Peter; Kaler, Eric W.
- Current Opinion in Colloid & Interface Science, Vol. 8, Issue 2
Polymerized Lyotropic Liquid Crystal Assemblies for Membrane Applications
journal, March 2008
- Gin, Douglas L.; Bara, Jason E.; Noble, Richard D.
- Macromolecular Rapid Communications, Vol. 29, Issue 5
Nanoporous, Bicontinuous Cubic Lyotropic Liquid Crystal Networks via Polymerizable Gemini Ammonium Surfactants
journal, August 2010
- Hatakeyama, Evan S.; Wiesenauer, Brian R.; Gabriel, Christopher J.
- Chemistry of Materials, Vol. 22, Issue 16
Cross-Linked Normal Hexagonal and Bicontinuous Cubic Assemblies via Polymerizable Gemini Amphiphiles
journal, March 2003
- Pindzola, Brad A.; Jin, Jizhu; Gin, Douglas L.
- Journal of the American Chemical Society, Vol. 125, Issue 10
Cross-Linking of Reactive Lyotropic Liquid Crystals for Nanostructure Retention
journal, March 2009
- Sievens-Figueroa, Lucas; Guymon, C. Allan
- Chemistry of Materials, Vol. 21, Issue 6
Photopolymerization in Polymer Templating †
journal, February 2008
- Clapper, Jason D.; Sievens-Figueroa, Lucas; Guymon, C. Allan
- Chemistry of Materials, Vol. 20, Issue 3
Photopolymerization kinetics in and of self-assembling lyotropic liquid crystal templates
journal, January 2017
- Worthington, Kristan S.; Baguenard, Céline; Forney, Bradley S.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 55, Issue 6
Radical polymerization behavior and molecular weight development of homologous monoacrylate monomers in lyotropic liquid crystal phases
journal, August 2015
- DePierro, Michael A.; Baguenard, Céline; Allan Guymon, C.
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 54, Issue 1
Morphology Variation of Porous Polymer Gels by Polymerization in Lyotropic Surfactant Phases
journal, March 1999
- Antonietti, Markus; Caruso, Rachel A.; Göltner, Christine G.
- Macromolecules, Vol. 32, Issue 5
Polymer Structure Development in Lyotropic Liquid Crystalline Solutions
journal, August 2014
- DePierro, Michael A.; Guymon, C. Allan
- Macromolecules, Vol. 47, Issue 16
Photoinitiation and Monomer Segregation Behavior in Polymerization of Lyotropic Liquid Crystalline Systems
journal, January 2006
- DePierro, Michael A.; Guymon, C. Allan
- Macromolecules, Vol. 39, Issue 2
Effects of Controlling Polymer Nanostructure Using Photopolymerization within Lyotropic Liquid Crystalline Templates
journal, July 2013
- Forney, Bradley S.; Baguenard, Céline; Guymon, C. Allan
- Chemistry of Materials, Vol. 25, Issue 15
Improved stimuli-response and mechanical properties of nanostructured poly(N-isopropylacrylamide-co-dimethylsiloxane) hydrogels generated through photopolymerization in lyotropic liquid crystal templates
journal, January 2013
- Forney, Bradley S.; Baguenard, Céline; Guymon, C. Allan
- Soft Matter, Vol. 9, Issue 31
Fast Deswelling Kinetics of Nanostructured Poly( N -Isopropylacrylamide) Photopolymerized in a Lyotropic Liquid Crystal Template: Fast Deswelling Kinetics of Nanostructured Poly( N -Isopropylacrylamide) Photopolymerized in …
journal, April 2011
- Forney, Bradley S.; Allan Guymon, C.
- Macromolecular Rapid Communications, Vol. 32, Issue 9-10
Photopolymerization Kinetics and Structure Development of Templated Lyotropic Liquid Crystalline Systems
journal, June 2001
- Lester, Christopher L.; Colson, Colleen D.; Guymon, C. Allan
- Macromolecules, Vol. 34, Issue 13
Unusually Stable Aqueous Lyotropic Gyroid Phases from Gemini Dicarboxylate Surfactants
journal, September 2011
- Sorenson, Gregory P.; Coppage, Keiva L.; Mahanthappa, Mahesh K.
- Journal of the American Chemical Society, Vol. 133, Issue 38
Linker Length-Dependent Control of Gemini Surfactant Aqueous Lyotropic Gyroid Phase Stability
journal, March 2015
- Perroni, Dominic V.; Baez-Cotto, Carlos M.; Sorenson, Gregory P.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 6
Impact of Oxygen on Photopolymerization Kinetics and Polymer Structure
journal, April 2006
- O'Brien, Allison K.; Bowman, Christopher N.
- Macromolecules, Vol. 39, Issue 7
Engineering bicontinuous cubic structures at the nanoscale—the role of chain splay
journal, January 2010
- Kulkarni, Chandrashekhar V.; Tang, Tsing-Young; Seddon, Annela M.
- Soft Matter, Vol. 6, Issue 14
Monoolein: a magic lipid?
journal, January 2011
- Kulkarni, Chandrashekhar V.; Wachter, Wolfgang; Iglesias-Salto, Guillermo
- Phys. Chem. Chem. Phys., Vol. 13, Issue 8
The Bending Elasticity of 1-Monoolein upon Relief of Packing Stress
journal, May 2000
- Vacklin, H.; Khoo, B. J.; Madan, K. H.
