3D Printing of Supramolecular Polymer Hydrogels with Hierarchical Structure
Abstract
Liquid crystalline hydrogels are an attractive class of soft materials to direct charge transport, mechanical actuation, and cell migration. When such systems contain supramolecular polymers, it is possible in principle to easily shear align nanoscale structures and create bulk anisotropic properties. However, reproducibly fabricating and patterning aligned supramolecular domains in 3D hydrogels remains a challenge using conventional fabrication techniques. Here, a method is reported for 3D printing of ionically crosslinked liquid crystalline hydrogels from aqueous supramolecular polymer inks. Using a combination of experimental techniques and molecular dynamics simulations, it is found that pH and salt concentration govern intermolecular interactions among the self-assembled structures where lower charge densities on the supramolecular polymers and higher charge screening from the electrolyte result in higher viscosity inks. Enhanced hierarchical interactions among assemblies in high viscosity inks increase the printability and ultimately lead to greater nanoscale alignment in extruded macroscopic filaments when using small nozzle diameters and fast print speeds. The use of this approach is demonstrated to create materials with anisotropic ionic and electronic charge transport as well as scaffolds that trigger the macroscopic alignment of cells due to the synergy of supramolecular self-assembly and additive manufacturing.
- Authors:
-
[1];
[2];
[2];
[2];
[2];
[2];
[3];
[4];
[5];
[1]
- Northwestern Univ., Evanston, IL (United States); Northwestern Univ., Chicago, IL (United States)
- Northwestern Univ., Chicago, IL (United States)
- Northwestern Univ., Evanston, IL (United States)
- Wright Patterson Air Force Base, Dayton, OH (United States); UES, Inc., Dayton, OH (United States)
- Wright Patterson Air Force Base, Dayton, OH (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1823087
- Alternate Identifier(s):
- OSTI ID: 1804819; OSTI ID: 1846607
- Grant/Contract Number:
- SC0000989; AC02‐06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Small
- Additional Journal Information:
- Journal Volume: 17; Journal Issue: 5; Journal ID: ISSN 1613-6810
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 99 GENERAL AND MISCELLANEOUS; 3D-printing; self-assembly; liquid crystals; hydrogels; hierarchical; 77 NANOSCIENCE AND NANOTECHNOLOGY
Citation Formats
Sather, Nicholas A., Sai, Hiroaki, Sasselli, Ivan R., Sato, Kohei, Ji, Wei, Synatschke, Christopher V., Zambrotta, Ryan T., Edelbrock, John F., Kohlmeyer, Ryan R., Hardin, James O., Berrigan, John Daniel, Durstock, Michael F., Mirau, Peter, and Stupp, Samuel I. 3D Printing of Supramolecular Polymer Hydrogels with Hierarchical Structure. United States: N. p., 2021.
Web. doi:10.1002/smll.202005743.
Sather, Nicholas A., Sai, Hiroaki, Sasselli, Ivan R., Sato, Kohei, Ji, Wei, Synatschke, Christopher V., Zambrotta, Ryan T., Edelbrock, John F., Kohlmeyer, Ryan R., Hardin, James O., Berrigan, John Daniel, Durstock, Michael F., Mirau, Peter, & Stupp, Samuel I. 3D Printing of Supramolecular Polymer Hydrogels with Hierarchical Structure. United States. https://doi.org/10.1002/smll.202005743
Sather, Nicholas A., Sai, Hiroaki, Sasselli, Ivan R., Sato, Kohei, Ji, Wei, Synatschke, Christopher V., Zambrotta, Ryan T., Edelbrock, John F., Kohlmeyer, Ryan R., Hardin, James O., Berrigan, John Daniel, Durstock, Michael F., Mirau, Peter, and Stupp, Samuel I. Fri .
"3D Printing of Supramolecular Polymer Hydrogels with Hierarchical Structure". United States. https://doi.org/10.1002/smll.202005743. https://www.osti.gov/servlets/purl/1823087.
