Synthesis and characterization of poly{N‐[3‐(dimethylamino) propyl] methacrylamide‐co‐itaconic acid} hydrogels for drug delivery

A novel pH‐sensitive hydrogel system composed of itaconic acid (IA) and N‐[3‐(dimethylamino) propyl] methacrylamide was designed. This system was prepared by aqueous copolymerization with N,N‐methylene bisacrylamide as a chemical crosslinker. The chemical structure of the hydrogels was characterized by Fourier transform infrared (FTIR) spectroscopy. The microstructure and morphology of the hydrogels were evaluated by X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The SEM study of hydrogels on higher magnification revealed a highly porous morphology with uniformly arranged pores ranging from 40 to 200 μm in size. XRD analysis revealed the amorphous nature of the hydrogels, and it was found that an increase in the IA content in the monomer feed greatly reduced the crystallinity of the hydrogels. Swelling experiments were carried out in buffer solutions at different pH values (1.2–10) at 37°C ± 1°C to investigate their pH‐dependent swelling behavior and dimensional stability. An increase in the acid part (IA) increased the swelling ratio of the hydrogels. Temperature‐sensitive swelling of the hydrogels was investigated at 20–70°C in simulated intestinal fluid. The hydrogels swelled at higher temperatures and shrank at lower temperatures. 5‐Aminosalicylic acid (5‐ASA) was selected as a model drug, and release experiments were carried out under simulated intestinal and gastric conditions. 5‐ASA release from the poly N‐[3‐(dimethylamino) propyl] methacrylamide‐co‐itaconic acid‐80 (PDMAPMAIA‐80) hydrogel was found to follow non‐Fickian diffusion mechanism under gastric conditions, and a super case II transport mechanism was found under intestinal conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and swelling properties of a pH‐ and temperature‐dual responsive hydrogel by inverse microemulsion polymerization

A novel pH‐ and temperature‐dual responsive hydrogel was synthesized by inverse microemulsion polymerization, using itonic acid (IA) as pH‐responsive monomer, N‐isopropylacrylamide (NPAM) as thermo‐responsive monomer and acrylamide (AM) as the nonionic hydrophilic monomer. Factors affecting water and salt absorption, as well as swellability of the dual responsive hydrogels, such as IA/NPAM mass ratio and crosslinker amount, were investigated. pH‐ and temperature‐sensitivity and dynamic viscoelasticity behaviors of the dual responsive hydrogels were also studied. The dual responsive responsive hydrogels showed suitable water and salt absorbency, remarkable pH‐, and temperature‐sensitivity, adjustable swellability and enhanced viscoelastic behaviors under high stress. Water absorbency and pH‐sensitivity increased while salt absorbency and temperature‐ sensitivity decreased with increasing IA/NIPAM mass ratio. Both water absorbency and salt absorbency increased first with crosslinker amount increased to 0.2 wt %, and then decreased with increasing crosslinker amount. Temperature‐induced shrinkage range of the dual responsive hydrogels was higher and broader than that of the conventional poly(N‐isopropylacrylamide) hydrogel. TEM indicated that the as‐synthesized hydrogel particles were regular and spherical‐like in shape and had the mean particle size of 49nm in the range of 30–78 nm. FTIR indicated the structure of the dual responsive hydrogels. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42139.     

Electrical actuation of electroresponsive hydrogels based on poly(acrylamide‐co‐acrylic acid)/graphite suitable for biomedical applications

A pH‐sensitive composite hydrogel based on poly(acrylamide‐co‐acrylic acid)/graphite was prepared by solution polymerization process in presence of redox initiator potassium persulfate/N,N,N′,N′‐tetramethylethylenediamine and cross‐linker (ethylene glycol dimethylacrylate). The structures of the hydrogels were confirmed using Fourier transform infrared, X‐ray diffraction, and scanning electron microscopy (SEM) study. Tensile strengths of the hydrogels were determined by using a universal tensile machine, whereas the electrical conductivities of the hydrogels were evaluated using Four‐probe method. The influence of cross‐linker, graphite content, and temperature on the conductivity of the hydrogel was also investigated. The bending behavior of the conducting hydrogels was investigated by exposing the hydrogels under electric field in aqueous medium. By studying the swelling ratio of the polymer synthesized under different conditions, optimization conditions were found for a polymer with the highest swelling ratio. Also, the hemolytic potentiality test revealed that prepared hydrogels are biocompatible in nature. POLYM. COMPOS., 35:27–36, 2014. © 2013 Society of Plastics Engineers     

