Carboxymethylated chitosan (CMCt) hydrogels were synthesized by γ-ray radiation-induced crosslinking in the presence of acids or polyfunctional monomers. Compared with that of CMCt hydrogels synthesized without additives, the gel fraction was improved and the gelation dose was decreased obviously after incorporating acids or polyfunctional monomers into CMCt hydrogels. The diffusion behavior of water in the CMCt gels prepared at different conditions was Fickian diffusion, and the swelling of the CMCt gels displayed characteristic pH sensitivity, which was analyzed by fluorescence molecular probes. Preliminary mechanism of radiation-induced crosslinking of CMCt in the presence of acids or polyfunctional monomers was discussed based on the FTIR and sol-gel analysis. Furthermore, it was found that CMCt hydrogels were hydrodegradable with high temperature (>60 °C), and incorporating polyfunctional monomers into the CMCt hydrogels also could improve the thermal stability of the CMCt hydrogels obviously. 相似文献
The complexation of Cu2+ ions with an alternating copolymer of maleic acid (MAc) and ethylene in aqueous solution was followed through turbidimetry and absorption spectrophotometry as a function of the polymer concentration and the metal ion-to-polymer molar ratio, r. The introduction of Cu2+ ions was performed in aqueous solution through neutralization of the polyacid with Cu(OH)2 powder. A gelation window between homogeneous and phase-separated solutions was observed in the phase diagram of the polymer/Cu2+ mixture and the viscoelastic properties of the hydrogels were evaluated through rheology measurements. It is found that the stiffness of the hydrogels can be tuned by the polymer concentration and the mixing ratio r. Moreover, the stiffness of the hydrogels increases substantially with time. In fact, this time evolution may be as long as one month or longer if the composition of the aqueous solution is close to the gelation threshold. The gelation properties can be qualitatively explained from the possible formation of binuclear polymer/Cu2+ complexes in aqueous solutions, as indicated from the absorption spectroscopy results. 相似文献
The influence of organic and inorganic acids on chitosan/glycerophosphate (CS/GP) hydrogel has been investigated by dissolving
chitosan in different acids. The results of gelation showed that all of the chitosan dissolved in monovalent acid solutions
(i.e., formic, acetic, propionic, butyric, isobutyric, lactic, nitric, hydrochloric, and chloroacetic acid), when neutralized
by GP solution, could transform into hydrogel after 2–5 min at 37 °C, while those dissolved in multivalent acids failed in
gel formation. The inner structures of CS/GP hydrogels prepared with monovalent acids depended on the ionic strength and chain
length of acids. Morphological examination by scanning electron microphotography demonstrated that large pores occurred during
the gel-forming process, and the aperture size was also related to different acids. The cytotoxicity studies indicated that
CS/GP systems prepared by dissolving chitosan in tested acids except chloroacetic acid were nontoxic to mouse embryonic fibroblasts
and Hela cells. 相似文献
Supramolecular hydrogels have been prepared on the basis of polymer inclusion complex (PIC) formation between poly(ethylene glycol) (PEG)-modified chitosans and alpha-cyclodextrin (alpha-CD). A series of PEG-modified chitosans were synthesized by coupling reactions between chitosan and monocarboxylated PEG using water-soluble carbodiimide (EDC) as coupling agent. With simple mixing, the resultant supramolecular assembly of the polymers and alpha-CD molecules led to hydrogel formation in aqueous media. The supramolecular structure of the PIC hydrogels was confirmed by differential scanning calorimetry (DSC), X-ray diffraction, and (13)C cross-polarized/magic-angle spinning (CP/MAS) NMR characterization. The PEG side-chains on the chitosan backbones were found to form inclusion complexes (ICs) with alpha-CD molecules, resulting in the formation of channel-type crystalline micro-domains. The IC domains play an important role in holding together hydrated chitosan chains as physical junctions. The gelation property was affected by several factors including the PEG content in the polymers, the solution concentration, the mixing ratio of host and guest molecules, temperature, pH, etc. All the hydrogels in acidic conditions exhibited thermo-reversible gel-sol transitions under appropriate conditions of mixing ratio and PEG content in the mixing process. The transitions were induced by supramolecular association and dissociation. These supramolecular hydrogels were found to have phase-separated structures that consist of hydrophobic crystalline PIC domains, which were formed by the host-guest interaction between alpha-CD and PEG, and hydrated chitosan matrices below the pK(a).The formation of inclusion complexes between alpha-cyclodextrin and PEG-modified chitosan leads to the formation of hydrogels that can undergo thermo-reversible supramolecular dissociation. 相似文献