@article{osti_1823087,
title = {3D Printing of Supramolecular Polymer Hydrogels with Hierarchical Structure},
author = {Sather, Nicholas A. and Sai, Hiroaki and Sasselli, Ivan R. and Sato, Kohei and Ji, Wei and Synatschke, Christopher V. and Zambrotta, Ryan T. and Edelbrock, John F. and Kohlmeyer, Ryan R. and Hardin, James O. and Berrigan, John Daniel and Durstock, Michael F. and Mirau, Peter and Stupp, Samuel I.},
abstractNote = {Liquid crystalline hydrogels are an attractive class of soft materials to direct charge transport, mechanical actuation, and cell migration. When such systems contain supramolecular polymers, it is possible in principle to easily shear align nanoscale structures and create bulk anisotropic properties. However, reproducibly fabricating and patterning aligned supramolecular domains in 3D hydrogels remains a challenge using conventional fabrication techniques. Here, a method is reported for 3D printing of ionically crosslinked liquid crystalline hydrogels from aqueous supramolecular polymer inks. Using a combination of experimental techniques and molecular dynamics simulations, it is found that pH and salt concentration govern intermolecular interactions among the self-assembled structures where lower charge densities on the supramolecular polymers and higher charge screening from the electrolyte result in higher viscosity inks. Enhanced hierarchical interactions among assemblies in high viscosity inks increase the printability and ultimately lead to greater nanoscale alignment in extruded macroscopic filaments when using small nozzle diameters and fast print speeds. The use of this approach is demonstrated to create materials with anisotropic ionic and electronic charge transport as well as scaffolds that trigger the macroscopic alignment of cells due to the synergy of supramolecular self-assembly and additive manufacturing.},
doi = {10.1002/smll.202005743},
journal = {Small},
number = 5,
volume = 17,
place = {United States},
year = {Fri Jan 15 00:00:00 EST 2021},
month = {Fri Jan 15 00:00:00 EST 2021}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
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:
Directed Assembly of Hybrid Nanomaterials and Nanocomposites
journal, March 2018
- Zhang, Shanju; Pelligra, Candice I.; Feng, Xunda
- Advanced Materials, Vol. 30, Issue 18
3D Printing of Liquid Crystal Elastomeric Actuators with Spatially Programed Nematic Order
journal, January 2018
- Kotikian, Arda; Truby, Ryan L.; Boley, John William
- Advanced Materials, Vol. 30, Issue 10
Biomimetic 4D printing
journal, January 2016
- Sydney Gladman, A.; Matsumoto, Elisabetta A.; Nuzzo, Ralph G.
- Nature Materials, Vol. 15, Issue 4
Micropatterning of bioactive self-assembling gels
journal, January 2009
- Mata, Alvaro; Hsu, Lorraine; Capito, Ramille
- Soft Matter, Vol. 5, Issue 6
Self-assembly of peptide amphiphiles: From molecules to nanostructures to biomaterials
journal, January 2010
- Cui, Honggang; Webber, Matthew J.; Stupp, Samuel I.
- Biopolymers, Vol. 94, Issue 1, p. 1-18
Liquid crystalline properties of solutions of persistent polymer chains
journal, June 1991
- DuPré, Donald B.; Yang, Shi‐jun
- The Journal of Chemical Physics, Vol. 94, Issue 11
Covalent-supramolecular hybrid polymers as muscle-inspired anisotropic actuators
journal, June 2018
- Chin, Stacey M.; Synatschke, Christopher V.; Liu, Shuangping
- Nature Communications, Vol. 9, Issue 1
Multi-Scale Assembly of Polythiophene-Surfactant Supramolecular Complexes for Charge Transport Anisotropy
journal, January 2017
- Bilger, David; Sarkar, Amrita; Danesh, Cameron
- Macromolecules, Vol. 50, Issue 3
Nanofluidic Ion Transport through Reconstructed Layered Materials
journal, September 2012
- Raidongia, Kalyan; Huang, Jiaxing
- Journal of the American Chemical Society, Vol. 134, Issue 40
Self-Assembly and Mineralization of Peptide-Amphiphile Nanofibers
journal, November 2001
- Hartgerink, Jeffrey D.; Beniash, Elia; Stupp, Samuel I.
- Science, Vol. 294, Issue 5547, p. 1684-1688
Functional Supramolecular Polymers
journal, February 2012
- Aida, T.; Meijer, E. W.; Stupp, S. I.
- Science, Vol. 335, Issue 6070
Aligned Macroscopic Domains of Optoelectronic Nanostructures Prepared via Shear-Flow Assembly of Peptide Hydrogels
journal, October 2011
- Wall, Brian D.; Diegelmann, Stephen R.; Zhang, Shuming
- Advanced Materials, Vol. 23, Issue 43, p. 5009-5014
Hydrodynamic alignment and assembly of nanofibrils resulting in strong cellulose filaments
journal, June 2014
- Håkansson, Karl M. O.; Fall, Andreas B.; Lundell, Fredrik
- Nature Communications, Vol. 5, Issue 1
Nonionic amphiphile nanoarchitectonics: self-assembly into micelles and lyotropic liquid crystals
journal, April 2015
- Shrestha, Lok Kumar; Strzelczyk, Karolina Maria; Shrestha, Rekha Goswami
- Nanotechnology, Vol. 26, Issue 20
Rheological Equations from Molecular Network Theories
journal, March 1972
- Carreau, Pierre J.
