Tough Stimuli-Responsive Supramolecular Hydrogels with Hydrogen-Bonding Network Junctions (original) (raw)

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 ...

Supramolecular polymer/peptide hybrid hydrogels with tunable stiffness mediated by interchain acid-amide hydrogen bonds

RSC Advances, 2022

Hydrogels are a class of biomaterials used in the field of tissue engineering and drug delivery. Many tissue engineering applications depend on the material properties of hydrogel scaffolds, such as mechanical stiffness, pore size, and interconnectivity. In this work, we describe the synthesis of peptide/polymer hybrid double-network (DN) hydrogels composed of supramolecular and covalent polymers. The DN hydrogels were prepared by combining the self-assembled pentafluorobenzyl diphenylalanyl aspartic acid (PFB-FFD) tripeptide for the first network and the polymeric PNIPAM-PEGDA copolymer for the second network. During this process, self-assembled peptide nanostructures are cross-linked to the polyacrylamide group in the polymer network through non-covalent interactions.

Ultrahigh-Water-Content Supramolecular Hydrogels Exhibiting Multistimuli Responsiveness

Journal of the American Chemical Society, 2012

Hydrogels are three-dimensional networked materials that are similar to soft biological tissues and have highly variable mechanical properties, making them increasingly important in a variety of biomedical and industrial applications. Herein we report the preparation of extremely high water content hydrogels (up to 99.7% water by weight) driven by strong host−guest complexation with cucurbit[8]uril (CB[8]). Cellulosic derivatives and commodity polymers such as poly(vinyl alcohol) were modified with strongly binding guests for CB[8] ternary complex formation (K eq = 10 12 M −2 ). When these polymers were mixed in the presence of CB[8], whereby the overall solid content was 90% cellulosic, a lightly colored, transparent hydrogel was formed instantaneously. The supramolecular nature of these hydrogels affords them with highly tunable mechanical properties, and the dynamics of the CB[8] ternary complex cross-links allows for rapid self-healing of the materials after damage caused by deformation. Moreover, these hydrogels display responsivity to a multitude of external stimuli, including temperature, chemical potential, and competing guests. These materials are easily processed, and the simplicity of their preparation, their availability from inexpensive renewable resources, and the tunability of their properties are distinguishing features for many important water-based applications.

Hydrophobically-Modified PEG Hydrogels with Controllable Hydrophilic/Hydrophobic Balance

Polymers, 2021

This work reports on a novel method to synthesize hydrophobically-modified hydrogels by curing epoxy monomers with amines. The resulting networks contain hydrophilic poly(ethylene glycol) (PEG) segments, poly(propylene glycol) (PPG) segments, and C18 alkyl segments. By varying the content of C18 segments, networks with different hydrophilic-lipophilic balance (HLB) are obtained. All networks show an amphiphilic behavior, swelling considerably both in organic solvents and in aqueous media. In the latter they display a thermosensitive behavior, which is highly affected by the network HLB and the pH of the solution. A decrease in HLB results in an increment of the polymer weight content (wp) due to hydrophobic association. Furthermore, a reduction in HLB induces a remarkable increase in initial modulus, elongation at break and tensile strength, especially when wp becomes greater than about 10%. Low field nuclear magnetic resonance (LF-NMR) experiments evidence that, when HLB decreases,...

Tough Supramolecular Hydrogel Based on Strong Hydrophobic Interactions in a Multiblock Segmented Copolymer

Macromolecules, 2017

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Supramolecular Self-Assembly to Control Structural and Biological Properties of Multicomponent Hydrogels

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.

