Mucoadhesive and elastic films based on blends of chitosan and hydroxyethylcellulose

Mucoadhesive polymeric films have been prepared based on blends of chitosan and hydroxyethylcellulose. The blends have been characterized by IR spectroscopy, DSC, WAXD, TGA, SEM, and mechanical testing. It is demonstrated that the mechanical properties of chitosan are improved significantly upon blending with hydroxyethylcellulose. An increase in hydroxyethylcellulose content in the blends makes the materials more elastic. The thermal treatment of the blends at 100 degrees C leads to partial cross-linking of the polymers and formation of water-insoluble but swellable materials. The adhesion of the films towards porcine buccal mucosa decreases with increasing hydroxyethylcellulose content in the blends.     

Synthesis and characterization of thermoresponsive hydrogels cross-linked with chitosan

Hydrogels composed of N-isopropylacrylamide (NIPAAm) and acrylic acid (AAc) were prepared by redox polymerization with degradable chitosan cross-linkers. Chitosan degradable cross-linkers were synthesized by the acrylation of the amine groups of glucosamine units within chitosan and characterized with ¹H NMR. With the chitosan cross-linkers, loosely cross-linked poly(N-isopropylacryamideco-acrylic acid) [P(NIPAAm-co-AAc)] hydrogels were prepared, and their phase transition behavior, lower critical solution temperature (LCST), water content and degradation properties were investigated. The chitosan cross-linked P(NIPAAm-co-AAc) hydrogels were pliable and transparent at room temperature. The LCST could be adjusted at 32∼39°C by alternating the feed ratio. Swelling was influenced by NIPAAm/AAc monomer ratio, cross-linking density, swelling media, and temperature. All hydrogels with different feeding ratios contained more than 95% water at 25°C in the ultra pure water and phosphate-buffered saline (PBS, pH = 7.4 ± 0.1), and had a prospective swelling in the simulated gastric fluids (SGF, pH = 1.2) > 72.54%. In degradation studies, breakdown of the chitosan cross-linked P(NIPAAm-co-AAc) hydrogels was dependent on the cross-linking density. The chitosan cross-linked P(NIPAAm-co-AAc) hydrogels which can be tailored to create environmentally-responsive artificial extracellular materials have great potential for future use.      

Structural and dynamical properties of aqueous mixtures of pectin and chitosan

In this study phase separation, structure, and dynamics of aqueous pectin-chitosan mixtures of different ratios and a pure aqueous pectin sample have been investigated under various conditions by turbidimetry, SANS and dynamic light scattering (DLS). Only the mixture with r = 0.75 gelled upon decreasing the temperature ((r ≡ m_pectin/(m_pectin + m_chitosan), where m denotes the mass of the considered component). The pure pectin sample (r = 1) did not gel and the decrease in temperature seemed to promote phase separation. The addition of chitosan reduced the tendency of pectin to phase separate in the mixtures of pectin and chitosan. The general trend when cooling the samples was that the turbidity and the growth of the turbidity became more pronounced as the amount of pectin in the mixture was increased. The wavelength dependence of the turbidity indicated a change of the conformation of pectin chains from an extended form to a more compact structure in pectin solutions without chitosan as the temperature decreased. This was not observed for the mixture of pectin and chitosan. SANS measurements revealed excess scattered intensity in the low wave vector area with the strongest upturn for the pure pectin sample (r = 1). DLS experiments showed longer slow relaxation times after a temperature quench for all samples, with the most pronounced effect for the mixture of pectin and chitosan with r = 0.75. The synergism between pectin and chitosan at high pectin contents (r = 0.75) generated large association complexes over time.     