A novel temperature and pH dual‐responsive hybrid hydrogel with polyhedral oligomeric silsesquioxane as crosslinker: synthesis,characterization and drug release properties

Octavinyl polyhedral oligomeric silsesquioxane (OVPS) is used as the crosslinker instead of N,N′‐methylenebisacrylamide (BIS) to copolymerize with 2‐(dimethylamino)ethyl methacrylate (DMAEMA) or DMAEMA and N‐isopropylacrylamide (NIPAM) to prepare hybrid hydrogels: P(OVPS‐co‐DMAEMA) and P(OVPS‐co‐DMAEMA‐co‐NIPAM). The prepared hydrogels are transparent and show dual response to temperature and pH. The hydrogels were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis and tensile tests. Their mechanical properties, swelling ratio, deswelling and reswelling behaviors as well as drug release properties were investigated. The results indicate that OVPS can be incorporated into polymer networks in proportion to feed ratios. The P(OVPS‐co‐DMAEMA) hydrogel exhibits more homogeneous interior structure, higher swelling ratio and faster response than the conventional hydrogel prepared with BIS. Moreover, the incorporation of OVPS enhances the compression and tensile properties of the hydrogels. The feed ratios of OVPS and NIPAM have a great effect on volume phase transition temperature, thermal sensitivity, swelling behavior, mechanical properties and drug release properties of the hybrid hydrogels. The prepared dual‐responsive OVPS‐containing hydrogels are expected to be used as biomedical materials in drug release and tissue engineering. © 2014 Society of Chemical Industry     

Fabrication of thermoresponsive,core‐crosslinked micelles based on poly[N‐isopropyl acrylamide‐co‐3‐(trimethoxysilyl)propylmethacrylate]‐b‐poly{N‐[3‐(dimethylamino)propyl]methacrylamide} for the codelivery of doxorubicin and nucleic acid

Thermoresponsive amphiphilic copolymer, poly[N‐isopropyl acrylamide‐co‐3‐(trimethoxysilyl)propylmethacrylate]‐b‐poly{N‐[3‐(dimethylamino)propyl]methacrylamide} with a branched structure was designed and synthesized by consecutive reversible addition–fragmentation chain‐transfer polymerization. The further hydrolysis of trimethoxysilyl functions in 3‐(trimethoxysilyl) propyl methacrylate units led to the fabrication of core‐crosslinked (CCL) micelles with silica crosslinks at temperatures above the lower critical solution temperature of the poly(N‐isopropyl acrylamide) block. The thermally induced structural and morphological changes of the CCL micelles in aqueous solution were investigated by transmission electron microscopy and ¹H‐NMR analyses. The resulting CCL micelles were further explored as nanocarriers for the codelivery of an anticancer drug and nucleic acid for enhanced therapeutic efficacy. The CCL micelles effectively condensed the nucleic acid and mediated higher gene transfer in the presence of serum than in serum‐free transduction. A cytotoxicity study revealed that whereas the pure CCL micelles exhibited unapparent cytotoxicity, the codelivery of p53 and doxorubicin with the CCL micelle formulation resulted in better treatment efficiency than sole chemotherapy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41752.     

pH‐thermoreversible hydrogels. I. Synthesis and swelling behaviors of the (N‐isopropylacrylamide‐co‐acrylamide‐co‐2‐hydroxyethyl methacrylate) copolymeric hydrogels

A series of pH‐thermoreversible hydrogels that exhibited volume phase transition was synthesized by various molar ratios of N‐isopropylacrylamide (NIPAAm), acrylamide (AAm), and 2‐hydroxyethyl methacrylate (HEMA). The influence of environmental conditions such as temperature and pH value on the swelling behavior of these copolymeric gels was investigated. Results showed that the hydrogels exhibited different equilibrium swelling ratios in different pH solutions. Amide groups could be hydrolyzed to form negatively charged carboxylate ion groups in their hydrophilic polymeric network in response to an external pH variation. The pH sensitivities of these gels also depended on the AAm content in the copolymeric gels; thus the greater the AAm content, the higher the pH sensitivity. These hydrogels, based on a temperature‐sensitive hydrogel, demonstrated a significant change of equilibrium swelling in aqueous media between a highly solvated, swollen gel state and a dehydrated network response to small variations of temperature. pH‐thermoreversible hydrogels were used for a study of the release of a model drug, caffeine, with changes in temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 221–231, 1999     

Chitosan–Quercetin Bioconjugate as Multi‐Functional Component of Antioxidants and Dual‐Responsive Hydrogel Networks

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.     