- Transactions of the Society of Rheology, Vol. 16, Issue 1
Exploring the sequence space for (tri-)peptide self-assembly to design and discover new hydrogels
journal, December 2014
- Frederix, Pim W. J. M.; Scott, Gary G.; Abul-Haija, Yousef M.
- Nature Chemistry, Vol. 7, Issue 1
Tubular hydrogels of circumferentially aligned nanofibers to encapsulate and orient vascular cells
journal, August 2012
- McClendon, Mark T.; Stupp, Samuel I.
- Biomaterials, Vol. 33, Issue 23
Supramolecular biomaterials
journal, December 2015
- Webber, Matthew J.; Appel, Eric A.; Meijer, E. W.
- Nature Materials, Vol. 15, Issue 1
Hydrophobic interactions of peptides with membrane interfaces
journal, November 1998
- White, Stephen H.; Wimley, William C.
- Biochimica et Biophysica Acta (BBA) - Reviews on Biomembranes, Vol. 1376, Issue 3
Hierarchical and Heterogeneous Bioinspired Composites-Merging Molecular Self-Assembly with Additive Manufacturing
journal, June 2017
- Rajasekharan, Anand K.; Bordes, Romain; Sandström, Carl
- Small, Vol. 13, Issue 28
Hierarchical nanostructured conducting polymer hydrogel with high electrochemical activity
journal, May 2012
- Pan, L.; Yu, G.; Zhai, D.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 24
The MARTINI Coarse-Grained Force Field: Extension to Proteins
journal, April 2008
- Monticelli, Luca; Kandasamy, Senthil K.; Periole, Xavier
- Journal of Chemical Theory and Computation, Vol. 4, Issue 5
Encapsulation of curcumin in self-assembling peptide hydrogels as injectable drug delivery vehicles
journal, September 2011
- Altunbas, Aysegul; Lee, Seung J.; Rajasekaran, Sigrid A.
- Biomaterials, Vol. 32, Issue 25
Energy landscapes and functions of supramolecular systems
journal, January 2016
- Tantakitti, Faifan; Boekhoven, Job; Wang, Xin
- Nature Materials, Vol. 15, Issue 4
GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers
journal, September 2015
- Abraham, Mark James; Murtola, Teemu; Schulz, Roland
- SoftwareX, Vol. 1-2
Gd(III)-Labeled Peptide Nanofibers for Reporting on Biomaterial Localization in Vivo
journal, June 2014
- Preslar, Adam T.; Parigi, Giacomo; McClendon, Mark T.
- ACS Nano, Vol. 8, Issue 7
Orientation of charged clay nanotubes in evaporating droplet meniscus
journal, February 2015
- Zhao, Yafei; Cavallaro, Giuseppe; Lvov, Yuri
- Journal of Colloid and Interface Science, Vol. 440
Three-dimensional printing of complex biological structures by freeform reversible embedding of suspended hydrogels
journal, October 2015
- Hinton, Thomas J.; Jallerat, Quentin; Palchesko, Rachelle N.
- Science Advances, Vol. 1, Issue 9
Bioprinting: 3D Bioprinting of Vascularized, Heterogeneous Cell-Laden Tissue Constructs (Adv. Mater. 19/2014)
journal, May 2014
- Kolesky, David B.; Truby, Ryan L.; Gladman, A. Sydney
- Advanced Materials, Vol. 26, Issue 19
Intermolecular Forces in the Self-Assembly of Peptide Amphiphile Nanofibers
journal, March 2006
- Stendahl, J. C.; Rao, M. S.; Guler, M. O.
- Advanced Functional Materials, Vol. 16, Issue 4
Peptide-amphiphile nanofibers: A versatile scaffold for the preparation of self-assembling materials
journal, April 2002
- Hartgerink, J. D.; Beniash, E.; Stupp, S. I.
- Proceedings of the National Academy of Sciences, Vol. 99, Issue 8, p. 5133-5138
A bioactive self-assembled membrane to promote angiogenesis
journal, February 2011
- Chow, Lesley W.; Bitton, Ronit; Webber, Matthew J.
