A series of physically cross-linked hydrogels composed poly(acrylic acid) and octylphenol polyoxyethylene acrylate with high mechanical strength are reported here with dual cross-linked networks that formed by silica nanoparticles (SNs) and hydrophobic association micro-domains (HAMDs). Acrylic acid (AA) and octylphenol polyoxyethylene acrylate with 10 ethoxyl units (OP-10-AC) as basic monomers in situ graft from the SNs surface to build poly(acrylic acid) hydrophilic backbone chains with randomly distributed OP-10-AC hydrophobic side chains. The entanglements among grafted backbone polymer chains and hydrophobic branch architecture lead to the SNs and HAMDs play the role of physical cross-links for the hydrogels network structure. The rheological behavior and polymer concentration for gelation process are measured to examine the critical gelation conditions. The correlation of the polymer dual cross-linked networks with hydrogels swelling behavior, gel-to-sol phase transition, and mechanical strength are addressed, and the results imply that the unique dual cross-linking networks contribute the hydrogels distinctive swelling behavior and excellent tensile strength. The effects of SNs content, molecular weight of polymer backbone, and temperature on hydrogels properties are studied, and the results indicate that the physical hydrogel network integrity is depended on the SNs and HAMDs concentration. 相似文献
ABSTRACT Rheological measurements were performed on Hyaluronic acid (HA) and its derivative solutions to evaluate steady flow viscosity and dynamics response with the aim to correlate the materials properties to the concentration, molecular weight and chemical structure. At low molecular weight and concentration, the HA solutions behaved as viscous liquid, whereas a soft-gel response was evident at higher molecular weight and concentration due to chains entanglement. Increasing the molecular weight was more effective than increasing concentration in promoting entanglement of molecular chains of HA. Comparing the behavior of HA solutions with that of Hyaluronic acid derivatives, it is showed that it is possible to modulate the rheological properties of HA based solutions by chemical modification preserving the bio-compatibility of the materials. The results of the rheological analysis provide a valuable tool to properly design optimal substitutes for specific biomedical application. 相似文献
One of the essential parts in the molecular mechanism of biological properties is the structural changes of proteins induced by stimuli. An amphiphilic copolymer, poly(L-leucine) grafted polyallylamine as a simple model of proteins, has been prepared by NCA polymerization with free amino groups of polyallylamine as an initiator. Here, we report the pH-induced reversible conformational and morphological regulation of the amphiphilic copolymer, whose hydrophobic peptide graft chains have no pH-sensitive groups, in an aqueous solution containing 50 vol % trifluoroethanol. The conformation of the poly(L-leucine) graft chain was found to be strongly pH dependent. Under acidic conditions, where electrostatic repulsion existed between the neighboring protonated amine moieties of the polyallylamine main chain, the rapid aggregation of the poly(l-leucine) graft chains was disturbed, and the peptide graft chains formed a beta-sheet structure owing to the intramolecular hydrogen bonding among the graft chains. Under this condition, the amphiphilic polymer formed amyloid-like fibrils, and then the fibrils grew into a planer plate composed of staked beta-sheets. On the other hand, under basic conditions, the poly(L-leucine) graft chains showed conformational transitions from a beta-sheet structure to an alpha-helical conformation owing to a distortion of the regular arrangement of the peptide graft chains by the conformational change of the polyallylamine main chain, whose amino groups were deprotonated. The conformational transition resulted in a disturbance of the regular sheet assembly of the amphiphilic copolymer and induced morphological changes to the amorphous globular aggregates. The pH-induced conformational and morphological changes of the poly(L-leucine) graft polyallylamine were reversible and synchronized with the protonation of the polyallylamine main chain. 相似文献