Synthesis and swelling behavior of thermosensitive IPN hydrogels based on sodium acrylate and N‐isopropyl acrylamide by a two‐step method

A series of interpenetrating polymer network (IPN) hydrogels having higher swelling ratio (SR) and thermosensitivity were synthesized from sodium acrylate (SA) and N‐isopropyl acrylamide (NIPAAm) by a two‐step method. A series of the porous poly(sodium acrylate ‐co‐1‐vinyl–2‐pyrrolidone) [poly(SA‐co‐VP)], (SV), hydrogels were prepared from acrylic acid having 90% degree of neutralization and VP monomer in the first step. The second step is to immerse the SV dried gels into the NIPAAm solution containing initiator, accelerator, and crosslinker to absorb NIPAAm solution and then polymerized to form the poly(SA‐co‐VP)/poly(NIPAAm) IPN hydrogels (SVN). The effect of the different molar ratios of SA/VP and the content of NIPAAm on the swelling behavior and physical properties of the SVN hydrogels was investigated. Results showed that the SVN hydrogels displayed an obviously thermoreversible behavior when the temperature turns across the critical gel transition temperature (CGTT) of poly(NIPAAm) hydrogel. The pore diameter distributions inside the hydrogel also indicated that the pore sizes inside the SVN hydrogels were smaller than those inside the SV hydrogels. At the same time, the more proportion of SA was added into the hydrogel, the larger pore diameter of the SV hydrogel was formed. The results also showed that the SR decreased with an increase of the VP content in the SV hydrogel and more obviously decreased in the SVN hydrogels. The SVN networks also showed stronger shear moduli than SV hydrogels. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of comonomer type and concentration on the equilibrium swelling and volume phase transition temperature of N‐isopropylacrylamide‐based hydrogels

The effect of incorporating a hydrophilic monomer into poly(N‐isopropylacrylamide) (polyNIPA) hydrogels on the equilibrium swelling and the volume phase transition temperature is reported here. A nonionizable monomer (acrylamide) and three ionizable monomers (itaconic acid, 2‐ethoxyethyl monoitaconate, and 2,2‐(2‐ethoxyethyl) monoitaconate) were studied. Hydrogels with larger swelling capacity than that of the polyNIPA hydrogel were obtained. With the exception of the hydrogel containing 2,2‐(2‐ethoxyethyl) monoitaconate, which did not exhibit the de‐swelling phenomena, the rest showed a volume phase transition. The hydrogels containing 85 wt % acrylamide and 15 wt % comonomer presented the higher shrinking ratio. For some compositions, the T_c of the polyNIPA hydrogel was within the desired temperature range (38–41°C) for controlled‐drug delivery in the human body. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of antimicrobial polycarboxybetaine‐based hydrogels for studies of drug loading and release

A series of cationic poly(N‐isopropyl acrylamide) (PNIPAM)‐g‐poly(carboxybetaine ester) (PCBMAE) hydrogels were prepared by reversible addition–fragmentation chain‐transfer polymerization with PCBMAE precursors reacting with N‐isopropyl acrylamide in the presence of N,N′‐methylene bisacrylamide. These hydrogels exhibited excellent antimicrobial activities against Staphylococcus aureus and could switch to nontoxic zwitterionic hydrogels after hydrolysis. Nonionic tetracycline hydrochloride (TCHC) and anionic sodium salicylate (SA) were selected to evaluate the loading capacities and release kinetics of the cationic hydrogels. We found that the loading efficiencies of TCHC in the PNIPAM‐g‐PCBMAE hydrogels were approximately twice as high as those of SA. However, the cumulative release amount of TCHC was lower than that of SA from the corresponding cationic hydrogel at 37°C. In addition, the PNIPAM‐g‐PCBMAE hydrogels exhibited accelerated release rates of both TCHC and SA with increasing content of (2‐carboxymethyl)?3‐acryloxyethyldimethylammonium chloride methyl ester. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39839.     

