Thermoresponsive Stiffening with Microgel Particles in a Semiflexible Fibrin Network
Abstract
We report here temperature-responsive soft composites of semiflexible biopolymer networks (fibrin) containing dispersed microgel colloidal particles of poly(N-isopropylacrylamide) (pNIPAM) that undergo a thermodynamically driven deswelling transition above the lower critical solution temperature. Unlike standard polymer particle composites, decreasing the inclusion volume of the particles (by increasing temperature) is concomitant with a striking increase of the overall elastic stiffness of the composite. We observe such a behavior over a wide composition space. The composite elastic shear modulus reversibly stiffens by up to 10-fold over a small change in temperature from 25 to 35 °C. In isolation, the fibrin network and microgel suspension both soften with increased temperature, making the stiffening of the composites particularly significant. We hypothesize that stiffening is caused by the shrinking microgel particles that deform fibrin filaments, and modify the network structure. We further develop a phenomenological model that quantifies this hypothesis, and the derived predictions are qualitatively consistent with our experimental data.
- Authors:
-
- Univ. of Illinois at Urbana-Champaign, IL (United States)
- Univ. of Illinois at Urbana-Champaign, IL (United States); Korea Inst. of Science and Technology, Seoul (South Korea)
- Publication Date:
- Research Org.:
- Univ. of Illinois at Urbana-Champaign, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1606375
- Grant/Contract Number:
- FG02-07ER46471
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 52; Journal Issue: 8; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Chaudhary, Gaurav, Ghosh, Ashesh, Bharadwaj, N. Ashwin, Kang, Jin Gu, Braun, Paul V., Schweizer, Kenneth S., and Ewoldt, Randy H. Thermoresponsive Stiffening with Microgel Particles in a Semiflexible Fibrin Network. United States: N. p., 2019.
Web. doi:10.1021/acs.macromol.9b00124.
Chaudhary, Gaurav, Ghosh, Ashesh, Bharadwaj, N. Ashwin, Kang, Jin Gu, Braun, Paul V., Schweizer, Kenneth S., & Ewoldt, Randy H. Thermoresponsive Stiffening with Microgel Particles in a Semiflexible Fibrin Network. United States. https://doi.org/10.1021/acs.macromol.9b00124
Chaudhary, Gaurav, Ghosh, Ashesh, Bharadwaj, N. Ashwin, Kang, Jin Gu, Braun, Paul V., Schweizer, Kenneth S., and Ewoldt, Randy H. 2019.
"Thermoresponsive Stiffening with Microgel Particles in a Semiflexible Fibrin Network". United States. https://doi.org/10.1021/acs.macromol.9b00124. https://www.osti.gov/servlets/purl/1606375.
@article{osti_1606375,
title = {Thermoresponsive Stiffening with Microgel Particles in a Semiflexible Fibrin Network},
author = {Chaudhary, Gaurav and Ghosh, Ashesh and Bharadwaj, N. Ashwin and Kang, Jin Gu and Braun, Paul V. and Schweizer, Kenneth S. and Ewoldt, Randy H.},
abstractNote = {We report here temperature-responsive soft composites of semiflexible biopolymer networks (fibrin) containing dispersed microgel colloidal particles of poly(N-isopropylacrylamide) (pNIPAM) that undergo a thermodynamically driven deswelling transition above the lower critical solution temperature. Unlike standard polymer particle composites, decreasing the inclusion volume of the particles (by increasing temperature) is concomitant with a striking increase of the overall elastic stiffness of the composite. We observe such a behavior over a wide composition space. The composite elastic shear modulus reversibly stiffens by up to 10-fold over a small change in temperature from 25 to 35 °C. In isolation, the fibrin network and microgel suspension both soften with increased temperature, making the stiffening of the composites particularly significant. We hypothesize that stiffening is caused by the shrinking microgel particles that deform fibrin filaments, and modify the network structure. We further develop a phenomenological model that quantifies this hypothesis, and the derived predictions are qualitatively consistent with our experimental data.},
doi = {10.1021/acs.macromol.9b00124},
url = {https://www.osti.gov/biblio/1606375},
journal = {Macromolecules},
issn = {0024-9297},
number = 8,
volume = 52,
place = {United States},
year = {Tue Apr 09 00:00:00 EDT 2019},
month = {Tue Apr 09 00:00:00 EDT 2019}
}
Web of Science
Works referenced in this record:
Emerging applications of stimuli-responsive polymer materials
journal, January 2010
- Stuart, Martien A. Cohen; Huck, Wilhelm T. S.; Genzer, Jan
- Nature Materials, Vol. 9, Issue 2, p. 101-113
Stimuli-responsive supramolecular polymeric materials
journal, January 2012
- Yan, Xuzhou; Wang, Feng; Zheng, Bo
- Chemical Society Reviews, Vol. 41, Issue 18
Light Robots: Bridging the Gap between Microrobotics and Photomechanics in Soft Materials
journal, October 2017
- Zeng, Hao; Wasylczyk, Piotr; Wiersma, Diederik S.
