Genipin‐cross‐linked chitosan‐based hydrogels: Reaction kinetics and structure‐related characteristics

The main aim of this work is the synthesis and characterization of cross‐linked chitosan systems. Chitosan hydrogels can be prepared by physical or chemical cross‐linking of polymer chains. Chemical cross‐linking, leading to the creation of hydrogel networks possessing improved mechanical properties and chemical stability, can be achieved using either synthetic agents or natural‐based agents. In this work, the cross‐linker Genipin, a naturally derived compound, was selected because of the lower acute toxicity compared to many other commonly used synthetic cross‐linking reagents. In particular, the chemical stabilization of chitosan through genipin cross‐linking molecules was performed and characterized by calorimetric analyses (differential scanning calorimetry), swelling measurements in different pHs, and ionic strength. The reaction kinetics was carried out by means of rheological measurements, and both the activation energy (E_a) and the reaction order (m) were calculated. The hydrogel analyses were carried out at different concentrations of genipin (GN1 and GN2). The results were used to evaluate the possibility to use the chemical cross‐linked chitosan–genipin hydrogel for biomedical applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42256.     

Preparation and characterization of pH‐sensitive hydrogels based on chitosan,itaconic acid and methacrylic acid

Novel pH‐sensitive hydrogels based on chitosan, itaconic acid and methacrylic acid were prepared in two steps. Chitosan was first ionically crosslinked with itaconic acid, after which a free radical polymerization and crosslinking of the chitosan/itaconic acid network was performed by adding methacrylic acid and a crosslinker in order to achieve better mechanical properties and tunable swelling. The samples were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, X‐ray diffraction, dynamic mechanical analysis and the swelling ratios of the hydrogels at various pH values (2.0–8.0). The hydrogel composition is found to have a great impact on the hydrogel structure, mechanical and thermal properties, morphology and swelling kinetics. The highly porous morphology of the gels is probably connected with the bulky chitosan/itaconic acid network which reduces the degree of crosslinking in the second step of the synthesis due to steric hindrances. The gels demonstrate substantial change in buffer absorbency with change of pH, low for acid buffers and the higher for pH values above 6 where the swelling is considerably slow, thus suggesting their strong candidature for use as oral drug‐delivery systems in the lower parts of the gastrointestinal tract and for drugs that require longer release times. Copyright © 2010 Society of Chemical Industry     

Radiation synthesis and characterization of 2‐hydroxyethyl‐methacrylate‐based hydrogels containing di‐ and tri‐protic acid and its application on wastewater treatment

Radiation‐crosslinked 2‐hydroxyethylmethacrylate/citric acid (HEMA/CAc), 2‐hydroxyethylmethacrylate/tartaric acid (HEMA/TA), and 2‐hydroxyethylmethacrylate/succinic acid (HEMA/Sc) copolymers were prepared by using ⁶⁰Co γ‐rays. The gel fraction yield and the swelling behavior of the prepared hydrogels were studied. It was shown that increasing irradiation doses was accompanied by an increase in yield of gel fraction and a decrease in swelling degree. The parameters of equilibrium swelling, maximum swelling, initial swelling rate, swelling exponent, and diffusion coefficient of the hydrogels were determined by studying the swelling behavior of the hydrogels prepared. It was seen that the equilibrium swelling degree increases as the content of acid increases, as a result of introducing more hydrophilic groups. When the hydrophilic polymer (acids) varies in the content range of 40–80 mg, swelling exponents (n) decreases, thereby indicating a shift in the water‐transport mechanism from the anomalous (non‐Fickian)‐type to the Fickian‐type. Characterization and some selected properties of the prepared hydrogels were studied, and accordingly the possibility of its practical use in the treatment of industrial wastes such as dyes and heavy metals (Fe, Ni, Co, and Cu) were also studied. The effect of treatment time, pH of feed solution, initial feed concentration, and temperature on the dye and heavy metals uptake was determined. The uptake order for a given metal was HEMA/TA hydrogel > HEMA/CAc > HEMA/Sc hydrogel. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Star‐shaped polycaprolactone/chitosan composite hydrogels: fabrication and characterization