Fabrication of Photothermally Responsive Nanocomposite Hydrogel through 3D Printing

The responsive hydrogels have received great attention in many fields. However, the molding method and response mode of such hydrogels are criticized when it comes to real applications. In this work, a novel class of poly(N‐isopropyl acrylamide)/graphene oxide (PNIPAm/GO) nanocomposite hydrogel through self‐assembly three‐dimensional (3D) printing via ultraviolet light polymerization. The precursor is ordinarily constituted by NIPAm monomer, crosslinker, and water mixed with a photoinitiator, besides the introduction of nanoclay adjusts the shear thinning properties to an optimal level, which is important for the 3D printing precision. Then, the graphite oxide as infrared light absorber endows the hydrogel fast photothermal excited responsivity instead of conventional temperature response. The shrinkage and swelling of the composite hydrogel can be controlled by turning the near‐infrared light on or off. Meanwhile, the reversible behavior of as‐prepared hydrogel is easily regulated by altering the content of GO and illumination time of near‐infrared light. Additionally, a round tube is obtained based on the as‐prepared hydrogel, which can be driven to get a pencil, indicating their potential applications in actuator and other functional program.     

Dual pH‐ and temperature‐responsive hydrogels with extraordinary swelling/deswelling behavior and enhanced mechanical performances

pH‐ and temperature‐responsive semi‐interpenetrating nanocomposite hydrogels (NC hydrogels) were prepared with surface‐functionalized graphene oxide (GO) as the crosslinker, N‐isopropylacrylamide (NIPAM) as the monomer, and chitosan (CS) as an additive. The effects of 3‐(trimethoxysilyl)propylmethacrylate‐modified GO sheets and CS content on various physical properties were investigated. Results show that PNIPAM/CS/GO hydrogels undergo a large volumetric change in response to temperature. Swelling ratios of PNIPAM/CS/GO hydrogels are much larger than those of the conventional organically crosslinked PNIPAM hydrogels. The deswelling test indicates that the deswelling rate was greatly enhanced by incorporating CS into the hydrogel network and using the surface‐functionalized GO as the crosslinker. The pH‐sensitivity of PNIPAM/CS/GO hydrogels is evident below their volume phase transition temperature. Moreover, the PNIPAM/CS/GO hydrogels have a much better mechanical property compared with traditional hydrogels even in a high water content of 90%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41530.     

Formulation design,optimization, characterization and swelling behaviour of a cationic superabsorbent based on a copolymer of [3‐(methacryloylamino)propyl]trimethylammonium chloride and acrylamide

A series of crosslinked copolymers with cationic nature have been prepared based on acrylamide (AAm) and [3‐(methacryloylamino)propyl]trimethyl ammonium chloride (MAPTAC) using N,N′ methylene‐bis‐acrylamide (MBA) as crosslinking agent. Taguchi's method has been employed for the purpose of formulation design and optimization as well as investigating the effects of various compositional parameters, such as total monomer concentration, cationic monomer and crosslinking agent concentration. The swelling behaviour of the synthesized gels in electrolyte solutions composed of ions with different valency has been studied and compared with an anionic‐based superabsorbent. The swelling capacity and absorbency were found to be enhanced with increase of the MAPTAC moieties of the copolymer chains, and therefore increase of their cationic character. All the cationic hydrogels prepared had greater swelling capacity, with less change in their swelling behaviour, when immersed into aqueous solutions containing multivalent cations. The anionic‐based hydrogels collapsed in similar ionic solutions with moderate‐to‐high ionic strength and did not show any tendency to re‐swell. The complex modulus (G*) of the crosslinked copolymers in the equilibrium swollen state was measured by rheomechanical spectroscopy and was correlated with the chemical composition of the network. Thermogravimetric analysis of the dry cationic superabsorbent showed more bound water but similar thermal behaviour to crosslinked polyacrylamide Copyright © 2003 Society of Chemical Industry     

Influences of monomer self‐association on the radical solution homopolymerization of N‐[3‐(dimethylamino)propyl](meth)acrylamide