Based on the preparation of biocompatible polysaccharide-based hydrogels with stimuli-responsive properties by the copolymerization of maleilated carboxymethyl chitosan with N-isopropylacrylamide, novel magnetic hybrid hydrogels were fabricated by the in situ embedding of magnetic iron oxide nanoparticles into the porous hydrogel networks. Scanning electron microscopy (SEM) and thermogravimetric (TG) analyses showed that the size, morphology, and content of the iron oxide nanoparticles formed could be modulated by controlling the amount of maleilated carboxymethyl chitosan. As confirmed by X-ray diffractometry (XRD), equilibrium swelling ratio, and differential scanning calorimetry (DSC) measurements, the embedding process did not induce a phase change of the magnetic iron oxide nanoparticles, and the resultant hybrid hydrogels could retain the pH- and temperature-responsive characteristics of their hydrogel precursors. By investigating the partition coefficients of bovine serum albumin as a model protein, this magnetic hydrogel material was found to hold a potential application in magnetically assisted bioseparation. 相似文献
This work investigates the polyanion initiated gelation process in fabricating chitosan-TPP (tripolyphosphate) nanoparticles in the size range of 100-250 nm intended to be used as carriers for the delivery of gene or protein macromolecules. It demonstrates that ionic gelation of cationic chitosan molecules offers a flexible and easily controllable process for systematically and predictably manipulating particle size and surface charge which are important properties in determining gene transfection efficacy if the nanoparticles are used as non-viral vectors for gene delivery, or as delivery carriers for protein molecules. Variations in chitosan molecular weight, chitosan concentration, chitosan to TPP weight ratio and solution pH value were examined systematically for their effects on nanoparticle size, intensity of surface charge, and tendency of particle aggregation so as to enable speedy fabrication of chitosan nanoparticles with predetermined properties. The chitosan-TPP nanoparticles exhibited a high positive surface charge across a wide pH range, and the isoelectric point (IEP) of the nanoparticles was found to be at pH 9.0. Detailed imaging analysis of the particle morphology revealed that the nanoparticles possess typical shapes of polyhedrons (e.g., pentagon and hexagon), indicating a similar crystallisation mechanism during the particle formation and growth process. This study demonstrates that systematic design and modulation of the surface charge and particle size of chitosan-TPP nanoparticles can be readily achieved with the right control of critical processing parameters, especially the chitosan to TPP weight ratio. 相似文献
Network microstructures of polyacrylamide (PAAm) hydrogels were investigated by static light scattering measurements. The gels were prepared by free‐radical crosslinking polymerization of acrylamide (AAm). To suppress the degree of gel inhomogeneity, the crosslinker reactivity during gelation was controlled by decreasing its availability in the reaction system. Our first approach was the addition of the crosslinker N,N′‐methylenebis(acrylamide) (BAAm) in one or three portions during the course of the gelation reactions. As a second approach, a slightly water soluble crosslinker, namely ethylene glycol dimethacrylate (EGDM) was used as a crosslinker in AAm polymerization. Due to the low water solubility of EGDM, EGDM phase in the gelation system act as a reservoir of crosslinker so that the crosslinker can be supplied continuously to the aqueous reaction zone during the course of gelation. It was found that the delayed crosslinker addition technique further increases the degree of inhomogeneity of PAAm hydrogels. The results were explained with increasing viscosity of the reaction solution at the time of the crosslinker addition so that the crosslinking reactions are limited to local regions in the reaction system. The second approach, namely use of the slightly water soluble crosslinker EGDM significantly increases the degree of structural homogeneity of PAAm hydrogels. 相似文献
Gelation time and degradation rate of thermally-sensitive aqueous solutions of chitosan/Gp (glycerophosphate disodium salt)
have been studied. The effects of different parameters such as Gp salt concentration, solution temperature, degree of deacetylation
of chitosan (DDA) and drug loading on the gelation time have been investigated. Gravimetric analysis, gel permeation chromatography
and FTIR spectrophotometry were used to investigate the influence of the DDA and concentration of chitosan solution on hydrogel
degradation. The presented results indicated that gelation time decreases by increasing Gp salt concentration, temperature,
concentration and DDA of chitosan solutions, while drug loading has no significant effect on gelation time. Slower degradation
