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1.
Comb‐type graft hydrogels, composed of chitosan and poly(N‐isopropylacrylamide) (PNIPAAm), were prepared to manifest rapid temperature and pH sensitivity. Instead of directly grafting the NIPAAm monomer onto the chitosan chain, semitelechelic PNIPAAm with carboxyl end group was synthesized by radical polymerization using 3‐mercaptopropionic acid as the chain‐transfer agent, and was grafted onto chitosan having amino groups. The comb‐type hydrogels were prepared with two different graft yields and grafting regions, such as surface‐ and bulk‐grafting, and then compared with a chitosan hydrogel. The synthesis of telechelic PNIPAAm and the formation of amide group were confirmed by using FTIR spectroscopy and gel permeation chromatography. Results from the water state and thermal stability revealed that the introduction of the PNIPAAm side chain disturbed the ordered arrangement of the chitosan molecule, resulting in an increase in the equilibrium water content. Comb‐type graft hydrogels showed rapid temperature and pH sensitivity because of the free‐ended PNIPAAm attached to the chitosan main chain and the chitosan amino group itself, respectively. In particular, the surface graft hydrogel maintained its dimension at low pH, although the chitosan main chain was not crosslinked, whereas chitosan and bulk graft hydrogel were dissolved as a result of the coating effect of pH‐independent PNIPAAm. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2612–2620, 2004  相似文献   

2.
Comb‐type grafted hydrogels composed of polyacrylamide (PAAm) and chitosan (CT) were prepared and used for DNA adsorption. Instead of direct grafting of the acrylamide monomer onto the CT chain, semitelechelic PAAm with carboxylic acid end groups (PAAm–COOH) was synthesized by free‐radical polymerization with mercaptoacetic acid as the chain‐transfer agent, and it was grafted onto CT with amino groups. The synthesis of telechelic PAAm–COOH and the formation of comb‐type grafted hydrogels were confirmed by attenuated total reflectance/Fourier transform infrared spectroscopy and scanning electron microscopy measurements. The prepared comb‐type grafted hydrogels were used as sorbents in DNA adsorption experiments conducted at +4°C in a tris(hydroxymethyl)aminomethane/ethylenediaminetetraacetic acid solution of pH 7.4. DNA adsorption capacities as high as 2.0 × 103 μg of DNA/g of dry gel could be achieved by the comb‐type hydrogels with higher PAAm contents. This value was approximately 6 times higher than that of CT alone. In addition, the comb‐type hydrogels showed a high adsorption/desorption rate depending on the PAAm content in the hydrogel. As a result, these comb‐type hydrogels carrying higher amounts of DNA may be considered good candidates for achieving higher removal rates for anti‐DNA antibodies and for effective gene therapy systems. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

3.
In this study, poly(N,N‐dimethylacrylamide) grafted chitosan (PDMAAm‐g‐CT) hydrogels were prepared for deoxyribonucleic acid (DNA) adsorption. Instead of directly grafting the N,N‐dimethylacrylamide (DMAAm) monomer onto the chitosan (CT) chains, poly(N,N‐dimethylacrylamide) with carboxylic acid end group (PDMAAm‐COOH) was firstly synthesized by free‐radical polymerization using mercaptoacetic acid (MAAc) as the chain‐transfer agent and then grafted onto the CT having amino groups. The synthesis of PDMAAm‐COOH and its grafting onto the CT chains were confirmed by attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy. From gel permeation chromatography measurements, the number‐average molecular weight (M n) and polydispersity index of PDMAAm‐COOH were found as 2400 g/mol and 2.3, respectively. The PDMAAm‐g‐CT hydrogels were utilized as the adsorbents in DNA adsorption experiments conducted at +4°C in a trisEDTA solution of pH 7.4. The hydrogels produced with higher PDMAAm‐COOH content exhibited higher DNA adsorption capacity. The DNA adsorption capacity up to 4620 μg DNA/g dry gel could be achieved with the PDMAAm‐g‐CT hydrogels prepared in 80.0 wt % PDMAAm‐COOH feed concentration. This value is approximately seven times higher than that of CT alone. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

4.
Graft copolymerization of epoxy‐terminated poly(dimethylsiloxane) (PDMS) onto chitosan was reacted without using a catalyst. pH‐sensitive hydrogels were obtained that are based on two different components: a natural polymer and a synthetic polymer. These PDMS substitutents provide the basis for hydrophobic interactions that contribute to the formation of hydrogels. Various graft hydrogels were prepared from different weight ratios of chitosan and PDMS. Swelling behavior of these hydrogels was studied by immersion of the gels in various buffer solution. Photocrosslinked hydrogels exhibited a high equilibrium water content (EWC). Particularly, the sample CP31 of the highest chitosan–PDMS weight ratio showed the highest EWC in time‐dependent, temperature‐dependent, and pH‐dependent swelling behavior. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2661–2666, 2002  相似文献   