Star‐shaped polycaprolactone (stPCL)/chitosan composite hydrogel was fabricated by simply melt/solution blending between chitosan/dicarboxylic acid solution and melted stPCL, using 1‐(3‐dimethylaminopropyl)‐3‐ethylcarbodiimide hydrochloride and N‐hydroxysuccinimide as conjugating agents to obtain a composite hydrogel. Here, stPCL and modified stPCL were investigated. The stPCL was modified to have a carboxyl‐terminated chain (stPCL‐COOH). The composite hydrogels were transparent. The network structure of the composite hydrogels was investigated. stPCL‐OH had no chemical bond to the chitosan network but stPCL‐COOH could co‐crosslink with the chitosan network. The porous structure and porosity of the composite hydrogels were similar to those of chitosan hydrogel. However, the hydrophobicity of stPCL resulted in a lower swelling ratio compared to chitosan hydrogel. The rheological analysis of the composite hydrogel exhibited a stable crosslinked network. Compression testing of the composite hydrogel obtained from stPCL‐COOH at a mole ratio of stPCL‐COOH and chitosan of 1:1 had optimum compressive mechanical properties comparable to chitosan hydrogel due to a synergistic effect of the flexibility in stPCL and the co‐crosslinking of stPCL‐COOH with the chitosan network. © 2020 Society of Chemical Industry     

Synthesis and swelling properties of 2‐hydroxyethyl methacrylate‐co‐1‐vinyl‐3‐(3‐sulfopropyl)imidazolium betaine hydrogels

A series of 2‐hydroxyethyl methacrylate/1‐vinyl‐3‐(3‐sulfopropyl)imidazolium betaine (HEMA/VSIB) copolymeric gels were prepared from various molar ratios of HEMA and the zwitterionic monomer VSIB. The influence of the amount of VSIB in copolymeric gels on their swelling behavior in water and various saline solutions at different temperatures and the drug‐release behavior, compression strength, and crosslinking density were investigated. Experimental results indicated that the PHEMA hydrogel and the lower VSIB content (3%) in the HEMA/VSIB gel exhibited an overshooting phenomenon in their dynamic swelling behavior, and the overshooting ratio decreased with increase of the temperature. In the equilibrium water content, the value increased with increase of the VSIB content in HEMA/VSIB hydrogels. In the saline solution, the water content for these gels was not affected by the ion concentration when the salt concentration was lower than the minimum salt concentration (MSC) of poly(VSIB). When the salt concentration was higher than the MSC of poly(VSIB), the deswelling behavior of the copolymeric gel was more effectively suppressed as more VSIB was added to the copolymeric gels. However, the swelling behavior of gels in KI, KBr, NaClO₄, and NaNO₃ solutions at a higher concentration would cause an antipolyelectrolyte phenomenon. Besides, the anion effects were larger than were the cation effects in the presence of a common anion (Cl^?) with different cations and a common cation (K⁺) with different anions for the hydrogel. In drug‐release behavior, the addition of VSIB increased the drug‐release ratio and the release rate. Finally, the addition of VSIB in the hydrogel improved the gel strength and crosslinking density of the gel. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2888–2900, 2001     

Synthesis and swelling properties of pH‐ and temperature‐sensitive interpenetrating polymer networks composed of polyacrylamide and poly(γ‐glutamic acid)

Novel hydrogels of interpenetrating polymer networks (IPNs) composed of polyacrylamide and poly(γ‐glutamic acid) were synthesized. In these systems, both polymers were crosslinked independently; this reduced the potential loss of a polymer during the washing process, as often occurs in semi‐IPN systems. Interpolymer interactions were investigated with Fourier transform infrared spectroscopy and differential scanning calorimetry. These studies suggested possible interactions between both polymers by the formation of hydrogen bonds. The swelling behavior of these hydrogels was analyzed by immersion of the hydrogel samples in deionized water at 25 and 37°C and in buffer solutions with pHs of 3, 7, and 10. The kinetics of swelling showed increases in the values of the swelling ratio with increasing immersion time in the swelling medium, molar proportion of the biopolymer in the hydrogel, temperature, and pH of the swelling medium. All of the hydrogels swelled rapidly and reached equilibrium in an average time of 40 min. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A novel pH‐sensitive and freeze‐thawed carboxymethyl chitosan/poly(vinyl alcohol) blended hydrogel for protein delivery