- Advanced Materials, Vol. 30, Issue 24
Stimuli-responsive polymer nano-science: Shape anisotropy, responsiveness, applications
journal, March 2018
- Lu, Chunliang; Urban, Marek W.
- Progress in Polymer Science, Vol. 78
Composite Polymer Colloids for SERS-Based Applications
journal, December 2017
- Strozyk, Malte S.; Jimenez de Aberasturi, Dorleta; Liz-Marzán, Luis M.
- The Chemical Record, Vol. 18, Issue 7-8
A bottom-up approach to cell mechanics
journal, April 2006
- Bausch, A. R.; Kroy, K.
- Nature Physics, Vol. 2, Issue 4
Cell mechanics and the cytoskeleton
journal, January 2010
- Fletcher, Daniel A.; Mullins, R. Dyche
- Nature, Vol. 463, Issue 7280
Polymer physics of the cytoskeleton
journal, October 2011
- Wen, Qi; Janmey, Paul A.
- Current Opinion in Solid State and Materials Science, Vol. 15, Issue 5
Cellular Motility Driven by Assembly and Disassembly of Actin Filaments
journal, February 2003
- Pollard, Thomas D.; Borisy, Gary G.
- Cell, Vol. 112, Issue 4
Dealing with mechanics: mechanisms of force transduction in cells
journal, July 2004
- Janmey, Paul A.; Weitz, David A.
- Trends in Biochemical Sciences, Vol. 29, Issue 7
Cell Migration: Integrating Signals from Front to Back
journal, December 2003
- Ridley, A. J.
- Science, Vol. 302, Issue 5651
Actin, a Central Player in Cell Shape and Movement
journal, November 2009
- Pollard, Thomas D.; Cooper, John A.
- Science, Vol. 326, Issue 5957
Prestressed F-actin networks cross-linked by hinged filamins replicate mechanical properties of cells
journal, January 2006
- Gardel, M. L.; Nakamura, F.; Hartwig, J. H.
- Proceedings of the National Academy of Sciences, Vol. 103, Issue 6
Stress-Dependent Elasticity of Composite Actin Networks as a Model for Cell Behavior
journal, March 2006
- Gardel, M. L.; Nakamura, F.; Hartwig, J.
- Physical Review Letters, Vol. 96, Issue 8
Structural Hierarchy Governs Fibrin Gel Mechanics
journal, May 2010
- Piechocka, Izabela K.; Bacabac, Rommel G.; Potters, Max
- Biophysical Journal, Vol. 98, Issue 10
Elasticity of Semiflexible Biopolymer Networks
journal, December 1995
- MacKintosh, F. C.; Käs, J.; Janmey, P. A.
- Physical Review Letters, Vol. 75, Issue 24
Constitutive modeling of the stress–strain behavior of F-actin filament networks
journal, May 2008
- Palmer, Jeffrey S.; Boyce, Mary C.
