Smart hydrogels from laterally-grafted peptide assembly

Small peptides carrying laterally-grafted azobenzene units self-assemble into photo-responsive hydrogels which are applied as a smart matrix for controlling the dye molecules release. We demonstrate that a delicate balance among peptides interactions plays a pivotal role in the photo-responsive gel-sol transition.     

Medical applications of radiation formed hydrogels

Polyvinylpyrrolidone was used as a main component of two new biomaterials: hydrogels wound dressings and therapeutic system for induction of labour. Ionizing radiation was applied as a tool for initiation of crosslinking and sterilization of these materials. Both products successfully passed clinical tests and have been commercialized. Draft of technology and some properties are shortly reviewed in this report.     

Enzyme responsive supramolecular hydrogels assembled from nonionic peptide amphiphiles

Smart peptide hydrogels are of great interest for their great potential applications. Here, we report a facile approach to prepare a class of enzyme-responsive hydrogels in a scalable manner. These hydrogels self-assemble from a family of nonionic peptide amphiphiles(PAs) synthesized by sequential ring-opening polymerization(ROP) of γ-benzyl-L-glutamate N-carboxyanhydride(BLG-NCA) and L-tyrosine N-carboxyanhydride(Tyr-NCA), followed by subsequent aminolysis. These PA samples can readily form a clear hydrogel with a critical gelation concentration as low as 0.5 wt%. The incorporation of tyrosine residues offers hydrophobicity, hydrogen-bonding interaction and enzyme-responsive properties. The hydrogel-to-nanogel transition is observed under physiological conditions in the presence of horseradish peroxidase(HRP) and hydrogen peroxide(H2 O2). The obtained PA hydrogels are ideal candidates for the new generation of smart scaffolds.     

Hybrid hydrogels self-assembled from HPMA copolymers containing peptide grafts

Graft copolymers were designed that self-assemble into hydrogels mediated by the interaction of coiled-coil peptide domains. A linear hydrophilic polymer of HPMA was chosen as the backbone, and coiled-coil forming peptides, covalently attached to the backbone, formed the grafts. Microrheology was used to evaluate the self-assembly of graft copolymers into hydrogels. The results revealed that the length and the number of coiled-coil grafts per chain had a significant influence on the gelation process. At least 4 heptads were needed to achieve the association of graft copolymers into hydrogels. CD spectra of the copolymer containing 5 heptad grafts further suggested that coiled-coil formation may contribute to the self-assembly. Gelation of graft copolymers containing CC4 peptides indicated that a threshold amount of grafts per macromolecule is needed to form a three-dimensional structure. These studies demonstrated a potential of the graft copolymers to create self-assembling hydrogels with desirable and controllable structures.     

Highly stable supramolecular hydrogels formed from 1,3,5-benzenetricarboxylic acid and hydroxyl pyridines

New supramolecular hydrogels with the maximal sol-gel transition temperature(T_(gel)) of 95℃were obtained by using gelators formed from 1,3,5-benzenetricarboxylic acid(BTA) and para-hydroxyl pyridine(PHP) or meta-hydroxyl pyridine(MHP).The single crystal structure of the complex formed from BTA and ortho-hydroxyl pyridine(OHP) indicated that the molecules assembled into superstructure via both hydrogen bonds andπ-πstacking interaction.     

Supramolecular assemblies formed by new L-lysine derivatives of viologens

L-Lysine derivatives of viologens form supramolecular assemblies of fibers and ribbons in some aromatic solvents, and the charge separation reaction in these self-assembling systems proceeds with a similar efficiency to the MV2+ system.     

Surfactant-induced healing of tough hydrogels formed via hydrophobic interactions

Different reversible molecular interactions have been used in the past few years to generate self-healing in synthetic hydrogels. However, self-healing hydrogels synthesized so far suffer from low mechanical strength which may limit their use in any stress-bearing applications. Here, we present a simple technique to heal mechanically strong polyacrylamide hydrogels formed via hydrophobic interactions between stearyl groups. A complete healing in the hydrogels was achieved by the treatment of the damaged areas with an aqueous solution of wormlike sodium dodecyl sulfate micelles. The micelles in the healing agent solubilize the hydrophobes in the cut surfaces, so that they easily find their partners in the other cut surface due to the hydrophobic interactions. Surfactant-induced healing produces high toughness (～1 MPa) gels withstanding 150 kPa of stress at a deformation ratio of 1,100 %. The healing technique developed here is generally applicable to the physical gels formed by hydrophobic associations.     