BACKGROUND: Blended hydrogels are widely applied in medical fields. They can provide many advantages, such as biocompatibility and biodegradability. Many materials and methods are used to obtain blended hydrogels. In this work, carboxymethyl chitosan (CMCS) and poly(vinyl alcohol) (PVA) blended hydrogels were prepared using the freezing and thawing technique. The properties of the hydrogels prepared, i.e. gel fraction, swelling and pH‐responsive behaviors, were investigated. RESULTS: The gel fraction increased with increasing time of freezing and thawing as determined through gravimetric analysis. It was also found that the equilibrium degree of swelling improved obviously due to the addition of CMCS compared to pure PVA hydrogel. The blended hydrogel with composition CMCS/PVA 80/20 (by weight) possessed the highest swelling ratio. The results of the influence of pH values on the swelling behavior showed that minimum swelling ratios of the hydrogels occurred near the isoelectric point of CMCS. Protein release studies were performed under various pH conditions: the release was much slower under acid than under basic conditions. The release showed a burst in the first 15 h and then steadily increased. CONCLUSION: The addition of CMCS can improve the physical properties of pure PVA hydrogels and provide pH sensitivity. It is concluded that PVA hydrogels containing CMCS could be potentially applied as oral delivery systems for protein drugs. Copyright © 2009 Society of Chemical Industry     

Semi‐interpenetrating polymer network hydrogels based on aspen hemicellulose and chitosan: Effect of crosslinking sequence on hydrogel properties

Semi‐interpenetrating network hydrogel films were prepared using hemicellulose and chemically crosslinked chitosan. Hemicellulose was extracted from aspen by using a novel alkaline treatment and characterized by HPSEC, and consisted of a mixture of high and low molecular weight polymeric fractions. HPLC analysis of the acid hydrolysate of the hemicellulose showed that its major constituent sugar was xylose. X‐ray analysis showed that the relative crystallinity of hydrogels increased with increasing hemicellulose content up to 31.3%. Strong intermolecular interactions between chitosan and hemicellulose were evidenced by FT‐IR analysis. Quantitative analysis of free amino groups showed that hemicellulose could interrupt the chemical crosslinking of chitosan macromolecules. Mechanical testing and swelling experiments were used to define the effective network crosslink density and average molecular weight between crosslinks. Swelling ratios increased with increasing hemicellulose content and mainly consisted of H‐bonded bound water. Results revealed that by altering the hydrogel preparation steps and hemicellulose content, crosslink density and swelling behavior of semi‐IPN hydrogels could be controlled without deteriorating their mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermoreversible hydrogels. IX. Swelling behaviors of thermosensitive hydrogels copolymerized by N‐isopropylacrylamide with 1‐vinyl‐3‐(3‐sulfopropyl) imidazolium betaine

A series of thermosensitive hydrogels were prepared from the various molar ratios of N‐isopropylacrylamide, 1‐vinyl‐3‐(3‐sulfopropyl) imidazolium betaine (VSIB), and N,N′‐methylene‐bis‐acrylamide. The influence of the amount of VSIB in the copolymeric gels on the swelling behaviors in water, in various saline solutions, and at various temperatures was investigated. The results indicated that the higher the VSIB content in the hydrogel system, the higher the swelling ratio and the gel transition temperature. In the saline solution the results showed that when the concentration of salt is higher than the minimum salt concentration (MSC) of poly(VSIB), the deswelling behavior of the copolymeric gel was more effectively suppressed as more VSIB was added to the copolymeric gels. In addition, only the sample containing 12 mol % VSIB (V4) exhibited an antipolyelectrolyte's swelling behavior when the concentration of salt was higher than the MSC of poly(VSIB). This means that the swelling ratio of the hydrogel can be improved with a higher concentration salt solution. In addition, the anion effects were larger than the cation effects in the presence of a common anion (Cl⁻) with different cations and a common cation (K⁺) with different anions for the hydrogel. Finally, the more VSIB in the hydrogel, the higher the diffusion coefficient in dynamic swelling. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 14–23, 2000     

Dual stimuli responsive glycidyl methacrylate chitosan‐quaternary ammonium hybrid hydrogel and its bovine serum albumin release