5.
Polyelectrolyte complex (PEC) hydrogels composed of chitosan as a cationic polyelectrolyte and poly (γ‐glutamic acid) (γ‐PGA) as an anionic polyelectrolyte were prepared from PEC dispersions based on a chitosan solution to which different amounts of γ‐PGA solutions were added to charge equivalency. The chemical structures of the PEC hydrogels were investigated by Fourier transform infrared spectroscopy. The physical properties, fixed charge concentration, crystallinity, mechanical properties, micromorphology, and swelling properties of the PEC hydrogels were also investigated. The total fixed charge concentration of the PEC hydrogels varied as a function of pH on the pK intervals between chitosan (pK = 6.5) and γ‐PGA (pK = 2.27). The isoelectric points (IEP) were shifted to a lower pH with a higher weight ratio of γ‐PGA to chitosan. The elastic modulus was decreased with the weight ratio increasing from 0 : 1 to 1 : 1 (γ‐PGA/chitosan) by ionic crosslinking between the amino groups of chitosan and the carboxyl groups of γ‐PGA. The results of the swelling study showed that the swelling properties of PEC hydrogels were more affected by the change in the elastic restoring force than by the change in the fixed charge concentration depending on the pH. Also, the cytotoxicity of the PEC hydrogels was investigated using normal human dermal fibroblast (NHDF) cell lines, and the results showed the PEC hydrogels were not toxic. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:386–394, 2007  相似文献   

6.
Multifunctional hydrogels based on chitosan–quercetin (CHITQ) conjugate are prepared by a thermo‐induced radical procedure in the presence of N‐isopropylacrylamide (NIPAAm), acrylamide (AAm), and N,N′‐methylenebis(acrylamide) (MEBA). At first, quercetin (Q) is grafted onto chitosan backbone with a functionalization degree of 275 mg of Q per gram of conjugate, as calculated by 1H‐NMR analyses to impart antioxidant properties to the polysaccharide. Then, a pH and temperature sensitive hydrogel was obtained by involving CHITQ and NIPAAm in the polymerization reaction. The accessibility of phenolic moieties is modified in response to the hydrogel swelling/deswelling, as confirmed by antioxidant tests performed at different temperatures. Dual stimuli‐responsive hydrogels are proposed for the delivery of caffeine as model drug. The release profiles of caffeine depict a system particularly performing as on/off device at acidic pH with excellent applicability prospects.  相似文献   

7.
A new family of cationic hybrid hydrogels from two new positively charged aqueous soluble precursors, glycidyl methacrylate‐chitosan (GMA‐chitosan), and 2‐(acryloyloxy) ethyl trimethylammonium (AETA), was developed via a simple photocrosslinking fabrication method. These hybrid hydrogels have pendant quaternary ammonium functional groups on the AETA segments. The chemical composition of GMA‐chitosan/AETA hybrid hydrogels were characterized by Fourier transform infrared spectroscopy and their mechanical, swelling, and morphological properties were examined as a function of the composition of the hybrids as well as the effect of pH and ionic strength of the surrounding medium. GMA‐chitosan/AETA hybrid hydrogels show a porous network structure with average pore diameter 20–50 μm. The compression moduli of these hybrid hydrogels ranged from 27.24 to 28.94 kPa, which are significantly higher than a pure GMA‐chitosan (17.64 kPa). GMA‐chitosan/AETA hybrid hydrogel shows pH/ionic strength responsive swelling behavior because of the presence of the positive charge pendant groups. These hybrid hydrogels showed a sustained BSA protein release and a significantly lower initial burst release than a pure GMA‐chitosan hydrogel. The two aqueous soluble precursors and the cationic charge characteristics of the resulting GMA‐chitosan/AETA hybrid hydrogels may suggest that this new family of biomaterials may have promising applications as the pH responsive protein drug delivery vehicles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3736–3745, 2013  相似文献   