Summary : Viscosity, asymmetric flow field-flow fractionation (AFFFF) methods, and dynamic light scattering (DLS) experiments were used to characterize the effect of pH on the behavior of dilute and semidilute aqueous buffered solutions of hyaluronic acid (HA). It is shown that degradation of HA occurs at pH < 4 and pH > 11, and in the domain 4 < pH < 11 virtually no disruption of the HA chains occurs. The pH-induced scission of HA is attributed to the cleavage of glycosidic bonds. In dilute solutions, intramolecular rupture of HA chains occurs and in the semidilute concentration regime network-fragmentation is observed at low and high pH values. The degree of degradation of HA is most marked at high pH. From the molecular weight and radius of gyration obtained from AFFFF at different pH values, it is clear that the degradation of HA starts at early times after preparation of the solution, and continues for a couple of days. The kinetics of degradation of HA is fastest at high pH. 相似文献
Recently, applications of hyaluronic acid (HA) as a biomaterial were investigated. However, the weak structure of HA gel and the effects of using cross‐linker raised concerns during in vivo resolution. In this study, we investigated the method to solve these two problems using physical cross‐linking and compositing with poly(vinyl alcohol) (PVA). Various weight ratios of HA and PVA solutions were mixed, adjustment of pH to 1.8 using HCl then used to fabricate HA‐PVA cryo‐gel by freezing‐thawing. Young's modulus of the prepared gel rose with the increase of both HA and PVA concentrations or either one of them. We estimated that HA and PVA have exhibited these mechanical properties due to forming a double network. HA‐PVA gel showed kinetic friction force of approximately 10 times of PVA gel, while water contact angle and protein adsorption of HA‐PVA gels were remarkably decreased. The properties of the prepared gel suggest that it can be used for postoperative adhesion prevention applications. 相似文献
Papidly curable hydrogels were prepared through chemical crosslinking of gelatin with poly(carboxylic acid)s including poly (L-glutamic acid) (PLGA), hyaluronic acid (HA), and poly (acrylic acid) (PAA) by use of water-soluble carbodiimide (WSC). The effects of the nature of added poly (carboxylic acid)s on gelation of mixed gelatinpoly (carboxylic acid) aqueous solutions and adhesion of the resulting hydrogels to the mouse skin were evaluated. The addition of poly (carboxylic acid) s reduced the gelation time of gelatin aqueous solutions except for HA. Mixed gelatin-PLGA solutions were cured more rapidly than other mixed solutions and the gelation time was shortened with the increasing PLGA molecular weight. The resulting gelatin-PLGA hydrogels exhibited stronger adhesion to the mouse skin than gelatin-HA and gelatin-PAA hydrogels. The bonding strength increased with the increase in PLGA molecular weight up to 83,000 and thereafter decreased. The longer gelation time and lower adhesion of the gelatin-PAA hydrogels than the gelatin-PLGA hydrogels seem to be due to poorer compatibility of gelatin with PAA than with PLGA. The mixed gelatin-PLGA solution underwent phase separation when the concentration and molecular weight of PLGA became higher than a threshold. The insignificant or suppressive effect of HA addition might be ascribed to the HA-WSC reaction which was the least effective in hydrogel formation. 相似文献
Traditional modifications to hydroxyapatite(HA) nanoparticles usually occurred after HA synthesis and thus are insufficient to avoid particle agglomeration.In this study,a new heterofunctional poly(ethylene glycol)(PEG) with phosphoric acid and carboxyl end groups,i.e.,α-(N-2-phosphoethyl phosphoric acid)-amide,ω-carboxyl-bismethyoxy poly(ethylene glycol)(ADP-PEG-COOH),was synthesized as an in situ surface modifier to HA nanoparticles.The resulting modified HA(ADP-PEG-HA) can disperse in methanol,forming a colloid stabilized by peripheral carboxyl-endcapped PEG chains.The colloidal particles resembled nanospheres which agglomerated to some extent under examination by transmission electron microscope.This highly dispersible HA nanoparticles in organic solvent might find application in preparing new HA nanocomposites. 相似文献
How to improve the therapeutic efficacy of cell delivery during mechanical injection has been a great challenge for tissue engineering. Here, we present a facile strategy based on dynamic chemistry to prepare injectable hydrogels for efficient stem cell delivery using hyaluronic acid (HA) and poly(γ-glutamic acid) (γ-PGA). The combination of the guest–host (GH) complexation and dynamic hydrazone bonds enable the HA/γ-PGA hydrogels with physical and chemical dual dynamic network and endow hydrogels a stable structure, rapid self-healing ability, and injectability. The mechanical properties, self-healing ability, and adaptability can be programmed by changing the ratio of GH network to hydrazine bond cross-linked network. Benefitting from the dynamic cross-linking networks, mild preparation process, and cytocompatibility of HA/γ-PGA hydrogels, bone marrow mesenchymal stem cells (BMSCs) show high cell viability in this system following mechanical injection. Moreover, HA/γ-PGA hydrogels can promote BMSC proliferation and upregulate the expression of cartilage-critical genes. Notably, in a rabbit auricular cartilage defect model, BMSC-laden HA/γ-PGA hydrogels can effectively promote cartilage regeneration. Together, we propose a general strategy to develop injectable self-healing HA/γ-PGA hydrogels for effective stem cell delivery in cartilage tissue engineering. 相似文献