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     

External Stimuli‐Responsive Characteristics of Ionic Poly[(N,N‐diethylaminoethyl methacrylate)‐co‐(N‐vinyl‐2‐pyrrolidone)] Hydrogels

Summary: Polyelectrolyte hydrogels containing diprotic acid moieties sensitive to ionic strength changes of the swelling medium were synthesized from N,N‐diethylaminoethyl methacrylate (DEAEMA), N‐vinyl‐2‐pyrrolidone (VP) and itaconic acid (IA) by using ammonium persulfate (APS) as a free radical initiator in the presence of the cross‐linker, methylenebisacrylamide (MBAAm). The swelling behavior of the ionic poly[(N,N‐diethylaminoethyl methacrylate)‐co‐(N‐vinyl‐2‐pyrrolidone)] [P(DEAEMA/VP)] hydrogels were investigated in pure water; in NaCI solutions with pH 4 and 9; and in water‐acetone mixtures depending on the IA content in the hydrogel. The average molecular mass between cross‐links ( ) and polymer‐solvent interaction parameter (χ) of the hydrogels were determined from equilibrium swelling values. The pulsatile swelling behavior was also observed in response to solvent changes between the solution in water and in acetone. The equilibrium swelling ratio of these hydrogels was basically unaffected with change in temperature. The swelling variations were explained according to the swelling theory based on the hydrogel chemical structure.

Pulsatile swelling behavior of ionic P(DEAEMA/VP) hydrogels in response to solvent changes between water and acetone at 25 °C.     

Hydrogel of Radiation‐Induced Cross‐Linked Hydroxypropylcellulose

Hydroxypropylcellulose (HPC) hydrogel being a material of natural origin, combines the properties of a polymer, which make up the network, with biodegradability. In this report the effects of high energy radiation on the ether of cellulose‐HPC are presented. The polymer irradiated in its solid state or in dilute aqueous solution underwent mainly degradation, induced by the cleavage of glycosidic bonds in its main chain. Irradiation of HPC in aqueous solutions at moderate concentrations resulted in the formation of hydrogels. Chemical cross‐links bond the chains of polymer, turning it to an insoluble macroscopic gel. We have found that in addition to concentration, dosage and dose rate can affect the results of irradiation. Electron beam irradiation gave higher gel fraction, up to 90%, than gamma irradiation, which has a maximum gel fraction of 65%. Swelling of the cross‐linked hydrogels was related to the density of cross‐links and was the highest at low irradiation doses. HPC hydrogels displayed thermally reversible character in their swelling. The volume of gel underwent continuous deswelling with an increase of the solution temperature, with the deswelling rate increasing rapidly over 40°C. At elevated temperatures the hydrogel collapsed, lost its transparency and changed color to translucent white. This transition was fully reversible when the gel was placed in the medium of low temperature. The hydrogel demonstrated superior mechanical properties. Despite of the stable three‐dimensional cross‐linked network, the gels underwent biodegradation under controlled conditions when enzyme was used.     

Synthesis of the copolymer hydrogel κ‐carrageenan‐graft‐PAAm: Evaluation of its absorbent and adhesive properties

κ‐Carrageenan‐graft‐PAAm, a copolymer hydrogel of κ‐carrageenan (kC) and acrylamide (AAm), has been synthesized in aqueous medium at ～ pH 7 in the presence of the initiator potassium persulfate (KPS), using microwave irradiation. The reaction conditions were optimized by varying the concentration of AAm and KPS to obtain copolymer hydrogels having different nitrogen contents e.g., %N 6.35, 10.56, and 11.05. It was observed that copolymer hydrogel having %N 11.05 gives superior adhesive properties whereas copolymer hydrogel with %N 10.56 produces superior absorbent properties in the presence of optimized concentrations of AAm (0.87 and 1.1428 mol/L respectively) and KPS (0.022 and 0.0296 mol/L respectively). The product with %N 6.35 is a soft gel (2–5% gel in 1% KCl) exhibiting low gel strength (135 g cm^?2). The one with %N 10.56 showed superior swelling property and maximum swelling was observed in the alkaline pH (22 g/g). The swelling behaviors of the hydrogels were studied at different pHs (pH 1.2–12.5) as well as in 1% aqueous solutions of NaCl, KCl, and CaCl₂. The 5% dispersion of the hydrogel having %N 11.05 in water had good binding properties with papers, polyethylene sheets, and wood pieces. To evaluate the measure of adhesive property, the viscosity and solid and liquid weights of the applied adhesive were measured. Characterization of the copolymer hydrogels was done by TGA, X‐ray diffraction, ¹³C‐NMR, FT‐IR, elemental analyses, and rheological studies. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5144–5152, 2006     