8.
This research synthesized graft copolymers of chitosan‐g‐poly(N‐isopropyl acrylamide) (CS‐g‐PNIPAAm) by UV‐initiated free‐radical polymerization of NIPAAm monomer to CS selectively at the C‐6 position of pyranose ring. First, amino groups in CS were protected by reaction with phthalic anhydride (PA) to form PACS. The degree of phthaloylation was carefully controlled to ensure that most amino groups were protected, and only a very small amount of hydroxyl groups were reacted. In the second step, the vinyl functional group was introduced to the PACS by reaction with a vinyl compound containing an isocyanate group (3‐isopropenyl‐αα′‐dimethylbenzyl isocyanate), through the urethane linkage with hydroxyl groups at the C‐6 position. The phthaloyl groups were then removed by hydrazine to recover the amino groups in CS. Finally, PNIPAAm was grafted to the vinyl CS at the C‐6 position by UV‐initiated free‐radical polymerization. The synthesized CS‐g‐PNIPAAm copolymers were confirmed to have a structure of an AB‐crosslinked graft copolymer. Respectively, these copolymer hydrogels exhibited pH‐ and thermal‐responsive swelling properties in an aqueous solution due to their CS and PNIPAAm components. The test of cell viability with L929 fibroblast revealed that the CS‐g‐PNIPAAm copolymers having a grafting ratio lower than 1.7 had cellular compatibility as good as pure CS. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

9.
Poly(3‐hydroxy octanoate) (PHO), poly(3‐hydroxy butyrate‐co‐3‐hydroxyvalerate) (PHBV), and linoleic acid were grafted onto chitosan via condensation reactions between carboxylic acids and amine groups. Unreacted PHAs and linoleic acid were eliminated via chloroform extraction and for elimination of unreacted chitosan were used 2 wt % of HOAc solution. The pure chitosan graft copolymers were isolated and then characterized by FTIR, 13C‐NMR (in solid state), DSC, and TGA. Microbial polyester percentage grafted onto chitosan backbone was varying from 7 to 52 wt % as a function of molecular weight of PHAs, namely as a function of steric effect. Solubility tests were also performed. Graft copolymers were soluble, partially soluble or insoluble in 2 wt % of HOAc depending on the amount of free primary amine groups on chitosan backbone or degree of grafting percent. Thermal analysis of PHO‐g‐Chitosan graft copolymers indicated that the plastizer effect of PHO by means that they showed melting transitions Tms at 80, 100, and 113°C or a broad Tms between 60.5–124.5°C and 75–125°C while pure chitosan showed a sharp Tm at 123°C. In comparison of the solubility and thermal properties of graft copolymers, linoleic acid derivatives of chitosan were used. Thus, the grafting of poly(3‐hydroxyalkanoate) and linoleic acid onto chitosan decrease the thermal stability of chitosan backbone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:81–89, 2007  相似文献   

10.
Modification of chitosan by grafting with 4‐vinylpyridine (VP) was carried out both in homogeneous and heterogeneous phases, using potassium persulfate (K2S2O8) and sodium bisulfite (NaHSO3) as redox initiators. The effect of monomer concentration, initiator concentration and redox ratio, time and temperature on the extent of grafting (G%), homopolymer formation, and the efficiency of grafting were studied. Values of grafting percentages up to 96% were reached in heterogeneous conditions and up to 130% in homogeneous conditions (in 5% acetic acid). The grafting was confirmed by FTIR and 1H NMR spectroscopy. The grafted samples were characterized by scanning electron microscopy, X‐ray diffraction, and thermogravimetric analysis. The crystallinity of the used chitosan was not affected by grafting, it even increased slightly. Dye uptake of the grafted samples towards the different types of dyes (acidic and basic) was investigated and was found to improve profoundly over the native chitosan with a higher uptake for the acidic dye. The grafted samples showed an increased swelling in water, which increased further upon quaternization of the graft copolymers. The extent of swelling is higher in acidic and basic media more than in neutral pH. The grafted copolymers are soluble with difficulty in warm acetic acid solution. The quaternized graft copolymer was found to be soluble in water. The biological activity of the quaternized graft copolymers (G = 130 and 80%) was investigated and was found to have an inhibition effect on both the Azotobacter fungus and the bacterium Fusarium oxysporium. The effect on the micro organisms is proportional to the amount of VP in the graft copolymer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3308–3317, 2006  相似文献   

11.
The grafting of a poly(ethylene glycol) diacrylate macromer onto a chitosan backbone was carried out with different macromer concentrations. The grafting was achieved by (NH4)2Ce(NO3)6‐induced free‐radical poly merization. Biodegradable, pH‐ and thermally responsive hydrogels of poly(ethylene glycol)‐g‐chitosan crosslinked with a lower amount of glutaraldehyde were prepared for controlled drug release studies. Both the graft copolymers and the hydrogels were characterized with Fourier transform infrared, elemental analysis, and scanning electron microscopy. The obtained hydrogels were subjected to equilibrium swelling studies at different temperatures (25, 37, and 45°C) in buffer solutions of pHs 2.1 and 7.4 (similar to those of gastric and intestinal fluids, respectively). 5‐Fluorouracil was entrapped in these hydrogels, and equilibrium swelling studies were carried out for the drug‐entrapped gels at pHs 2.1 and 7.4 and 37°C. The in vitro release profile of the drug was established at 37°C and pHs 2.1 and 7.4. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 977–985, 2006  相似文献   