Fabrication and drug release behavior of ionically cross-linked chitosan microspheres

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Adsorptive removal of Cr(III) from aqueous solution using tripolyphosphate cross-linked chitosan beads

Chitosan tripolyphosphate (CTPP) beads were prepared at two different cross-linking densities and adsorption of Cr(III) onto it were studied as a function of different operational parameters such as solution pH, equilibration time and initial Cr(III) ion concentration. Higher cross-linked beads were found to have more adsorption capacity at all the experimental pH employed (pH = 3–5), whereas adsorption capacity is found to increase with increase in pH. Adsorption data were analyzed using Langmuir and Freundlich isotherm models. Langmuir model is found be more suitable to explain the experimental results with a monolayer adsorption capacity of 469.5 mg/g. Among the kinetic models used, pseudo-second order kinetic model could best describe the adsorption process. Competition experiments done in presence of Na(I), Mg(II), Ca(II), Al(III) and Fe(III) revealed that, except in the case of Al(III), adsorption of Cr(III) is not significantly affected by the presence of foreign cations. NaCl is found to be a suitable leaching agent for the desorption of adsorbed Cr(III) from CTPP beads. FTIR spectroscopic investigations confirmed that phosphate groups are the principal binding site responsible for the sorption of Cr(III) onto CTPP beads.     

Sorption behaviour of fluoride on carboxylated cross-linked chitosan beads

Carboxylated cross-linked chitosan beads (CCB) showed a significant defluoridation capacity (DC) of 1385 mgF(-)/kg than the raw chitosan beads (CB) which displayed only 52 mgF(-)/kg. Sorption experiments were performed by varying contact time, pH, presence of co-anions and temperature. The nature and morphology of the sorbent were discussed using FTIR and SEM with EDAX analysis. The stability of the beads in solution was explained in terms of swelling ratio of the beads. The fluoride uptake onto CCB obeys both Freundlich and Langmuir isotherms. Thermodynamic studies revealed that the nature of fluoride sorption is spontaneous and endothermic. Sorption kinetics is mainly controlled by pseudo-second-order and intraparticle diffusion models. 0.1M HCl was identified as the best eluent. The suitability of CCB at field conditions has been tested with field sample collected from a nearby fluoride-endemic area.     

Compatibility of Bombyx mori chitosan with pectin and Na-carboxymethyl cellulose in solutions

Solutions and blends of Bombyx mori chitosan with pectin and Na-carboxymethyl cellulose were studied by viscometry. The intermolecular interaction parameters and the parameter of the distance of hydrodynamic interaction of a pair of separate molecules were calculated, and the polymer compatibility was assessed.     

Chromium (VI) ion adsorption features of chitosan film and its chitosan/zeolite conjugate 13X film

This research evaluated the importance of the adsorption properties of chitosan a chitosan/zeolite conjugate film for the removal of Cr(VI) ions from solutions in the 5-260 mg/L concentration range, when the pH was adjusted to 4.0 and 6.0. The uptake capacities of the films formed by chitosan and by the chitosan/zeolite conjugate were calculated by mass balance. The equilibrium isotherms were fitted to the Langmuir, Freundlich and Redlich-Peterson models. The chitosan film seems to be a good sorbent for Cr(VI) at pH 4, but its physical instability suggests the need for a more resilient support. Due to this fact zeolite was added to the chitosan matrix in solution and a chitosan/zeolite (CS/Zeo) film was thus formed. The solubility of the film and the characterization of the different matrices by FTIR, TGA and X-Ray showed that a cross-linked structure was formed between the chitosan and zeolite and the solubility of the film increased. In this study, the low manufacturing cost of the CS/Zeo matrix, the good uptake of Cr(VI) at acidic pH (17.28 mg/g) and the non desorption of Cr(VI) from the film in water suggests this combination should be tested in industrial environment.     

Adsorption behavior of mercury and precious metals on cross-linked chitosan and the removal of ultratrace amounts of mercury in concentrated hydrochloric acid by a column treatment with cross-linked chitosan.