profile was recorded for hydrogel with the higher DDA and concentration of chitosan in the primary solution. FTIR studies
indicated that the chemical structure of chitosan macromolecules does not change significantly during the degradation. It
could be concluded that biodegradation of chitosan hydrogel occurred via its surfaces. 相似文献
Strong injectable chitosan thermosensitive hydrogels can be created, without chemical modification, by combining sodium hydrogen carbonate with another weak base, namely, beta‐glycerophosphate (BGP) or phosphate buffer (PB). Here the influence of gelling agent concentration on the mechanical properties, gelation kinetics, osmolality, swelling, and compatibility for cell encapsulation, is studied in order to find the most optimal formulations and demonstrate their potential for cell therapy and tissue engineering. The new formulations present up to a 50‐fold increase of the Young's modulus after gelation compared with conventional chitosan‐BGP hydrogels, while reducing the ionic strength to the level of iso‐osmolality. Increasing PB concentration accelerates gelation but reduces the mechanical properties. Increasing BGP also has this effect, but to a lesser extent. Cells can be easily encapsulated by mixing the cell suspension within the hydrogel solution at room temperature, prior to rapid gelation at body temperature. After encapsulation, L929 mouse fibroblasts are homogeneously distributed within scaffolds and present a strongly increased viability and growth, when compared with conventional chitosan‐BGP hydrogels. Two particularly promising formulations are evaluated with human mesenchymal stem cells. Their viability and metabolic activity are maintained over 7 d in vitro.
In this study, uniform-sized pH-sensitive quaternized chitosan microsphere was prepared by combining Shirasu porous glass (SPG) membrane emulsification technique and a novel thermal-gelation method. In this preparation process, the mixture of quaternized chitosan solution and alpha-beta-glycerophosphate (alpha-beta-GP) was used as water phase and dispersed in oil phase to form uniform W/O emulsion by SPG membrane emulsification technique. The droplets solidified into microspheres at 37 degrees C by thermal-gelation method. The whole process was simple and mild. The influence of process conditions on the property of prepared microspheres was investigated and the optimized preparation condition was obtained. As a result, the coefficient of variation (C.V.) of obtained microspheres diameters was below 15%. The obtained microsphere had porous structure and showed apparent pH-sensitivity. It dissolved rapidly in acid solution (pH 5) and kept stable in neutral solution (pH 7.4). The pH-sensitivity of microspheres also affected its drug release behavior. Bovine serum albumin (BSA) as a model drug was encapsulated in microspheres, and it was released rapidly in acid solution and slowly in neutral medium. The novel quaternized chitosan microspheres with pH-sensitivity can be used as drug delivery system in the biomedical field, such as tumor-targeted drug carrier. 相似文献
Two chitosan hydrogels (prepared by NaOH neutralization and by polyphosphate ionotropic gelation) have been tested in the
dry state for Pd(II) and Pt(IV) sorption at pH 2. Similar sorption isotherms with maximum sorption capacities close to 190 mg Pd g−1 and 235 mg Pt g−1 were achieved. The sorption mechanism involves electrostatic attraction of the chloro-anionic species onto protonated amine
groups; the drastic decrease of sorption capacity with the addition of chloride ions supports this hypothesis. SEM-EDAX analysis
suggests that sorption proceeds, in kinetic terms, through a shrinking core mechanism. Metal ions can diffuse throughout all
the sorbent volume. The main differences between the sorbents are revealed by kinetics. The hydrogels prepared by ionotropic
gelation in polyphosphate (C-PPh) allows reaching equilibrium much faster than the hydrogels prepared by the neutralization
process (C-NaOH). While for C-PPh sorbent the chemical reaction rate seems to control sorption profiles, in the case of C-NaOH
a combination of mechanisms including intraparticle diffusion resistance controls uptake kinetics. Metal desorption from loaded
sorbents is possible using thiourea alone or in association with HCl solutions. The recycling of the sorbents is possible
but for a limited number of cycles. 相似文献