12.
Chitosan was graft copolymerized with HEMA (2‐Hydroxyethylmethacrylate) for the development of blood‐compatible dialysis membranes. The permeation characteristics of HEMA‐grafted chitosan films for four different solutes creatinine, urea, glucose, and albumin was studied in vitro at 37°C for assessment of the suitability as dialysis membranes. The grafted film CH‐12.5 composition (425% grafting) showed very high permeation to creatinine by reaching the equilibrium within 45 min. The compositions CH‐7.5 and CH‐12.5 showed excellent permeation to glucose when compared to virgin chitosan films. In the case of urea permeation, all the grafted compositions exhibited higher percent permeation than the virgin chitosan films. The copolymer films CH‐7.5 and CH‐12.5 showed enhanced permeability for the high molecular weight solute, albumin. The other grafted copolymer compositions followed almost the same trend as that of chitosan for the low molecular weight solutes as well as the high molecular weight solute. The copolymer films were also found to be highly blood compatible, noncytotoxic, and biodegradable. Hence, the need for developing blood‐compatible chitosan membranes with desirable permeability properties is achieved by the graft copolymerization of HEMA onto chitosan. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2960–2966, 2006  相似文献   

13.
The new macrocyclic polyamine derivatives of chitosan were synthesized by reacting epoxy‐activated macrocyclic tetra‐amine with C6 hydroxyl or C2 amino group in chitosan. The obtained copolymers contain amino functional groups in its skeleton and secondary amines, and more polar hydroxyl groups. Elemental analysis, infrared spectra, and solid‐state 13C NMR analysis confirmed their structures. The adsorption behavior of the macrocyclic polyamine grafted chitosan for Ag+, Pb2+, Hg2+, and Cr3+ were investigated. The experimental results showed that the two novel derivatives of chitosan have high adsorption capacity and good selectivity for some metal ions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3018–3023, 2006  相似文献   

14.
In this study, hydrophilic monomers were photografted onto the PP plates at different monomer concentrations and temperatures, and grafted PP plates were bonded with enzymatically modified chitosan solutions. Their adhesive strength properties were discussed in relation to the grafting conditions and hydrophilic properties such as wettability and water‐absorptivity. In addition, the location of failure was investigated by X‐ray photoelectron spectroscopy analysis of failed surfaces. Wettability of the grafted PP plates except for the PP grafted with acrylic acid (PP‐g‐PAA) plates remained constant above the grafted amounts at which the PP surfaces were fully covered with grafted polymer chains. On the other hand, wettability of the PP‐g‐PAA plates passed through the maximum value and then gradually decreased with the grafted amount probably because of the aggregation of grafted PAA chains. Water‐absorptivity of the grafted layers formed at lower monomer concentrations or temperatures sharply increased at lower grafted amounts. The adhesive strength increased with an increase in the grafted amount and substrate breaking was observed for PP‐g‐PAA plates because enzymatically modified chitosan solutions were successfully penetrated in the grafted layers and quinone derivatives reacted with carboxy groups of grafted PAA chains. Failure occurred in the layers composed of grafted PAA chains and components containing in enzymatically modified chitosan solutions and the location was shifted to the inside of grafted layer, as the grafted amount increased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1369‐1376, 2013  相似文献   

15.
Temperature‐ and pH‐responsive semi‐interpenetrating polymer network (semi‐IPN) hydrogels constructed with chitosan and polyacrylonitrile (PAN) were studied. The characterizations of semi‐IPN hydrogels were investigated using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). IPN hydrogels exhibited a relatively high swelling ratio, 23.31%–145.20% at room temperature. The swelling ratio of hydrogels depends on pH and temperature. DSC was used to determine the amount of free water in IPN hydrogels. The amount of free water increased with increasing chitosan content in the semi‐IPN hydrogels. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2011–2015, 2003  相似文献   

16.
Graft copolymerization of D,L ‐lactic acid (LA) onto chitosan (CS) was attempted without using a catalyst. pH‐sensitive hydrogels were obtained which are based on two different components: a natural polymer and a synthetic polymer. These polyester substituents provide the basis for hydrophobic interactions that contribute to the formation of hydrogels. The swelling mechanisms in enzyme‐free simulated gastric fluid (SGF, pH 2.2) or simulated intestinal fluid (SIF, pH 7.4) at 37°C were investigated. Meanwhile, structural changes of the graft copolymers in the different pH buffers were studied by FTIR, and these are discussed together with the swelling mechanisms. The effect of pH on the water uptake of hydrogel was investigated by using McIlvaine buffer with the same ionic strength. The morphological change of hydrogels in different aqueous solutions is investigated by scanning electron microscopy (SEM). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3186–3192, 1999  相似文献   