Responsive hydrogels from the intramolecular folding and self-assembly of a designed peptide

A general peptide design is presented that links the pH-dependent intramolecular folding of beta-hairpin peptides to their propensity to self-assemble, affording hydrogels rich in beta-sheet. Chemical responsiveness has been specifically engineered into the material by linking intramolecular folding to changes in solution pH, and mechanical responsiveness, by linking hydrogelation to self-assembly. Circular dichroic and infrared spectroscopies show that at low pH individual peptides are unstructured, affording a low-viscosity aqueous solution. Under basic conditions, intramolecular folding takes place, affording amphiphilic beta-hairpins that intermolecularly self-assemble. Rheology shows that the resulting hydrogel is rigid but is shear-thinning. However, quick mechanical strength recovery after cessation of shear is observed due to the inherent self-assembled nature of the scaffold. Characterization of the gelation process, from the molecular level up through the macroscopic properties of the material, suggests that by linking the intramolecular folding of small designed peptides to their ability to self-assemble, responsive materials can be prepared. Cryo-transmission electron and laser scanning confocal microscopies reveal a water-filled porous scaffold on both the nano- and microscale. The environmental responsiveness, morphology, and peptidic nature make this hydrogel a possible material candidate for biomedical and engineering technology.     

Fibrillar superstructure from extended nanotapes formed by a collagen-stimulating peptide

The nanostructure of a peptide amphiphile in commercial use in anti-wrinkle creams is investigated. The peptide contains a matrikine, collagen-stimulating, pentapeptide sequence. Self-assembly into giant nanotapes is observed and the internal structure was found to comprise bilayers parallel to the flat tape surfaces.     

Theoretical study on tertiary structural elements of beta-peptides: nanotubes formed from parallel-sheet-derived assemblies of beta-peptides

Parallel or polar strands of beta-peptides spontaneously form nanotubes of different sizes in a vacuum as determined by ab initio calculations. Stability and conformational features of [CH3CO-(beta-Ala)k-NHCH3]l (1 < or = k < or = 4, 2 < or = l < or = 4) models were computed at different levels of theory (e.g., B3LYP/6-311++G(d,p)// B3LYP/6-31G(d), with consideration of BSSE). For the first time, calculations demonstrate that sheets of beta-peptides display nanotubular characteristics rather than two-dimensional extended beta-layers, as is the case of alpha-peptides. Of the configurations studied, k = l = 4 gave the most stable nanotubular structure, but larger assemblies are expected to produce even more stable nanotubes. As with other nanosystems such as cyclodextrane, these nanotubes can also incorporate small molecules, creating a diverse range of applications for these flexible, biocompatible, and highly stable molecules. The various side chains of beta-peptides can make these nanosystems rather versatile. Energetic and structural features of these tubular model systems are detailed in this paper. It is hoped that the results presented in this paper will stimulate experimental research in the field of nanostructure technology involving beta-peptides.     

Fibrous crystalline hydrogels formed from polymers possessing a linear poly(ethyleneimine) backbone

Novel thermoreversible physical hydrogels formed from polymers with linear and star architectures possessing a linear poly(ethyleneimine) (PEI) backbone have been investigated. The hydrogelation occurred simply upon natural cooling of hot aqueous solutions of PEIs to room temperature. The X-ray diffraction and differential scanning calorimetry measurements for the resultant hydrogels unambiguously indicated that the hydrogelation originated from the formation of dihydrate crystalline structures of PEI. These crystalline hydrogels are structurally unique and hierarchical. Microscopic images revealed that the morphologies of the crystalline hydrogels depend on their molecular architectures. The linear PEI resulted in branched fibrous bundles organized by unit crystalline nanofibers with a width of ca. 5-7 nm. The six-armed star with benzene ring core produced fanlike fibrous bundles while the four-armed star with porphyrin core assembled into asterlike aggregates. The critical concentration of gelation (C(G)) was low (about 0.2 approximately 0.3%) and the thermoreversible gel-sol transition temperatures (T(G)) were controllable from approximately 43 to approximately 79 degrees C. The hydrogels formed in the presence of the various aqueous additives including organic solvents, hydrophilic polymers, physical cross-linker, chemical cross-linker, and base enabling modification and functionalization during synthesis. The mechanical properties of the hydrogels could be improved by chemical cross-linking of preformed hydrogels by glutaraldehyde. Physically and physical/chemical cross-linked hydrogels served as excellent template roles in biomimetic silicification, which produced silica-PEI hybrid powder or monolith constructed by nanofibers.     

Nanostructured polymer assemblies formed at interfaces: applications from immobilization and encapsulation to stimuli-responsive release

In recent years, interfacial properties have been tailored with nanostructured polymer assemblies to generate materials with specific properties and functions for application in diverse fields, including biomaterials, drug delivery, catalysis, sensing, optics and corrosion. This perspective begins with a brief introduction of the assembly techniques that are commonly employed for the synthesis of nanostructured polymer materials, followed by discussions on how the interfaces influence the properties and thus the functionalities of the polymer materials prepared. Applications of the interfacial polymer nanostructures, particularly for the immobilization and encapsulation of cargo, are then reviewed, focusing on stimuli-responsive cargo release from the polymer nanostructured assemblies for controlled delivery applications. Finally, future research directions in these areas are briefly discussed.     