The specific dependencies of the initial reduced polymerization rate on the initial monomer concentration were introduced for the radical homopolymerization of N‐[3‐(dimethylamino)propyl]acrylamide (DMAPA) and N‐[3‐(dimethylamino)propyl]methacrylamide (DMAPMA) in toluene, DMF, and water at 60 °С. The degree of the monomer self‐association and the ratio of the amides constituting various types of associates were evaluated using FT‐IR spectroscopy and computer simulation for the solutions of DMAPA and DMAPMA in toluene with different monomer concentrations. The hypothesis linking the type of predominant pre‐reaction monomer assemblies and the revealed concentration effects was proposed for the homopolymerization of aminoamide monomers and explaining unconventional experimental data. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44412.     

Removal of textile dyes from single and ternary solutions using poly(acrylamide‐co‐N‐methylacrylamide) grafted katira gum hydrogel

A novel hydrogel poly(acrylamide‐co‐poly‐N‐methylacrylamide) grafted katira gum (KG) was synthesized via free radical copolymerization using a mixture of acrylamide and N‐methylacrylamide in presence of N,N′‐methylene‐bis‐acrylamide as a crosslinking agent. A series of hydrogels (KG‐1 to KG‐6) were prepared by varying amount of acrylamide and N‐methylacryamide. Poly‐acrylamide‐g‐katira gum (PAM‐g‐KG) and poly‐N‐methylacrylamide‐g‐katira gum (PNMA‐g‐KG) hydrogels were also prepared using same crosslinking agent. Swelling characteristics of all the prepared hydrogels in water were evaluated and the hydrogel with best swelling property (KG‐6) was identified. The hydrogel KG‐6 was characterized by FTIR, X‐ray diffractometer, and scanning electron microscopy and was used for the adsorption of textile dyes namely methylene blue (MB), malachite green (MG), and congo red (CR) from single and ternary solutions. Adsorption dynamics, kinetics, isotherm, and thermodynamics of all the prepared hydrogels were studied in the ternary dye solutions. The sorption kinetics data were fitted well to pseudo‐second order and the equilibrium adsorption data were found to follow Freundlich isotherm model. The thermodynamics studies showed that the adsorption process was spontaneous and exothermic in nature. The preferential dye adsorption by the hydrogel was followed in the order MB > MG > CR. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45958.     

Radiation synthesis and characterization of poly(N‐vinyl‐2‐pyrrolidone/acrylic acid) and poly(N‐vinyl‐2‐pyrrolidone/acrylamide) hydrogels for some metal‐ion separation

Two different hydrogels, prepared from N‐vinyl‐2‐pyrrolidone/acrylic acid (NVP/AAc) and N‐vinyl‐2‐pyrrolidone/acrylamide (NVP/AAm), were studied for the separation and extraction of some heavy‐metal ions from wastewater. The hydrogels were prepared by the γ‐radiation‐induced copolymerization of the aforementioned binary monomer mixtures. Further modification was carried out for the NVP/AAc copolymer through an alkaline treatment to improve the swelling behavior by the conversion of the carboxylic acid groups into its sodium salts. The thermal stability and swelling properties were also investigated as functions of the N‐vinyl‐2‐pyrrolidone content. The characterization and some selected properties of the prepared hydrogels were studied, and the possibility of their practical use in wastewater treatment for heavy metals such as Cu, Ni, Co, and Cr was investigated. The maximum uptake for a given metal was higher for a treated NVP/AAc hydrogel than for an untreated NVP/AAc hydrogel and was higher for an untreated NVP/AAc hydrogel than for an NVP/AAm hydrogel. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2642–2652, 2004     

Synthesis and properties of P(NIPAAm‐co‐AM)/SiO2 hybrid temperature‐sensitive hydrogels