17.
A novel, physically stabilized hydrogel system composed of chitosan (Chi) or its derivatives [e.g., carboxymethyl chitosan (CMC), sodium carboxymethyl chitosan, or trimethyl carboxymethyl chitosan (TMCMC)] with poly(vinyl pyrrolidone) (PVP) or opened‐ring poly(vinyl pyrrolidone) (OR–PVP) were prepared and characterized. TMCMC was synthesized by a novel method with dimethylsulfate as the methylation agent. The synthesized materials were characterized by Fourier transform infrared spectroscopy, 1H‐NMR, 13C‐NMR, and size exclusion chromatography. The mechanical properties, gel fraction, swelling behavior, and water state of the prepared hydrogels were investigated. Gelation occurred when the OR–PVP and Chi solutions were blended within a few seconds. However, the gelation of the OR–PVP and CMC solutions needed pH adjustment. No gelation occurred when the solutions of TMCMC and PVP or OR–PVP were blended. The quaternization or protonization of  NH2 groups may have prevented the gelation of the solutions. The amino groups of Chi derivatives should have been free to take part in hydrophilic bonds between the two polymers. The physical entanglement of polymeric chains and strong hydrogen bonds between the polymers were considered as mechanisms for the formation of the physical hydrogels. The physical hydrogels showed ionic and pH‐sensitive swelling properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

18.
Three polyesters—poly(ethylene terephthalate), poly(2‐methyl‐1,3‐propylene terephthalate‐co‐ethylene terephthalate), and poly(1,4‐cyclohexylene terephthalate‐co‐ethylene terephthalate)—were preirradiated with 60Co‐γ‐rays. Then, acrylic acid and N‐vinylformamide were grafted to these irradiated fibers. Fibers grafted with N‐vinylformamide were further hydrolyzed with acid so that the amide groups would convert into amino groups, and they were treated with glutaraldehyde so that aldehyde groups would be introduced. Chitosan or chitooligosaccharide was then grafted to these fibers via either esterification or imine formation. Four pathogenic bacteria—methicillin‐resistant Staphylococcus aureus‐1 (MRSA), Staphylococcus aureus‐2, Escherichid coli, and Pseudomonas aeruginosa—were tested to determine the antibacterial activities of chitosan‐grafted and chitooligosaccharide‐grafted fibers. The results showed that grafting chitosan via imine formation could achieve a higher surface density for amino groups and give higher antibacterial activity to those four bacteria tested. The antibacterial activity for E. coli was the highest and that for MRSA was the lowest among the four bacteria tested. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2977–2983, 2002  相似文献   

19.
The swelling properties of different chitosan–poly(vinyl alcohol) (PVA) hydrogels were investigated as functions of the medium pH and salt concentration. The maximum swelling ability of the hydrogels was at a buffer pH of approximately 3, regardless of the PVA content in the hydrogels. The maximum mass of the swollen hydrogels was about 13 times that of their contracted counterparts. The cyclical swelling and contraction between pH 3 and pH 7 buffers and pH 3 and pH 3 buffers with salt confirmed the Donnan swelling mechanism of these hydrogels. The swelling mechanism was considered the transfer of water molecules driven by a concentration gradient. This was represented by a simplified mass‐balance model, which neglected the effect of the ionization reaction, for the initial swelling period. The effective mass‐transfer coefficient of water molecules during swelling, estimated with this model, gradually decreased with increasing PVA content in the hydrogels. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4665–4671, 2006  相似文献   

20.
Two anionic soluble monomers, mono(2‐methacryloyl oxyethyl)acid phosphate and vinylsulfonic acid sodium salt, were grafted onto chitosan to obtain copolymers with zwitterionic property. Graft reaction improved the antimicrobial activities of chitosan. Antimicrobial activities of chitosan and graft copolymers depended largely on the amount and type of grafted chains as well as changes of pH, against Candida albicans, Trichophyton rubrum, and Trichophyton violaceum. The most excellent antimicrobial activity among tested samples was shown at pH 5.75 with demonstrating strain selectivity against Candida albicans and Trichophyton violaceum due to the difference in affinity between cell wall of fungi and chitosan or its derivatives. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1713–1719, 1999  相似文献   

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