- Biomaterials, Vol. 32, Issue 6
Modeling the Self-Assembly of Peptide Amphiphiles into Fibers Using Coarse-Grained Molecular Dynamics
journal, January 2012
- Lee, One-Sun; Cho, Vince; Schatz, George C.
- Nano Letters, Vol. 12, Issue 9
Direct-Write Assembly of 3D Silk/Hydroxyapatite Scaffolds for Bone Co-Cultures
journal, May 2012
- Sun, Lin; Parker, Sara T.; Syoji, Daisuke
- Advanced Healthcare Materials, Vol. 1, Issue 6
Improved Parameters for the Martini Coarse-Grained Protein Force Field
journal, November 2012
- de Jong, Djurre H.; Singh, Gurpreet; Bennett, W. F. Drew
- Journal of Chemical Theory and Computation, Vol. 9, Issue 1
Self-assembling hydrogel scaffolds for photocatalytic hydrogen production
journal, October 2014
- Weingarten, Adam S.; Kazantsev, Roman V.; Palmer, Liam C.
- Nature Chemistry, Vol. 6, Issue 11
Aligned neurite outgrowth and directed cell migration in self-assembled monodomain gels
journal, January 2014
- Berns, Eric J.; Sur, Shantanu; Pan, Liuliu
- Biomaterials, Vol. 35, Issue 1
Three-dimensional printing of hierarchical liquid-crystal-polymer structures
journal, September 2018
- Gantenbein, Silvan; Masania, Kunal; Woigk, Wilhelm
- Nature, Vol. 561, Issue 7722
Dynamics of Cellulose Nanocrystal Alignment during 3D Printing
journal, June 2018
- Hausmann, Michael K.; Rühs, Patrick A.; Siqueira, Gilberto
- ACS Nano, Vol. 12, Issue 7
Supramolecular Energy Materials
journal, March 2020
- Dumele, Oliver; Chen, Jiahao; Passarelli, James V.
- Advanced Materials, Vol. 32, Issue 17
Expanding the Nanoarchitectural Diversity Through Aromatic Di- and Tri-Peptide Coassembly: Nanostructures and Molecular Mechanisms
journal, August 2016
- Guo, Cong; Arnon, Zohar A.; Qi, Ruxi
- ACS Nano, Vol. 10, Issue 9
Converging flow of polymer melts in extrusion dies
journal, January 1972
- Cogswell, F. N.
- Polymer Engineering and Science, Vol. 12, Issue 1
3D nanostructured conductive polymer hydrogels for high-performance electrochemical devices
journal, January 2013
- Zhao, Yu; Liu, Borui; Pan, Lijia
- Energy & Environmental Science, Vol. 6, Issue 10
Molecular dynamics simulations reveal disruptive self-assembly in dynamic peptide libraries
journal, January 2017
- Sasselli, I. R.; Moreira, I. P.; Ulijn, R. V.
- Organic & Biomolecular Chemistry, Vol. 15, Issue 31
Injectable biomimetic liquid crystalline scaffolds enhance muscle stem cell transplantation
journal, September 2017
- Sleep, Eduard; Cosgrove, Benjamin D.; McClendon, Mark T.
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 38
Synthesis and Alignment of Discrete Polydiacetylene-Peptide Nanostructures
journal, January 2012
- Diegelmann, Stephen R.; Hartman, Nikolaus; Markovic, Nina
- Journal of the American Chemical Society, Vol. 134, Issue 4
Additive manufacturing of biologically-inspired materials
journal, January 2016
- Studart, André R.
- Chemical Society Reviews, Vol. 45, Issue 2
Review article: Fabrication of nanofluidic devices
journal, March 2013
- Duan, Chuanhua; Wang, Wei; Xie, Quan
- Biomicrofluidics, Vol. 7, Issue 2
The Powerful Functions of Peptide-Based Bioactive Matrices for Regenerative Medicine
journal, November 2014
- Rubert Pérez, Charles M.; Stephanopoulos, Nicholas; Sur, Shantanu
- Annals of Biomedical Engineering, Vol. 43, Issue 3
Dopant-Enabled Supramolecular Approach for Controlled Synthesis of Nanostructured Conductive Polymer Hydrogels
journal, October 2015
- Wang, Yaqun; Shi, Ye; Pan, Lijia
- Nano Letters, Vol. 15, Issue 11
Nanostructured scaffolds for bone tissue engineering
journal, February 2013
- Li, Xiaoming; Wang, Lu; Fan, Yubo
- Journal of Biomedical Materials Research Part A, Vol. 101A, Issue 8
Direct-Write Assembly of 3D Hydrogel Scaffolds for Guided Cell Growth
journal, June 2009
- Barry, Robert A.; Shepherd, Robert F.; Hanson, Jennifer N.
