Competitive Supramolecular Associations Mediate the Viscoelasticity of Binary Hydrogels (original) (raw)
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Modulation of physical properties of supramolecular hydrogels based on a hydrophobic core
Physical chemistry chemical physics : PCCP, 2015
We demonstrate herein the variation in viscoelastic properties of supramolecular hydrogels (SMGs) composed of two amphiphiles, N-Palmitoyl-Gly-His (PalGH) and sodium palmitate (PalNa). PalGH molecules in water form lamellar-like assemblies, which stack into sheet-shaped aggregates, resulting in the evolution of three-dimensional network structures. Once PalNa is added to PalGH, the alkyl groups of PalNa incorporate themselves into the hydrophobic cores of PalGH lamellar-like assemblies, resulting in a change in the assembly from lamellar-like to fibrous micelle-like. Consequently, sheet-shaped aggregates turn into flexible fibrils, which form bundles, resulting in network structures. Mixed hydrogel network structures differ in morphology from those in homogenous PalGH and PalNa hydrogels. Changes in the network structure eventually alter the bulk viscoelastic properties of hydrogels. These results demonstrate that the viscoelastic properties of supramolecular hydrogels can be tuned ...
Advanced Materials, 2021
Rational design of dynamic hydrogels with desirable viscoelastic behaviors relies on an in-depth understanding of the principles correlating molecular parameters and macroscopic properties. To quantitatively elucidate such principles, we designed a series of dynamic covalent hydrogels crosslinked via hydrazone bonds. We tuned the exchange rate of hydrazone bond by varying the concentration of an organic catalyst, while maintaining the crosslinking density unchanged. This strategy of independently tuning exchange dynamics of crosslinks and crosslinking density allowed unambiguous analysis of the viscoelastic response of the dynamic hydrogels as a function of their network parameters. We found that the terminal relaxation time of the dynamic hydrogels is primarily determined by two factors: the exchange rate of crosslinks and the number of effective crosslinks per polymer chain, and is independent of the network architecture. Furthermore, a universal correlation is identified between the terminal relaxation time determined from stress relaxation and the exchange rate determined via reaction kinetics, which can be generalized to any viscoelastic hydrogel networks in principle. This quantitative correlation facilitates the development of dynamic hydrogels with variable desired viscoelastic response based on molecular design.
Macromolecules
We investigate the conformational properties of stimuliresponsive hydrogels from triblock polyelectrolytes PtBA-b-P2VP-b-PtBA (PtBA and P2VP are poly(tert-butyl acrylate) and poly(2-vinylpyridine)) and the corresponding polyampholytes PAA-b-P2VP-b-PAA (PAA is poly(acrylic acid)), the latter with nonquaternized or quaternized P2VP blocks. The block lengths are the same in all three polymers with relatively short end blocks and long middle blocks. The mechanical properties of the hydrogels have previously been found to depend strongly on the pH value and on the nature of the blocks (Polymer 2008, 49, 1249). Here, we present results from rheological studies and small-angle neutron scattering revealing the underlying hydrogel structures. The hydrogel structure of the polyampholyte depends on the charge asymmetry, controlled by the pH value, and reveals several transitions with increasing charge ratio. A low charge asymmetry causes the collapse of the chains into large globular structures due to the fluctuation-induced attractions between oppositely charged moieties. In contrast, at higher charge asymmetry, a network is formed. The latter is also found for the polyelectrolyte system. These results demonstrate the origin of the strong changes in mechanical properties upon change of pH.
The Effect of Network Solvation on the Viscoelastic Response of Polymer Hydrogels
Polymers
The majority of investigations consider the deformation response of hydrogels, fully controlled by the deformation behavior of their polymer network, neglecting the contribution caused by the presence of water. Here, we use molecular dynamics simulation in an attempt to include the effect of physically bound water via polymer chain solvation on the viscoelastic response of hydrogels. Our model allows us to control the solvation of chains as an independent variable. The solvation of the chain is independent of other factors, mainly the effect (pH) which interferes significantly in experiments. The solvation of hydrophilic chains was controlled by setting a partial charge on the chains and quantified by the Bjerrum length (BL). The BL was calculated from the partial electric charge of the solvent and macromolecular network. When the BL is short, the repulsive Van der Waals interactions are predominant in the vicinity of macromolecules and solvation is not observed. For a long BL, the water molecules in the solvation zone of network are in the same range as attractive intermolecular forces and the solvation occurs. The model also allows the consideration of molecules of water attached to two chains simultaneously, forming a temporary bridging. By elucidating the relations between solvation of the network and structural changes during the network deformation, one may predict the viscoelastic properties of hydrogels knowing the molecular structure of its polymer chains.