- Langmuir, Vol. 16, Issue 10
Membrane Protein Crystallization In Meso: Lipid Type-Tailoring of the Cubic Phase
journal, December 2002
- Cherezov, Vadim; Clogston, Jeffrey; Misquitta, Yohann
- Biophysical Journal, Vol. 83, Issue 6
How the chain configuration governs the packing of inverted micelles in the cubic Fd3m-phase
journal, January 2013
- Rappolt, Michael; Cacho-Nerin, Fernando; Morello, Christian
- Soft Matter, Vol. 9, Issue 27
Calculations of and Evidence for Chain Packing Stress in Inverse Lyotropic Bicontinuous Cubic Phases
journal, June 2007
- Shearman, Gemma C.; Khoo, Bee J.; Motherwell, Mary-Lynn
- Langmuir, Vol. 23, Issue 13
Discovery of a tetracontinuous, aqueous lyotropic network phase with unusual 3D-hexagonal symmetry
journal, January 2014
- Sorenson, Gregory P.; Schmitt, Adam K.; Mahanthappa, Mahesh K.
- Soft Matter, Vol. 10, Issue 41
Gemini Surfactants
journal, June 2000
- Menger, Fredric M.; Keiper, Jason S.
- Angewandte Chemie International Edition, Vol. 39, Issue 11
Lyotropic liquid crystal engineering moving beyond binary compositional space – ordered nanostructured amphiphile self-assembly materials by design
journal, January 2017
- van ‘t Hag, Leonie; Gras, Sally L.; Conn, Charlotte E.
- Chemical Society Reviews, Vol. 46, Issue 10
Phase Behavior of Lipid–Based Lyotropic Liquid Crystals in Presence of Colloidal Nanoparticles
journal, August 2011
- Venugopal, Edakkal; Bhat, Suresh K.; Vallooran, Jijo J.
- Langmuir, Vol. 27, Issue 16
Competition brings out the best: modelling the frustration between curvature energy and chain stretching energy of lyotropic liquid crystals in bicontinuous cubic phases
journal, June 2017
- Chen, Hao; Jin, Chenyu
- Interface Focus, Vol. 7, Issue 4
Comparison between Phase Behavior of Anionic Dimeric (Gemini-Type) and Monomeric Surfactants in Water and Water−Oil
journal, August 2000
- Kunieda, Hironobu; Masuda, Nagahiro; Tsubone, Kazuyuki
- Langmuir, Vol. 16, Issue 16
Physical Behavior of Cross-Linked PEG Hydrogels Photopolymerized within Nanostructured Lyotropic Liquid Crystalline Templates
journal, February 2007
- Clapper, Jason D.; Guymon, C. Allan
- Macromolecules, Vol. 40, Issue 4
Influence of Polymerization Conditions on Nanostructure and Properties of Polyacrylamide Hydrogels Templated from Lyotropic Liquid Crystals
journal, November 2006
- DePierro, Michael A.; Carpenter, Kyle G.; Guymon, C. Allan
- Chemistry of Materials, Vol. 18, Issue 23
Dimethacrylate derivatives of dimer acid
journal, June 2006
- Trujillo-Lemon, Marianela; Ge, Junhao; Lu, Hui
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 44, Issue 12
Nanostructure Evolution during Photopolymerization in Lyotropic Liquid Crystal Templates
journal, October 2010
- Forney, Bradley S.; Guymon, C. Allan
- Macromolecules, Vol. 43, Issue 20
Self-Assembly of Gemini Surfactants: A Computer Simulation Study
journal, September 2012
- Mondal, Jagannath; Mahanthappa, Mahesh; Yethiraj, Arun
- The Journal of Physical Chemistry B, Vol. 117, Issue 16
Electrostatic Interactions Govern “Odd/Even” Effects in Water-Induced Gemini Surfactant Self-Assembly
journal, January 2017
- Mantha, Sriteja; McDaniel, Jesse G.; Perroni, Dominic V.
- The Journal of Physical Chemistry B, Vol. 121, Issue 3
Effect of Oil on the Surfactant Molecular Curvatures in Liquid Crystals
journal, January 1998
- Kunieda, Hironobu; Ozawa, Kazuyo; Huang, Kuo-Lun
- The Journal of Physical Chemistry B, Vol. 102, Issue 5
Physical Properties of Hydrogels Synthesized from Lyotropic Liquid Crystalline Templates
journal, August 2003
- Lester, Christopher L.; Smith, Shannon M.; Colson, Colleen D.
- Chemistry of Materials, Vol. 15, Issue 17
Mechanical properties of hydrogels and their experimental determination
journal, January 1996
- Anseth, Kristi S.; Bowman, Christopher N.; Brannon-Peppas, Lisa
- Biomaterials, Vol. 17, Issue 17
Fundamental studies of a novel, biodegradable PEG-b-PLA hydrogel
journal, May 2000
- Metters, A.
- Polymer, Vol. 41, Issue 11
Works referencing / citing this record:
Multimodal control of liquid crystalline mesophases from surfactants with photoswitchable tails
journal, January 2019
- Houston, Judith E.; Kelly, Elaine A.; Kruteva, Margarita
- Journal of Materials Chemistry C, Vol. 7, Issue 35
Molecularly-ordered hydrogels with controllable, anisotropic stimulus response
journal, January 2019
- Boothby, Jennifer M.; Samuel, Jeremy; Ware, Taylor H.
- Soft Matter, Vol. 15, Issue 22
Multimodal Control of Liquid Crystalline Mesophases from Surfactants with Photoswitchable Tails
text, January 2019
- Evans, Rachel Claire; Houston, Judith E.; Kelly, Elaine
- Apollo - University of Cambridge Repository