Cross-linked chitosan was synthesized with chitosan and ethylene glycol diglycidyl ether. The adsorption behavior of trace amounts of metal ions on the cross-linked chitosan was systematically examined by packing it in a mini-column, passing a metal solution through it and measuring metal ions in the effluent by ICP-MS. The cross-linked chitosan adsorbed mercury and precious metals (Pd, Pt, and Au) at pH values from acidic to neutral. Especially, mercury in concentrated hydrochloric acids could be adsorbed on cross-linked chitosan quantitatively by an anion-exchange mechanism in the form of a stable chloride complex. This method was applied to the removal of mercury from commercially available hydrochloric acid; more than 97% of mercury was removed, and the residual mercury in the hydrochloric acid (Grade: for trace analysis) was found to be 0.15 ppb. Mercury adsorbed on the cross-linked chitosan could be easily desorbed with an eluent containing I M hydrochloric acid and 0.05 M thiourea. The thus-refreshed cross-linked chitosan could be repeatedly used for the removal of mercury in hydrochloric acid.     

Surface fabrication of hollow microspheres from N-methylated chitosan cross-linked with glutaraldehyde

We have successfully prepared biocompatible and biodegradable hollow microspheres with sizes between 2 and 5 mum using cyclohexane droplets as a template and the N-methylated chitosan (NMC) cross-linked with glutaraldehyde (GA) as the shell. The structure, morphology, and formation process of the hollow microspheres were characterized by FT-IR, (1)H and (13)C NMR, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results revealed that the microspheres exhibited a very smooth and hollow structure. This work confirmed that the hollow microspheres were accomplished by fabricating on the basis of chemical cross-linking on the surface of the emulsion droplets and by removing cyclohexane as core. The results from SEM and TEM indicated that the emulsion droplets covered with cross-linked NMC in the oil-in-water system aggregated together to form a precipitate of microspheres by coagulating with acetone. Moreover, the cross-linked NMC on the surface of the microspheres continuously cured to form the tight shell, whereas the inner area became a cavity with increase of the aging time, leading to the hollow microspheres. In addition, an anti-infective drug, ofloxacin (Floxin), encapsulated in the microspheres more rapidly released to reach 90 wt % at pH 7.4 within 8 h than at pH 1.2.     

Enhanced functional properties of chitosan films cross-linked by biosourced dicarboxylic acids

Chitosan-based films were developed using different biosourced dicarboxylic acid solutions (succinic acid, adipic acid, suberic acid and sebacic acid). The effect of incorporating these nontoxic solutions on water vapor barrier, tensile and antimicrobial properties of chitosan films was evaluated. Fourier Transform Infrared (FTIR) and cross polarization magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR) analyses were also performed to investigate functional groups interactions between chitosan and dicarboxylic acids. Acetic acid-chitosan films showed significantly higher water vapor permeability (WVP) and lower tensile strength (TS) and elongation at break (%E) than dicarboxylic acid-prepared films (p < 0.05). Using either adipic acid or suberic acid solutions to fabricate chitosan films reduced WVP by 85% and enhanced TS by 21 to 27% and %E by more than 60% when compared with the acetic acid-prepared films. Chitosan films modified with either adipic acid or suberic acid exhibited antimicrobial activity against all tested microorganisms.     

Solid-phase modification of chitosan,pectin, and arabinogalactan with poorly soluble herbicide chlorsulfuron

The chemical modification of chitosan, pectin, and arabinogalactan with poorly soluble herbicide chlorsulfuron under mechanical effect is studied. It is shown that the mechanical stress on polysaccharides and herbicide provokes conformational and configurational transformations and disordering in biopolymer macromolecules as well as an increase in the concentration of defects in the crystalline phase of the polysaccharides and herbicide. The change in the conformational state of the polysaccharides under shock-shear impacts gives rise to intermolecular complexes stabilized by hydrogen bonds.     