Isomeric control of the mechanical properties of supramolecular filament hydrogels
Biomaterials science, 2017
Supramolecular filament hydrogels are an emerging class of biomaterials that hold great promise for regenerative medicine, tissue engineering, and drug delivery. However, fine-tuning of their bulk mechanical properties at the molecular level without altering their network structures remains a significant challenge. Here we report an isomeric strategy to construct amphiphilic peptides through the conjugation of isomeric hydrocarbons to influence the local viscoelastic properties of their resulting supramolecular hydrogels. In this case, the packing requirements of the chosen isomeric hydrocarbons within the supramolecular filaments are dictated by their atomic arrangements at the molecular and intermolecular levels. Atomistic molecular dynamics simulations suggest that this design strategy can subtly alter the molecular packing at the interface between the peptide domain and the hydrophobic core of the supramolecular assemblies, without changing both the filament width and morphology...
Advanced Methods for the Characterization of Supramolecular Hydrogels
Gels
With the increased research on supramolecular hydrogels, many spectroscopic, diffraction, microscopic, and rheological techniques have been employed to better understand and characterize the material properties of these hydrogels. Specifically, spectroscopic methods are used to characterize the structure of supramolecular hydrogels on the atomic and molecular scales. Diffraction techniques rely on measurements of crystallinity and help in analyzing the structure of supramolecular hydrogels, whereas microscopy allows researchers to inspect these hydrogels at high resolution and acquire a deeper understanding of the morphology and structure of the materials. Furthermore, mechanical characterization is also important for the application of supramolecular hydrogels in different fields. This can be achieved through atomic force microscopy measurements where a probe interacts with the surface of the material. Additionally, rheological characterization can investigate the stiffness as well...
Chemistry of Materials
Self-assembled nanofibers are ubiquitous in nature and serve as inspiration for the design of supramolecular hydrogels. A multicomponent approach offers the possibility of enhancing the tunability and functionality of this class of materials. We report on the synergistic multicomponent self-assembly involving a peptide amphiphile (PA) and a 1,3:2,4-dibenzylidene-D-sorbitol (DBS) gelator to generate hydrogels with tunable nanoscale morphology, improved stiffness, enhanced self-healing, and stability to enzymatic degradation. Using induced circular dichroism of Thioflavin T (ThT), electron microscopy, small-angle neutron scattering, and molecular dynamics approaches, we confirm that the PA undergoes self-sorting, while the DBS gelator acts as an additive modifier for the PA nanofibers. The supramolecular interactions between the PA and DBS gelators result in improved bulk properties and cytocompatibility of the two-component hydrogels as compared to those of the single-component systems. The tunable mechanical properties, self-healing ability, resistance to proteolysis, and biocompatibility of the hydrogels suggest future opportunities for the hydrogels as scaffolds for tissue engineering and drug delivery vehicles.
Communications Materials, 2021
About ten years ago, chemically fueled systems have emerged as a new class of synthetic materials with tunable properties. Yet, applications of these materials are still scarce. In part, this is due to an incomplete characterization of the viscoelastic properties of those materials, which has – so far – mostly been limited to assessing their linear response under shear load. Here, we fill some of these gaps by comparing the viscoelastic behavior of two different, carbodiimide fueled Fmoc-peptide systems. We find that both, the linear and non-linear response of the hydrogels formed by those Fmoc-peptides depends on the amount of fuel driving the self-assembly process – but hardly on the direction of force application. In addition, we identify the concentration of accumulated waste products as a novel, so far neglected parameter that crucially affects the behavior of such chemically fueled hydrogels. With the mechanistic insights gained here, it should be possible to engineer a new ge...
2020
Many biopolymer hydrogels are environmentally responsive because they are held together by physical associations that depend on pH and temperature. Here we investigate how the pH and temperature response of the rheology of hyaluronan hydrogels is connected to the underlying molecular interactions. Hyaluronan is an essential structural biopolymer in the human body with many applications in biomedicine. Using two-dimensional infrared (2DIR) spectroscopy, we show that hyaluronan chains become connected by hydrogen bonds when the pH is changed from 7.0 to 2.5, and that the bond density at pH 2.5 is independent of temperature. Temperature-dependent rheology measurements show that due to this hydrogen bonding the stress relaxation at pH 2.5 is strongly slowed down in comparison to pH 7.0, consistent with the sticky reptation model of associative polymers. From the flow activation energy we conclude that each polymer is crosslinked by multiple (5-15) hydrogen bonds to others, causing slow ...