Using N, N′‐methylene bisacrylamide as crosslinking agent and potassium peroxydisulfate as initiator, the temperature‐sensitive hydrogels were prepared with organic monomer N‐isopropylacrylamide (NIPAAm) and acrylic amide and inorganic material ethyl orthosilicate (TEOS). The structure of hybrid hydrogels was represented by scanning electron microscopy and Fourier transform infrared spectroscopy. The volume phase transition temperature (VPTT) of hybrid hydrogels was determined by differential scanning calorimetry thermograms of the swollen hydrogel. The results showed that the VPTT of the hydrogels increased with the increasing of TEOS dosage. When the temperature was lower than VPTT, the hydrogels exhibited excellent temperature sensitivity and kept at a swelling state, but when the temperature was higher than VPTT, the hydrogels deswelled significantly. In addition, the compressive strength of hydrogels was studied, the results showed that hybrid hydrogels had more ideal mechanical properties than organic hydrogels. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation,water absorbency,and enzyme degradability of novel chitin‐ and cellulose/chitin‐based superabsorbent hydrogels

Superabsorbent hydrogels were prepared from chitin dissolved in lithium chloride and N‐methyl‐2‐pyrrolidinone by esterification crosslinking with 1,2,3,4‐butanetetracarboxylic dianhydride (BTCA). The absorbency of the chitin hydrogel was strongly dependent on the ratio of BTCA feed to chitin. The hydrogel prepared at the feed ratio of 5 showed the highest absorbency (345 g/g‐polymer), and the hydrogel was composed of 0.65 molecules of BTCA per monomer unit of chitin. The hydrogels exhibited good biodegradability by chitinase with a maximum degradation of 91% within 7 days. This method for obtaining the chitin hydrogel was also applicable to cellulose and chitin mixtures, and 1 : 1 cellulose/chitin hybrid hydrogels could be obtained by the esterification crosslinking of a mixture with a 1 : 1 molar ratio of cellulose and chitin. The optimal BTCA feed ratio of 5 resulted in the cellulose/chitin hydrogel with the highest water absorbency (329 g/g‐polymer), and the hydrogel contained 0.65 molecules of BTCA per polysaccharide monomer unit. In addition, the hybrid hydrogels were degraded by cellulase as well as chitinase. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of novel pH‐sensitive chitosan‐poly(acrylamide‐co‐itaconic acid) hydrogels

Novel pH‐sensitive chitosan‐poly(acrylamide‐co‐itaconic acid) hydrogels were prepared by free radical copolymerization of acrylamide and itaconic acid (IA) in chitosan solution. The hydrogels were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry and the swelling ratios of the hydrogels in water (pH 6.8) and pH 1.2. The influence of composition on the thermal properties of the hydrogels was assessed. The glass transition temperatures of the samples increased with IA content, ranging from 110 to 136 °C. Swelling of the hydrogels was found to obey second‐order kinetics with respect to the remnant swelling, indicating that diffusion is controlled by the relaxation of chains. The equilibrium swelling degree was strongly dependent on pH and composition. At both pH values the highest water uptake was obtained for the IA‐free sample M1. From the equilibrium swelling results the average molar mass between crosslinks, M_c, and the crosslink density of the chitosan‐poly(acrylamide‐co‐itaconic acid) samples were calculated. The results evidenced the reinforcing effect of IA on the hydrogel structure. It is concluded that these highly swellable pH‐sensitive hydrogels can be useful for applications in biomedicine and pharmacy. © 2013 Society of Chemical Industry     

Preparation and application in drug controlled delivery of pH‐sensitive P(CE‐co‐DMAEMA‐co‐MEG) hydrogel

A pH‐sensitive hydrogel [P(CE‐co‐DMAEMA‐co‐MEG)] was synthesized by the free‐radical crosslinking polymerization of N,N‐dimethylaminoethyl methacrylate (DMAEMA), poly(ethylene glycol) methyl ether methacrylate(MPEG‐Mac) and methoxyl poly(ethylene glycol)‐poly(caprolactone)‐methacryloyl methchloride (PCE‐Mac). The effects of pH and monomer content on swelling property, swelling and deswelling kinetics of the hydrogels were examined and hydrogel microstructures were investigated by SEM. Sodium salicylate was chosen as a model drug and the controlled‐release properties of hydrogels were pilot studied. The results indicated that the swelling ratios of the gels in stimulated gastric fluids (SGF, pH = 1.4) were higher than those in stimulated intestinal fluids (SIF, pH = 7.4), and followed a non‐Fickian and a Fickian diffusion mechanism, respectively. In vitro release studies showed that its release rate depends on different swelling of the network as a function of the environmental pH and DMAEMA content. SEM micrographs showed homogenous pore structure of the hydrogel with open pores at pH 1.4. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40737.