- Advanced Materials, Vol. 21, Issue 23
Assembly of Viral Hydrogels for Three-Dimensional Conducting Nanocomposites
journal, April 2014
- Chen, Po-Yen; Hyder, Md Nasim; Mackanic, David
- Advanced Materials, Vol. 26, Issue 30
25th Anniversary Article: Supramolecular Materials for Regenerative Medicine
journal, February 2014
- Boekhoven, Job; Stupp, Samuel I.
- Advanced Materials, Vol. 26, Issue 11
A self-assembly pathway to aligned monodomain gels
journal, June 2010
- Zhang, Shuming; Greenfield, Megan A.; Mata, Alvaro
- Nature Materials, Vol. 9, Issue 7
The MARTINI Force Field: Coarse Grained Model for Biomolecular Simulations
journal, July 2007
- Marrink, Siewert J.; Risselada, H. Jelger; Yefimov, Serge
- The Journal of Physical Chemistry B, Vol. 111, Issue 27
Bioinspired Nanocomposite Hydrogels with Highly Ordered Structures
journal, October 2017
- Zhao, Ziguang; Fang, Ruochen; Rong, Qinfeng
- Advanced Materials, Vol. 29, Issue 45
Liquid crystal phase formation by biopolymers
journal, January 2010
- Hamley, I. W.
- Soft Matter, Vol. 6, Issue 9
Tuning supramolecular mechanics to guide neuron development
journal, July 2013
- Sur, Shantanu; Newcomb, Christina J.; Webber, Matthew J.
- Biomaterials, Vol. 34, Issue 20
pH and Amphiphilic Structure Direct Supramolecular Behavior in Biofunctional Assemblies
journal, October 2014
- Moyer, Tyson J.; Finbloom, Joel A.; Chen, Feng
- Journal of the American Chemical Society, Vol. 136, Issue 42
Supramolecular Packing Controls H 2 Photocatalysis in Chromophore Amphiphile Hydrogels
journal, November 2015
- Weingarten, Adam S.; Kazantsev, Roman V.; Palmer, Liam C.
- Journal of the American Chemical Society, Vol. 137, Issue 48
Cellulose Nanocrystal Inks for 3D Printing of Textured Cellular Architectures
journal, February 2017
- Siqueira, Gilberto; Kokkinis, Dimitri; Libanori, Rafael
- Advanced Functional Materials, Vol. 27, Issue 12
Transforms and Operators for Directional Bioimage Analysis: A Survey
book, May 2016
- Püspöki, Zsuzsanna; Storath, Martin; Sage, Daniel
- Focus on Bio-Image Informatics
Avogadro: an advanced semantic chemical editor, visualization, and analysis platform
journal, August 2012
- Hanwell, Marcus D.; Curtis, Donald E.; Lonie, David C.
- Journal of Cheminformatics, Vol. 4, Issue 1
Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds
journal, April 2017
- Kazantsev, Roman V.; Dannenhoffer, Adam J.; Weingarten, Adam S.
- Journal of the American Chemical Society, Vol. 139, Issue 17
Transition from Bioinert to Bioactive Material by Tailoring the Biological Cell Response to Carboxylated Nanocellulose
journal, February 2016
- Hua, Kai; Rocha, Igor; Zhang, Peng
- Biomacromolecules, Vol. 17, Issue 3
Direct Ink Writing of 3D Functional Materials
journal, November 2006
- Lewis, J. A.
- Advanced Functional Materials, Vol. 16, Issue 17
VMD: Visual molecular dynamics
journal, February 1996
- Humphrey, William; Dalke, Andrew; Schulten, Klaus
- Journal of Molecular Graphics, Vol. 14, Issue 1
Understanding anisotropic transport in self-assembled membranes and maximizing ionic conductivity by microstructure alignment
journal, January 2013
- Majewski, Pawel W.; Gopinadhan, Manesh; Osuji, Chinedum O.
- Soft Matter, Vol. 9, Issue 29
Impact of charge switching stimuli on supramolecular perylene monoimide assemblies
journal, January 2019
- Dannenhoffer, Adam; Sai, Hiroaki; Huang, Dongxu
- Chemical Science, Vol. 10, Issue 22