In this study, various surfactants were added to control the gelation time of silk fibroin (SF) aqueous solution. The gelation behaviors of SF aqueous solution in the presence of surfactant were investigated with attenuated total reflectance infrared, SEM, and a viscometer. When surfactants other than chitooligosaccharide were added into an SF aqueous solution, the gelation time of the solution was decreased under the fixed conditions. Particularly, anionic surfactant was found to be more effective than non-ionic and cationic surfactants in accelerating the gelation of SF. In addition, the conformational changes of SF hydrogel with or without surfactant were investigated in a time-resolved manner using infrared spectroscopy. Conformational transitions of SF nanofibers from random coil to β-sheet forms were strongly dependent on the inherent properties of surfactant, and on the different interactions between surfactant and SF molecules in aqueous solution. This approach to controlling the gelation of SF aqueous solution by the surfactant, and to monitoring their conformational changes on a real-time scale, may be critical in the design and tailoring of SF hydrogels useful for biomedical applications. 相似文献
This article highlights the aggregation behaviour of potential low molecular weight hydrogelators on attracting surfaces. Our goal was the development of a method, which enables the finding of new hydrogelators that are not easily recognizable as such because they only form instable or no hydrogels in aqueous solution. To this end, a series of negatively charges azo-dyes was synthesized and positive charged glass slides were immersed into their aqueous solutions. All dyes showed supramolecular organization and significant concentration on the attracting glass surface. Microscopic investigations mostly revealed the formation of crystals. However, one compound, (1-(2-n-octylphenylazo)-2-hydroxy-6-naphthalenesulphonate, selectively formed a hydrogel on the surface whereas it does not gel in aqueous solution. This reveals the hydrogel as the stable form of this compound under equilibrium conditions. This method of surface-induced hydrogelation might facilitate the identification of new hydrogelators. Further more, it might also allow the mimicking of surface gelation as a process of biological relevance. 相似文献
The microstructure of complex and composite poly(vinyl alcohol) (PVA) cryogels containing water-soluble chitosan hydrochloride (ChHC) of dispersed particles of water-insoluble chitosan base (Ch), respectively, has been studied by optical microscopy and attenuated total reflection FTIR spectroscopy. The macroporous morphology of cryogels has been studied using preparations in the form of thin (~10 μm) sections and discs 1 mm thick. The introduction of non-gelling additives (NaCl and ChHC) into an initial PVA solution causes significant changes in the size and shapes of macropores in the complex cryogels formed by freezing–defrosting, as compared with the pores in the samples obtained under the same conditions without additives. The reasons for the changes are the process of phase segregation and the influence of low- and high-molecular-weight electrolytes on crystallization of ice, which plays the role of a porogen upon cryotropic gelation of aqueous PVA solutions. As a result of an alkaline treatment of the complex cryogels, which transforms ChHC into Ch, microcoagulation of chitosan yields discrete, almost spherical, particles with sizes of about 1–5 μm. IR spectral studies have shown that concentration gradients of the gelling and nongelling polymers arise along the thickness of the gel discs, with PVA concentration prevailing near the lower surface and ChHC or Ch concentration dominating near the upper surface of the disc. 相似文献
A series of thermo/pH sensitive N‐succinyl hydroxybutyl chitosan (NSHBC) hydrogels with different substitution degrees of succinyl are prepared for drug delivery. Rheology analysis shows that the gelation temperature of NSHBC hydrogels is 3.8 °C higher than that of hydroxybutyl chitosan (HBC) hydrogels. A model drug bovine serum albumin (BSA) is successfully loaded and released. NSHBC hydrogels show excellent pH sensitivity drug release behaviors. After incubation for 24 h, 93.7% of BSA is released from NSHBC hydrogels in phosphate buffer saline (PBS) (pH 7.4), which is significantly greater than that of 24.6% at pH 3.0. In contrast, the release rate of BSA from HBC is about 70.0% at pH 3.0 and 7.4. Thus, these novel hydrogels have the prominent merits of high adaptability to soluble drugs and pH sensitivity triggered release, indicating that NSHBC hydrogels have promising applications in oral drug delivery. 相似文献
A new type of multistimuli‐responsive hydrogels cross‐linked by metal ions and biopolymers is reported. By mixing the biopolymer chitosan (CS) with a variety of metal ions at the appropriate pH values, we obtained a series of transparent and stable hydrogels within a few seconds through supramolecular complexation. In particular, the CS–Ag hydrogel was chosen as the model and the gelation mechanism was revealed by various measurements. It was found that the facile association of Ag+ ions with amino and hydroxy groups in CS chains promoted rapid gel‐network formation. Interestingly, the CS–Ag hydrogel exhibits sharp phase transitions in response to multiple external stimuli, including pH value, chemical redox reactions, cations, anions, and neutral species. Furthermore, this soft matter showed a remarkable moldability to form shape‐persistent, free‐standing objects by a fast in situ gelation procedure. 相似文献