Hydrolyzed collagen‐based hydrogel with salt and pH‐responsiveness properties

A novel hydrolyzed collagen‐based hydrogel has been prepared by grafting the binary mixture of acrylamide and 2‐acrylamido‐2‐methylpropanesulfonic acid onto the collagen backbone in the presence of a crosslinking agent. Its physicochemical properties in aqueous solution were studied. The effect of reaction variables on both gel content and swelling capacity was investigated to achieve a hydrogel with improved absorbency and gel content. The absorbency under load of optimized hydrogel was also investigated by using an absorbency under load tester at various applied pressures. The swelling ratio in various salt solutions was also determined and additionally, the swelling of hydrogels was measured in solutions with pH ranged 1–13. The synthesized hydrogel exhibited a pH‐responsiveness character so that a swelling‐collapsing pulsatile behavior was recorded at pH 2 and 8. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation of alginate/poly(N‐isopropylacrylamide) semi‐interpenetrating and fully interpenetrating polymer network hydrogels with γ‐ray irradiation and their swelling behaviors

Semi‐interpenetrating polymer network (semi‐IPN) and fully interpenetrating polymer network (full‐IPN) hydrogels composed of alginate and poly(N‐isopropylacrylamide) were prepared with γ‐ray irradiation. The semi‐IPN hydrogels were prepared through the irradiation of a mixed solution composed of alginate and N‐isopropylacrylamide (NIPAAm) monomer to simultaneously achieve the polymerization and self‐crosslinking of NIPAAm. The full‐IPN hydrogels were formed through the immersion of the semi‐IPN film in a calcium‐ion solution. The results for the swelling and deswelling behaviors showed that the swelling ratio of semi‐IPN hydrogels was higher than that of full‐IPN hydrogels. A semi‐IPN hydrogel containing more alginate exhibited relatively rapid swelling and deswelling rates, whereas a full‐IPN hydrogel showed an adverse tendency. All the hydrogels with NIPAAm exhibited a change in the swelling ratio around 30–40°C, and full‐IPN hydrogels showed more sensitive and reversible behavior than semi‐IPN hydrogels under a stepwise stimulus. In addition, the swelling ratio of the hydrogels continuously increased with the pH values, and the swelling processes were proven to be repeatable with pH changes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4439–4446, 2006     

Swelling and drug‐release behavior of the poly(AA‐co‐N‐vinyl pyrrolidone)/chitosan interpenetrating polymer network hydrogels

A series of novel hydrogels were prepared from acrylic acid (AA), N‐vinyl pyrrolidone (NVP), and chitosan by photopolymerization. The swelling behavior, gel strength, and drug release behavior of the poly(AA/NVP) copolymeric hydrogels and corresponding interpenetrating polymer network hydrogels were investigated. Results showed that the swelling ratios for the present hydrogels decreased with an increase of NVP content in the gel, but the gel strength increased with an increase of NVP content in the gel. Results also showed that the drug‐release behavior for the gels is related to the ionicity of drug and the swelling ratio of the gel. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2135–2142, 2004     

Selected properties of pH‐sensitive,biodegradable chitosan–poly(vinyl alcohol) hydrogel