- Acta Biomaterialia, Vol. 4, Issue 3
Stretching Semiflexible Filaments and Their Networks
journal, May 2009
- Blundell, J. R.; Terentjev, E. M.
- Macromolecules, Vol. 42, Issue 14
Radial Distribution Function of Semiflexible Polymers
journal, September 1996
- Wilhelm, Jan; Frey, Erwin
- Physical Review Letters, Vol. 77, Issue 12
Directing Colloidal Assembly and a Metal-Insulator Transition Using a Quench-Disordered Porous Rod Template
journal, November 2014
- Jadrich, Ryan B.; Schweizer, Kenneth S.
- Physical Review Letters, Vol. 113, Issue 20
Cytoskeletal stiffening in synthetic hydrogels
journal, February 2019
- de Almeida, Paula; Jaspers, Maarten; Vaessen, Sarah
- Nature Communications, Vol. 10, Issue 1
Biomaterials & scaffolds for tissue engineering
journal, March 2011
- O'Brien, Fergal J.
- Materials Today, Vol. 14, Issue 3
Matrix geometry determines optimal cancer cell migration strategy and modulates response to interventions
journal, June 2013
- Tozluoğlu, Melda; Tournier, Alexander L.; Jenkins, Robert P.
- Nature Cell Biology, Vol. 15, Issue 7
Structural changes in PNIPAM microgel particles as seen by SANS, DLS, and EM techniques
journal, July 2001
- Kratz, Karl; Hellweg, Thomas; Eimer, Wolfgang
- Polymer, Vol. 42, Issue 15
Dynamic assembly of ultrasoft colloidal networks enables cell invasion within restrictive fibrillar polymers
journal, January 2017
- Douglas, Alison M.; Fragkopoulos, Alexandros A.; Gaines, Michelle K.
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 5
Ultra-responsive soft matter from strain-stiffening hydrogels
journal, December 2014
- Jaspers, Maarten; Dennison, Matthew; Mabesoone, Mathijs F. J.
- Nature Communications, Vol. 5, Issue 1
Bundle Formation in Biomimetic Hydrogels
journal, July 2016
- Jaspers, Maarten; Pape, A. C. H.; Voets, Ilja K.
- Biomacromolecules, Vol. 17, Issue 8
Nonlinear mechanics of hybrid polymer networks that mimic the complex mechanical environment of cells
journal, May 2017
- Jaspers, Maarten; Vaessen, Sarah L.; van Schayik, Pim
- Nature Communications, Vol. 8, Issue 1
Cross-Linker-Free N -Isopropylacrylamide Gel Nanospheres
journal, June 2003
- Gao, Jun; Frisken, Barbara J.
- Langmuir, Vol. 19, Issue 13
Local and global deformations in a strain-stiffening fibrin gel
journal, November 2007
- Wen, Qi; Basu, Anindita; Winer, Jessamine P.
- New Journal of Physics, Vol. 9, Issue 11
Mechanical properties of individual microgel particles through the deswelling transition
journal, January 2009
- Hashmi, Sara M.; Dufresne, Eric R.
- Soft Matter, Vol. 5, Issue 19
Mechanics and chemical thermodynamics of phase transition in temperature-sensitive hydrogels
journal, November 2011
- Cai, Shengqiang; Suo, Zhigang
- Journal of the Mechanics and Physics of Solids, Vol. 59, Issue 11
An efficient method for the fabrication of temperature-sensitive hydrogel microactuators
journal, January 2004
- van der Linden, Heiko; Olthuis, Wouter; Bergveld, Piet
- Lab on a Chip, Vol. 4, Issue 6
Elastic properties of soft particle pastes
journal, May 2006
- Seth, Jyoti R.; Cloitre, Michel; Bonnecaze, Roger T.