Assembling and releasing performance of supramolecular hydrogels formed from simple drug molecule as the hydrogelator

A simple drug compound, 4-oxo-4-（2-pyridinylamino） butanoic acid （defined as AP）, was able to gel water at 4 wt% concentration under various conditions. In the superstructure, AP molecules assembled into fibrous aggregates driving by hydrogen bonds and π-π stacking interaction. The gels with different backbone structures released drug molecules in different speeds.     

Fractal structures of the hydrogels formed in situ from poly(N-isopropylacrylamide) microgel dispersions

Dispersions of poly(N-isopropylacrylamide) (PNIPAM) microgel thermally gel in the presence of inorganic salts. The in situ-formed hydrogels, with a network of soft particles, represent a new type of colloidal gels. Here, their fractal structures were determined by rheological measurements, using the models of both Shih et al. and Wu and Morbidelli. According to the definition of Shih et al., the colloidal PNIPAM gels fall into the strong-link regime. Yet the calculated fractal dimension of the floc backbone, x, yielded unrealistic negative values, suggesting this model is inapplicable for the present system. The Wu-Morbidelli model gives physically sounder results. According to this model, the strengths of the inter- and intrafloc links are comparable, and the in situ-formed gels are in the transition regime. The fractal dimension, d(f), of the hydrogel decreases from ～2.5 to ～1.8 when the heating temperature increases from 34 to 40 °C. The d(f) values suggest different aggregation mechanisms at different temperatures, that is, a reaction-limited one accompanied by rearrangement at low temperature, a typical reaction-limited one at the intermediate temperature, and a diffusion-limited one at high temperature. With increasing salt concentration, the d(f) of the hydrogel decreases from ～2.1 to ～1.7, suggesting the aggregation mechanism changes from reaction-limited to diffusion-limited. The effects of both temperature and salt concentration can be explained by the changes in the interactions among the microgel particles. The thermogellable PNIPAM microgel dispersions may serve as a model system for the study of heat-induced gelation of globular proteins.     

DNA hydrogels formed of bended DNA scaffolds and properties study

In recent years,DNA supramolecular hydrogels have attracted much attention due to their injectability,biocompatibility,responsiveness and self-healing properties.In this work,we designed a linear DNA brick containing one duplex with two cytosine (C)-rich sequence on both ends.This brick can first assemble to form duplex under pH 8 condition.After adjusting the pH to 5,the C-rich sequence tends to form intermolecular i-motif structure,which joins the linear DNA molecules together to form interlocked cyclic structures and yield the DNA hydrogel.By adjusting the length and bending curvature of the duplex part of the molecule,one can change the basic unit of the hydrogel structure to tune the properties of the DNA hydrogel.     

Enzyme-triggered self-assembly of peptide hydrogels via reversed hydrolysis

We demonstrate that proteases can be used to selectively trigger the self-assembly of peptide hydrogels via reversed hydrolysis.     

Enhanced photoluminescence from poly(phenylene vinylene):dendrimer polyelectrolyte assemblies in solution

Poly(2,5-methoxy-propyloxy sulfonate phenylene vinylene)(MPS-PPV) and DAB-Am-16, a generation 3.0 polypropylenimine hexadecamine dendrimer (DAB), are shown to form a tunable photoresponsive polyelectrolyte assembly in aqueous solution with an enhanced emission signal of up to 18-times that of MPS-PPV alone.     

医用水凝胶力学性能的研究进展

水凝胶是一类由亲水性聚合物链通过多种交联机制而形成的三维网络结构,具有良好的生物相容性、降解性及可调节的力学性能,广泛用于医药领域。针对不同的临床应用场景,水凝胶需要具备不同的力学性能,但目前尚无统一、系统的量化评价标准,无法针对不同临床应用需求特异性地调节水凝胶性能,限制了此类制剂应用。本文系统总结了医用水凝胶的临床应用及相应的力学性能要求、力学性能的表征手段及调节方法,并对医用水凝胶的发展现状进行总结和展望,希望为医用水凝胶力学性能的研究和发展提供理论基础。     

Cyclocarbophosphazene-containing tetrameric assemblies formed by the mediation of P-O-P and P-O-Cu linkages

Cyclocarbophosphazene-containing tetrameric assemblies formed by the mediation of P-O-P and P-O-Cu linkages have been isolated and characterized.