Degradation of covalently cross-linked carboxymethyl chitosan and its potential application for peripheral nerve regeneration

Chitosan has been widely used in a variety of biomedical applications including peripheral nerve repair because of its excellent mechanical properties and biocompatibility. However, chitosan itself has a very slow degradation rate, and its molecules degrade in an uncontrollable manner. We hypothesized that the cross-linking of carboxymethyl chitosan (CM-chitosan), which is soluble in water, would result in a higher degradation rate in lysozyme solutions, while retaining its excellent mechanical properties and nerve cell affinity. In this study, we characterized the constructed matrix formed using a combination of carboxymethylation of chitosan chains and thereafter 1-ethyl-3(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) cross-linking. Specifically, after EDC cross-linking, the hydrophilicity and elastic modulus of the CM-chitosan films decreased. These changes are beneficial in the application of chitosan derivatives for nerve repair. The porous conduits degraded to 30% in weight during eight weeks of incubation in lysozyme solution (pH 7.4, 37 °C). In addition, the cross-linked CM-chitosan films enhanced the spread of Neuro-2a cells and provided a good proliferation substratum for Neuro-2a cells, as compared to chitosan films. Therefore, cross-linking with EDC is a promising way to modify chitosan derivatives for peripheral nerve regeneration.     

Preparation of a cross-linked gelatin/bacteriorhodopsin film and its photochromic properties

Bacteriorhodopsin (BR) is a photochromic membrane protein isolated from a strain of halobacteria.Embedment of BR into a polymeric matrix enables the application of the photoactive protein as an optical material.In this work,a chemically crosslinked BR/gelatin film was prepared.The cross-linked film was found to be highly stable even under extreme alkaline or detergent circumstance while BR maintained its bioactivity.The treatments of base and detergents also led to dramatic prolongation of the lifetime of M...     

Anti-microbial activity and film characterization of thiazolidinone derivatives of chitosan

Thiazolidinone derivatives (TDCs) were prepared by converting chitosan into chitosan's Schiff's bases (CSBs), followed by treatment with mercaptoacetic acid. Both CSBs and TDCs were tested for antimicrobial activity against four different bacteria. All TDCs showed comparatively better anti-microbial activity without much affecting basic physical properties of chitosan such as film-forming capacity, tensile strength, etc. This indicates that chitosan derivatives with a thiazolidinone moiety might be a better material for wound dressing.     

Preparation of enzymatically cross-linked sulfated chitosan hydrogel and its potential application in thick tissue engineering

For the requirement of preliminary vascularization, the scaffolds for thick tissue engineering should possess not only good cell affinity, but also anticoagulant ability. In this paper, an enzymatically crosslinked hydrogel scaffold based on sulfated chitosan (SCTS) was prepared. Firstly, sulfated chitosan-hydroxyphenylpionic acid (SCTS-HPA) conjugate was synthesized, and its structure was identified by FITR and ¹H NMR. And then an enzymatically crosslinked hydrogel was prepared in the presence of horseradish peroxidase (HRP) and hydrogen peroxide (H₂O₂). The gelation time, mechanical property, morphology and cytotoxicity to human umbilical vein endothelial cells (HUVECs) of the hydrogel was evaluated in vitro, the tissue compatibility of SCTS scaffold was studied in vivo. The results showed that the gelation time, mechanical property, morphology of the dehydrated hydrogel could be controlled by the HRP and H₂O₂ concentration. The cytotoxicity test showed that the hydrogel extracts had no cytotoxicity to HUVECs. The in vivo assay indicated that SCTS-HPA scaffold showed good tissue compatibility, and no thrombus formation. All these results indicated that the SCTS-HPA scaffold could be used as thick tissue engineering scaffold.     

甲壳胺药膜的控制释放研究

以阿司匹林为模型药物研究了小分子药物在甲壳腹膜中的释放行为，结果表明释放是扩散控制的，与膜厚、介质pH值，膜交联度及膜分散性密切相关。改变这些参数可达到比较恒定的延长释放和不同的给药途径。