- Journal of Rheology, Vol. 50, Issue 3
Glassy dynamics and mechanical response in dense fluids of soft repulsive spheres. II. Shear modulus, relaxation-elasticity connections, and rheology
journal, May 2011
- Yang, Jian; Schweizer, Kenneth S.
- The Journal of Chemical Physics, Vol. 134, Issue 20
Yield stress materials in soft condensed matter
journal, August 2017
- Bonn, Daniel; Denn, Morton M.; Berthier, Ludovic
- Reviews of Modern Physics, Vol. 89, Issue 3
Temperature-Controlled Transitions Between Glass, Liquid, and Gel States in Dense p-NIPA Suspensions
journal, April 2010
- Romeo, Giovanni; Fernandez-Nieves, Alberto; Wyss, Hans M.
- Advanced Materials, Vol. 22, Issue 31
Jamming and overpacking fuzzy microgels: Deformation, interpenetration, and compression
journal, October 2017
- Conley, Gaurasundar M.; Aebischer, Philippe; Nöjd, Sofi
- Science Advances, Vol. 3, Issue 10
Structural Origins of Fibrin Clot Rheology
journal, November 1999
- Ryan, Esther A.; Mockros, Lyle F.; Weisel, John W.
- Biophysical Journal, Vol. 77, Issue 5
Elastic Behavior of Cross-Linked and Bundled Actin Networks
journal, May 2004
- Gardel, M. L.
- Science, Vol. 304, Issue 5675
Alternative Explanation of Stiffening in Cross-Linked Semiflexible Networks
journal, October 2005
- Onck, P. R.; Koeman, T.; van Dillen, T.
- Physical Review Letters, Vol. 95, Issue 17
Effects of particle size, particle/matrix interface adhesion and particle loading on mechanical properties of particulate–polymer composites
journal, September 2008
- Fu, Shao-Yun; Feng, Xi-Qiao; Lauke, Bernd
- Composites Part B: Engineering, Vol. 39, Issue 6
Defining nonlinear rheological material functions for oscillatory shear
journal, January 2013
- Ewoldt, Randy H.
- Journal of Rheology, Vol. 57, Issue 1
Microgel-Reinforced Hydrogel Films with High Mechanical Strength and Their Visible Mesoscale Fracture Structure
journal, October 2011
- Hu, Jian; Hiwatashi, Kenta; Kurokawa, Takayuki
- Macromolecules, Vol. 44, Issue 19
Composite hydrogels with temperature sensitive heterogeneities: influence of gel matrix on the volume phase transition of embedded poly-(N-isopropylacrylamide) microgels
journal, January 2011
- Meid, Judith; Friedrich, Tatjana; Tieke, Bernd
- Phys. Chem. Chem. Phys., Vol. 13, Issue 8
Mechanical properties of temperature sensitive microgel/polyacrylamide composite hydrogels—from soft to hard fillers
journal, January 2012
- Meid, Judith; Dierkes, Fiete; Cui, Jun
- Soft Matter, Vol. 8, Issue 15
Adsorption of Fibrinogen to Droplets of Liquid Hydrophobic Phases: Functionality of the Bound Protein and Biological Implications
journal, December 1998
- Retzinger, Gregory S.; DeAnglis, Ashley P.; Patuto, Samantha J.
- Arteriosclerosis, Thrombosis, and Vascular Biology, Vol. 18, Issue 12
Effects of surface wettability and contact time on protein adhesion to biomaterial surfaces
journal, August 2007
- Xu, Li-Chong; Siedlecki, Christopher A.
- Biomaterials, Vol. 28, Issue 22
Uncoupling shear and uniaxial elastic moduli of semiflexible biopolymer networks: compression-softening and stretch-stiffening
journal, January 2016
- van Oosten, Anne S. G.; Vahabi, Mahsa; Licup, Albert J.
- Scientific Reports, Vol. 6, Issue 1
Theory of Semiflexible Filaments and Networks
journal, February 2017
- Meng, Fanlong; Terentjev, Eugene
- Polymers, Vol. 9, Issue 12