Responsive copolymers have been prepared by grafting onto a poly(acrylamide-co-sodium acrylate) backbone [PAM-co-PANa] poly(N-isopropylacrylamide) stickers [PNIPA] characterized by a lower critical solution temperature (LCST) in water. From adsorption isotherms and DSC studies performed on PNIPA/silica mixtures, it was shown that PNIPA chains irreversibly interact with silica particles and that at low coverage they partially lose their responsiveness with temperature. When PNIPA is grafted onto a PAM-co-PANa backbone, which has no specific attraction to silica surfaces (only electrostatic repulsions), their binding process remains very similar to the one analyzed with PNIPA chains alone. Above critical copolymer and silica concentrations (Cp congruent with 1 g/L and CSi congruent with 30 g/L), hybrid networks can be formed following the rules of percolation theory. The viscoelastic properties of these networks are controlled by the concentration of inorganic cross links and the fraction of PNIPA grafts participating in bridges between particles, the others being involved in inelastic loops or pendant chains. For all of the mixtures investigated, an optimum weight ratio of RSi/PNIPA = 10-15 was found for the viscoelastic properties, in agreement with the saturation of silica beads by the copolymer. Because of the responsive behavior of PNIPA in aqueous solutions, graft copolymers are able to self-assemble with temperature, giving rise to a sol/gel transition upon heating. In the presence of added silica, hybrid aggregates (silica/PNIPA) coexist at high temperature with organic ones (PNIPA/PNIPA) with synergistic or antagonistic effects on the elastic properties depending on the proportion of PNIPA grafts per silica particle. 相似文献
Interactions between cationic bottle-brush polyelectrolyte layers adsorbed on mica across salt and oppositely charged surfactant solutions were investigated with the interferometric surface force apparatus, and the results were compared with what is known for similarly charged linear polyelectrolytes. Ellipsometric measurements demonstrated that the bottle-brush polyelectrolytes, which contain 45 units long poly(ethylene oxide) side chains, are more readily desorbed than linear equivalents when the ionic strength of the solution is increased. It is argued that this is due to the steric repulsion between the poly(ethylene oxide) side chains that reduces the surface affinity. The preadsorbed bottle-brush polyelectrolyte layers were also exposed to sodium dodecyl sulfate (SDS) solutions. It was found that the presence of SDS affected the force profiles less than observed for similarly charged linear polyelectrolytes. This observation was attributed to excluded volume constraints imposed by the poly(ethylene oxide) side chains that reduces the accessibility of the charged polyelectrolyte segments and counteracts formation of large aggregates within the layer. 相似文献
The present paper is concerned with studies for elucidation of the relationship between the structure of HA copolymers and their adsorption property toward lymphocyte subpopulations, B cell and T cell. HA is a polyamine graft copolymer of poly(hydroxyethyl methacrylate) as the backbone. In the earlier part of this paper, discussion will be made on our synthetic approach to HA copolymers having polyamine graft chains of controlled length and number, while, in the later part, the outline of our recent studies of biomedical behavior of HA copolymers in terms of selective adsorption of B cell against T cell will be presented. A possible mechanism for the cell separation will also be discussed. 相似文献
Summary: Specific temperature‐responsive biodegradable hydrogels were synthesized and characterized in terms of their regulation of enzymatic accessibility based on the physical properties of the temperature‐responsive polymers. The hydrogels consist of glycidyl methacrylate‐modified dextran grafted with the poly(N‐isopropylacrylamide) (PNIPAAm) homopolymer, and cross‐linked by co‐polymerization with NIPAAm and N,N‐dimethylacrylamide (DMAAm). The coil‐globule change in the grafted poly(NIPAAm) chains and only a slight dehydration of the poly(NIPAAm‐co‐DMAAm) cross‐linkers are effective in controlling the enzymatic degradation over a specific temperature range.