Shape Memory Hydrogels Based on Noncovalent Interactions

Shape-Memory Materials, 2018

Shape memory polymers (SMPs) are polymeric materials that are capable of fixing temporary shape and recovering the permanent shape in response to external stimuli. In particular, supramolecular interactions and dynamic covalent bond have recently been introduced as temporary switches to construct supramolecular shape memory hydrogels (SSMHs), arising as promising materials since they can exhibit excellent cycled shape memory behavior at room temperature. On the other hand, hydrogels, conventionally, are flexible but sometimes extremely soft, and they can be easily damaged under external force, which could limit their long-time application. Therefore, self-healing hydrogels that can be rapidly auto-repaired when the damage occurs have been recently developed to solve this problem. These materials present more than one triggering stimulus that can be used to induce the shape memory and self-healing effect. These driven forces can be originated from hydrogen bonds, hydrophobic interactions, and reversible covalent bonds, among others. Beyond all these, hybrid organic-inorganic interactions represent an interesting possibility due to their versatility and favorable properties that allow the fabrication of multiresponsive hydrogels. In this chapter, shape memory hydrogels based on noncovalent interactions are described.

Multicomponent self-assembly: Supramolecular design of complex hydrogels for biomedical applications

Elsevier eBooks, 2018

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.

Supramolecular Hydrogel Based on pNIPAm Microgels Connected via Host–Guest Interactions

Polymers, 2018

In this work, host-guest supramolecular hydrogels were prepared from poly(N-isopropylacrylamide) (pNIPAm) microgels utilizing electrostatic and host/guest self-assembly. First, pNIPAm microgels bearing a poly(acrylic acid) (pAAc) shell were coated with positively charged β-cyclodextrin polymers. Addition of adamantane-substituted dextrans (Dex-Ada) allowed us to establish interparticle connections through β-cyclodextrin-adamantane (βCD-Ada) inclusion complex formation, and thus to prepare hierarchical hydrogels. Under the conditions of hydrogel formation, close contact between the microgels was ensured. To the best of our knowledge, this is the first example of doubly crosslinked microgels prepared by noncovalent crosslinking via host-guest interactions. The prepared macrogels were studied with rheology, and fast mechanical response to temperature variation was found. Furthermore, the hydrogels exhibit fully reversible temperature-induced gel-sol transition at the physiological temperature range (37-41 • C), due to the synergetic effect between shrinking of the microgels and dissociation of βCD-Ada crosslinks at higher temperatures. This opens up attractive prospects of their potential use in biomedical applications.

Supramolecular hydrogels cross-linked by preassembled host–guest PEG cross-linkers resist excessive, ultrafast, and non-resting cyclic compression

NPG Asia Materials, 2018

Poly(ethylene glycol) (PEG)-based hydrogels are promising materials for biomedical applications because of their excellent hydrophilicity and biocompatibility. However, conventional chemically cross-linked PEG hydrogels are brittle under mechanical loading. The mechanical resilience and rapid recovery abilities of hydrogel implants are critical in load-bearing tissues, such as articular cartilage, which are routinely subjected to cyclic loadings of high magnitude and frequency. Here, we report the fabrication of novel supramolecular PEG hydrogels by polymerizing N,Ndimethylacrylamide with supramolecular cross-linkers self-assembled from adamantane-grafted PEG and monoacrylated β-cyclodextrin. The resultant PEG-ADA supramolecular hydrogels exhibit substantial deformability, excellent capacity to dissipate massive amounts of loading energy, and have a rapid, full recovery during excessive, ultrafast, and non-resting cyclic compression. Furthermore, the energy dissipation capacity of the PEG-ADA (adamantane-grafted Poly(ethylene glycol)) hydrogels can be regulated by changing the concentration, molecular weight and cross-linking density of PEG. According to in vitro cell metabolism and viability tests, the PEG-ADA hydrogels are non-cytotoxic. When placed over a monolayer of myoblasts that were subjected to instantaneous compressive loading, the PEG-ADA hydrogel cushion significantly enhanced cell survival under this deleterious mechanical insult compared with the effects of the conventional PEG hydrogel. Therefore, PEG-ADA hydrogels are promising prosthetic biomaterials for the repair and regeneration of load-bearing tissues.