Chitosan and poly(vinyl alcohol) (PVA) were used to form a semi‐interpenetrating polymeric network with glutaraldehyde as the cross‐linker. The molecular weight and degree of deacetylation of the chitosan were 612 kDa and 72 %, respectively. The chemical bonds formed by the cross‐linking reaction and transition of these bonds in different pH media were investigated. The gelation property of the chitosan–PVA pregel solution and mechanical properties of the hydrogel were studied. The FTIR spectra of the hydrogel before and after swelling at pH 3 and pH 7 indicated formation of Schiff's base (C?N) and ? NH₃⁺. They also showed pH‐induced transition of C?N to C? N, and ? NH₃⁺ to ? NH₂, as well as the instability of the Schiff's base. The chitosan is essential for hydrogel formation through Schiff's base reaction between the amino groups of the chitosan and the aldehyde groups of the glutaraldehyde. The addition of PVA improved the mechanical properties of the hydrogel. However, PVA tends to leach out at longer swelling times in the acidic medium due to hydrolysis of the gel networks, Schiff's base. Copyright © 2004 Society of Chemical Industry     

Temperature and pH‐response swelling behavior of poly(2‐ethyl‐2‐oxazoline)/chitosan interpenetrating polymer network hydrogels

Interpenetrating polymer network (IPN) hydrogels composed of poly(2‐ethyl‐2‐oxazoline) (PEtOz) and chitosan (CS) were prepared with radical polymerization and were characterized for their swelling properties. Sample OC11 (hydrogel weight ratio PEtOz/CS = 1/1) swelled more than samples OC21 (PEtOz/CS = 2/1) and OC31 (PEtOz/CS =3/1), exhibiting a swelling ratio of about 2000 wt % in deionized water; the swelling ratios of the other samples were about 1000 and 700 wt %. The swelling behavior of the IPN hydrogels was observed under various pH and temperature conditions. The swelling ratios of the samples ranged from about 2000 to 6500 wt % at lower pHs, with a maximum swelling ratio of about 6500 wt % in a pH 2 aqueous solution. They exhibited low critical solution temperature behavior, with sample OC31 more sensitive to temperature and sample OC11 more sensitive to pH. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1100–1103, 2006     

Medicated wound dressings based on poly(vinyl alcohol)/poly(N‐vinyl pyrrolidone)/chitosan hydrogels

Poly(vinyl alcohol)/poly(N‐vinyl pyrrolidone) (PVP)/chitosan hydrogels were prepared by a low‐temperature treatment and subsequent ⁶⁰Co γ‐ray irradiation and then were medicated with ciprofloxacin lactate (an antibiotic) and chitosan oligomer (molecular weight = 3000 g/mol). The gel content, swelling ratio, tensile strength, and crystallinity of the hydrogels were determined. The effects of the chitosan molecular weight, the low‐temperature treatment procedure, and the radiation dosage on the hydrogel properties were examined. The molecular weight of chitosan was lowered by the irradiation, but its basic polysaccharide structure was not destroyed. Repeating the low‐temperature treatment and γ‐ray irradiation caused effective physical crosslinking and chemical crosslinking, respectively, and contributed to the mechanical strength of the final hydrogels. The incorporation of PVP and chitosan resulted in a significant improvement in the equilibrium swelling ratio and elongation ratio of the prepared hydrogels. The ciprofloxacin lactate and chitosan oligomer were soaked into the hydrogels. Their in vitro release behaviors were examined, and they were found to follow diffusion‐controlled kinetics. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2453–2463, 2006     

Release of vitamin B12 from poly(N‐vinyl‐2‐pyrrolidone)‐crosslinked polyacrylamide hydrogels: A kinetic study

Hydrogels, composed of poly(N‐vinyl‐2‐pyrrolidone) and crosslinked polyacrylamide, were synthesized and the release of vitamin B₁₂ from these hydrogels was studied as a function of the degree of crosslinking and pH of the external swelling media. The three drug‐loaded hydrogel samples synthesized with different crosslinking ratios of 0.3, 0.7, and 1.2 (in mol %) follow different drug‐release mechanisms, that is, chain relaxation with zero‐order, non‐Fickian and Fickian, or diffusion‐controlled mechanisms. To establish a correlation between their swelling behavior and drug‐release mechanism, the former was studied by the weight‐gain method and, at the same time, the concentration of the drug released was studied colorimetrically. Various swelling parameters such as the swelling exponent n, gel‐characteristic constant k, penetration velocity v, and diffusion coefficient D were evaluated to reflect the quantitative aspect of the swelling behavior of these hydrogels. Finally, the drug‐release behavior of the hydrogels was explained by proposing the swelling‐dependent mechanism. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1706–1714, 2000