The thermo‐responses of the graft chains (steric hindrance) and the crosslinkers (slight deswelling of the hydrogel networks) control the enzymatic degradation of the hydrogel. 相似文献
The stability and properties of dilute solution hydrogels, synthesized by transition metal mediated polymerization of amino acid N-carboxyanhydrides (NCAs), have been studied in deionized (DI) water as well as various ionic media. These hydrogels are diblock amphiphilic copolymers of hydrophilic, charged segments of poly(l-lysine HBr) or poly(l-glutamic acid sodium salt), and helical, hydrophobic segments of poly(l-leucine). While many of these samples are able to form strong gels in deionized water at polymer concentrations as low as 0.25 wt %, stability in salt or buffer solutions was found to be only achieved at moderately higher polymer concentrations ( approximately 3.0 wt %). We have adjusted relative copolymer compositions and molecular weights to optimize hydrogel strength and polymer solubility in salt concentrations up to 0.5 M NaCl, as well as in cell growth media and aqueous buffers of varying pH. These materials are unique since they do not collapse in high ionic strength media, even though gel formation is contingent upon the presence of highly charged polyelectrolyte segments. The remarkable properties of these hydrogels make them excellent candidates for use as scaffolds in biomedical applications, such as tissue regeneration. 相似文献
Semi-IPN hydrogels in which poly(vinyl pyrrolidone) (PVP) chains were physically dispersed throughout poly(acrylamide) (PAM) gel networks were synthesized. These semi-IPN hydrogel networks can act as excellent nanoreactors for producing and stabilizing metal nanoparticles. The current methodology allows us to entrap metal nanoparticles throughout hydrogel networks via PVP chains. An optimized semi-IPN hydrogel formulation was found to produce silver nanoparticles, ca. 3-5 nm. The synthesized semi-IPN hydrogel-silver nanocomposites were fully characterized by using UV-vis, X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The developed semi-IPN hydrogel-silver nanocomposite (SHSNC) was evaluated for preliminary antibacterial applications. 相似文献
Using the theory of branching processes, structural parameters such as the molecular weights of elastically active network chains (EANCs), including dangling chains, backbone EANCs and dangling chains of networks built up by the alternating polyaddition of a bi- and trifunctional monomer, are characterized. The theory is compared with viscoelastic data on polyurethane networks prepared from poly(oxypropylene)triols and diisocyanate at various initial ratios of functional groups; in the calculation, the distribution of functionalities of the triols used and the possible incompleteness of the reaction is taken into account. The comparison reveals that both the length of the backbone EANC and the length of dangling chains contribute to the total width of the retardation spectrum. 相似文献
The association of poly(N,N-diethylacrylamide)(PDEA) chains has been investigated by a combination of static and dynamic laser light scattering(LLS).Unlike poly(N-isopropylacrylamide)(PNIPAM),PDEA chains can not form the C=O…H-N hydrogen bonds.Our results demonstrate that a limited number of PDEA chains collapse and associate into metastable globules in dilute solutions.The heating rate has great effect on the mesoglobule size.The formation of such mesoglobules is attributed to the competition between in... 相似文献
The polycondensation of p-aminobenzoic acid by the use of triphenylphospine and hexachloroethane is described. One way to obtain a mixed solution of rigid rod and flexible coil polymers is the polycondensation of the rigid chains in a solution of a flexible polymer matrix. Results on matrix polycondensation of poly(p-benzamide) in solutions of poly(methyl methacrylate), poly(methyl methacrylate-co-styrene), polystyrene and polyacrylonitrile are reported. It is shown that there exists an interrelation between the phase behavior of the mixed polymer solutions and the influence of the matrix polymer on the synthesis of poly(1.4.-benzamide). The ternary phase diagrams of the rigid rod/flexible coil polymer solutions were determined. 相似文献
The effects of the oriented fiber filler particles on the microscopic properties of the matrix network chains were investigated by using nanofiber filler particles as reinforcing material. Monte Carlo Rotational Isomeric State simulations were carried out for filled poly(ethylene) (PE) networks to study the dependence of the conformational distribution functions of polymer chains and their elastomeric properties on filler loadings. We were especially interested how the excluded volume effect of the nanofiber particles and their orientation (specifically orientational anisotropy) in the matrix influence elastomeric properties of the network. Distribution functions of the end-to-end distances of polymer chains for both unfilled and filled networks were calculated. Effects of nanofiber reinforcements with varying fiber radii and fiber volume fractions were investigated. We have found that the presence of nanofibers significantly increase the non-Gaussian behavior of polymer chains in the composite. The anisotropic effects of the nanofibers on mechanical properties of polymeric composites were studied as a function of their relative orientation to the direction of deformation. The modulus (reduced nominal stress per unit strain) was calculated from the distribution of end-to-end distances of polymer chains using the Mark–Curro method. Relatively small amount of nanofibers was found to increase the normalized moduli of the composite. Our results are quite in satisfactory qualitative agreement with experimental data reported in the literature. This shows that computer simulations provide a powerful tool in predicting physical properties of composite materials. 相似文献