skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Harnessing biomimetic cryptic bonds to form self-reinforcing gels

Journal Article · · Soft Matter
DOI:https://doi.org/10.1039/d0sm00145g· OSTI ID:1800720

Cryptic sites, which lay hidden in folded biomolecules, become exposed by applied force and form new bonds that reinforce the biomaterial. While these binding interactions effectively inhibit mechanical deformation, there are few synthetic materials that harness mechano-responsive cryptic sites to forestall damage. Here, we develop a computational model to design polymer gels encompassing cryptic sites and a lower critical solution temperature (LCST). LCST gels swell with a decrease in temperature, thereby generating internal stresses within the sample. The gels also encompass loops held together by the cryptic sites, as well as dangling chains with chemically reactive ends. A decrease in temperature or an applied force causes the loops to unfold and expose the cryptic sites, which then bind to the dangling chains. We show that these binding interactions act as “struts” that reinforce the network, as indicated by a significant decrease in the volume of the gel (from 44% to 80%) and shifts in the volume phase transition temperature. Once the temperature is increased or the deformation is removed, the latter “cryptic bonds” are broken, allowing the loops to refold and the gel to return to its original state. These findings provide guidelines for designing polymer networks with reversible, mechano-responsive bonds, which allow gels to undergo a self-stiffening behavior in response to a temperature-induced internal stress or external force. When applied as a coating, these gels can prevent the underlying materials from undergoing damage and thus, extend the lifetime of the system.

Research Organization:
Univ. of Pittsburgh, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
FG02-90ER45438
OSTI ID:
1800720
Alternate ID(s):
OSTI ID: 1617390
Journal Information:
Soft Matter, Vol. 16, Issue 22; ISSN 1744-683X
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

References (45)

Fibronectin forms the most extensible biological fibers displaying switchable force-exposed cryptic binding sites journal October 2009
One-Pot Synthesis of Hairy Nanoparticles by Emulsion ATRP journal March 2009
Thermodynamic control over energy dissipation modes in dual-network hydrogels based on metal–ligand coordination journal January 2020
Finite Elasticity and Viscoelasticity book January 1996
Strain recovery and self-healing in dual cross-linked nanoparticle networks journal January 2013
Softening of bulk modulus and negative Poisson’s ratio near the volume phase transition of polymer gels journal March 1991
The development of microgels/nanogels for drug delivery applications journal April 2008
Modeling the response of dual cross-linked nanoparticle networks to mechanical deformation journal January 2013
Elasticity of polymer networks cross-linked in states of strain journal January 1960
Kinetics of solvent absorption and permeation through a highly swellable elastomeric network: Solvent Absorption and Permeation journal December 2002
Counting primary loops in polymer gels journal November 2012
Synthetic homeostatic materials with chemo-mechano-chemical self-regulation journal July 2012
Fibronectin and wound healing journal January 1984
Mechano-chemical oscillations and waves in reactive gels journal May 2012
Direct correlation of single-molecule properties with bulk mechanical performance for the biomimetic design of polymers journal September 2014
Multiple point adsorption in a heteropolymer gel and the Tanaka approach to imprinting: experiment and theory journal October 2003
Theoretical and computational modeling of self-oscillating polymer gels journal March 2007
Theory of phase transition in polymer gels book January 1993
Modeling autonomously oscillating chemo-responsive gels journal January 2010
A constitutive model for compressible elastomeric solids journal September 1996
Gel Dynamics journal May 2009
Global signaling of localized impact in chemo-responsive gels journal January 2009
Stimuli-responsive behavior of composites integrating thermo-responsive gels with photo-responsive fibers journal January 2016
Self-healing and thermoreversible rubber from supramolecular assembly journal February 2008
Mechanical Resuscitation of Chemical Oscillations in Belousov-Zhabotinsky Gels journal March 2012
Synthesis and Single-Molecule Studies of a Well-Defined Biomimetic Modular Multidomain Polymer Using a Peptidomimetic β-Sheet Module journal November 2004
Inverse Miniemulsion ATRP:  A New Method for Synthesis and Functionalization of Well-Defined Water-Soluble/Cross-Linked Polymeric Particles journal April 2006
Three-dimensional model for chemoresponsive polymer gels undergoing the Belousov-Zhabotinsky reaction journal October 2008
Fibronectin at a glance journal October 2002
Fibers with Integrated Mechanochemical Switches: Minimalistic Design Principles Derived from Fibronectin journal November 2012
Models for the specific adhesion of cells to cells journal May 1978
Computational Design of Active, Self-Reinforcing Gels journal May 2010
Ductility, toughness and strain recovery in self-healing dual cross-linked nanoparticle networks studied by computer simulations journal January 2015
Modeling the Photoinduced Reconfiguration and Directed Motion of Polymer Gels journal July 2013
Designing Dual-functionalized Gels for Self-reconfiguration and Autonomous Motion journal April 2015
UV patternable thin film chemistry for shape and functionally versatile self-oscillating gels journal January 2013
Designing Mechanomutable Composites: Reconfiguring the Structure of Nanoparticle Networks through Mechanical Deformation journal July 2014
Autonomous viscosity oscillation by reversible complex formation of terpyridine-terminated poly(ethylene glycol) in the BZ reaction journal January 2010
Influence of Confinement on the Chain Conformation of Cyclic Poly( N -isopropylacrylamide) journal November 2015
Strain-stiffening gels based on latent crosslinking journal January 2017
Modeling polymer grafted nanoparticle networks reinforced by high-strength chains journal January 2014
Controlling chemical oscillations in heterogeneous Belousov-Zhabotinsky gels via mechanical strain journal April 2009
“Patterning with loops” to dynamically reconfigure polymer gels journal January 2018
Pattern Formation and Shape Changes in Self-Oscillating Polymer Gels journal November 2006
Modular Domain Structure:  A Biomimetic Strategy for Advanced Polymeric Materials journal February 2004

Similar Records

Dynamic behavior of chemically tunable mechano-responsive hydrogels
Journal Article · Wed Nov 03 00:00:00 EDT 2021 · Soft Matter · OSTI ID:1800720

Evaluation of the mechanical properties of a hydrogel fiber in the development of a polymeric actuator
Journal Article · Sun May 01 00:00:00 EDT 1994 · Journal of Intelligent Material Systems and Structures · OSTI ID:1800720

Control over emergence and alignment of transient blisters in thermo-responsive gels using hierarchically patterned substrates
Journal Article · Mon Jul 25 00:00:00 EDT 2022 · Soft Matter · OSTI ID:1800720