Radiation synthesis of superabsorbent polyethylene oxide/tragacanth hydrogel

A new superabsorbent hydrogel has been prepared from tragacanth and polyethylene oxide (PEO) by gamma radiation at room temperature. Tragacanth solutions with different concentrations (1%, 3% and 5%) have been blended with 5% aqueous solution of PEO at a ratio of 1:1 and irradiated at doses 5–20 kGy. The properties of the prepared composite hydrogels were evaluated in terms of the gel fraction and the swelling behavior. An unexpected growth of the gel fraction was observed in PEO/tragacanth hydrogels irradiated at 5 kGy. Incorporation of 5% tragacanth into the aqueous PEO increased significantly the swelling percent of the hydrogels to more than 14,000% and thus makes it a superabsorbent material.     

Synthesis and Swelling Behaviors of P(AMPS-co-AAc) Superabsorbent Hydrogel Produced by Glow-Discharge Electrolysis Plasma

Highly swelling P(2-acrylamido-2-methyl-1-propanesulfonic acid- co-acrylic acid) (P(AMPS-co-AAc)) superabsorbent hydrogel was synthesized in aqueous solution by a simple one-step using glow-discharge electrolysis plasma technique, in which N,N’-methylenebisacrylamide was used as a crosslinking agent. The structure, thermal stability and morphology of P(AMPS-co-AAc) superabsorbent hydrogel were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. A mechanism for synthesis of P(AMPS-co-AAc) superabsorbent hydrogel was proposed. The reaction parameters affecting the equilibrium swelling (i.e., discharge voltage, discharge time, macroscopic temperature of the liquid phase, mass ratio of AMPS to AAc, and content of crosslinker) were systematically optimized to achieve a superabsorbent hydrogel with a maximum swelling capacity. The hydrogel formed which absorbed about 1,685 g H₂O/g dry hydrogel of the optimized product was used to study the influence of various pH values and salts solutions (NaCl, KCl, MgCl₂, and CaCl₂) on the equilibrium swelling. In addition, swelling kinetics in distilled water and on–off switching behavior were preliminarily investigated. The results showed that superabsorbent hydrogel was responsive to the pH and salts.     

Synthesis and characterization of thermoresponsive isopropylacrylamide-acrylamide hydrogels

In this study, hydrogels of poly(N-isopropylacrylamide-co-acrylamide) having a thermoresponsive character were prepared by a redox polymerization method. NIPAM-co-AAm hydrogels with different thermoresponsive properties were obtained by changing the initial NIPAM/AAm mole ratio and crosslinker concentration.Equilibrium-swelling ratio, dynamic swelling ratio and dynamic deswelling ratio were evaluated for all hydrogel systems. The fast shrinking was observed with all gels. The time required for equilibrium shrinking increased with the increase of acrylamide content in the gel.     

Modified carrageenan 3. Synthesis of a novel polysaccharide-based superabsorbent hydrogel via graft copolymerization of acrylic acid onto kappa-carrageenan in air

A novel biopolymer-based superabsorbent hydrogel was synthesized through chemically crosslinking graft copolymerization of acrylic acid (AA) onto kappa-carrageenan (κC), in the presence of a crosslinking agent and a free radical initiator. A proposed mechanism for κC-g-polyacrylic acid was suggested and the affecting variables onto graft polymerization (i.e. the crosslinker, the monomer and the initiator concentration, the neutralization percent and reaction temperature) were systematically optimized to achieve a hydrogel with swelling capacity as high as possible. Maximum water absorbency of the optimized final product was found to be 789 g/g. The swelling capacity of the synthesized hydrogels was also measured in various salt solutions. The time-temperature profile of the polymerization reaction, in order to investigate the effect of molecular oxygen was conducted in terms of the absence and presence of the atmospheric oxygen. The overall activation energy (E_a) of the graft polymerization reaction was found to be 2.93 KJ/mol.     

Collagen-based highly porous hydrogel without any porogen: Synthesis and characteristics

In this contribution we have developed a collagen-based highly porous hydrogel by neutralizing the grafted poly(acrylamide-co-acrylic acid) after gel formation. Preparation of the hydrogels involved free radical polymerization of a combination of hydrolyzed collagen, acrylic acid (AA), acrylamide (AAm) and distilled water, in appropriate amounts and contained a crosslinking agent called N,N′-methylene bisacrylamide (MBA). The chemical structure of the hydrogels was characterized by means of FTIR spectroscopy, DSC and TGA thermal methods. Morphology of the samples was examined by scanning electron microscopy (SEM). Systematically, the certain variables of the graft copolymerization were optimized to achieve maximum swelling capacity. The absorbency under load (AUL) and centrifuge retention capacity (CRC) were measured. 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.     

Taguchi optimized synthesis of collagen-g-poly(acrylic acid)/kaolin composite superabsorbent hydrogel

A novel biopolymer-based hydrogel composite was synthesized through chemical crosslinking by graft copolymerization of partially neutralized acrylic acid onto the hydrolyzed collagen. The Taguchi method, a robust experimental design, was employed for the optimization of the synthesis based on the swelling capacity of the hydrogels. This method was applied for the experiments and standard L16 orthogonal array with five factors and four levels. In the synthesis of the composite superabsorbent, N,N′-methylene bisacrylamide (MBA) as crosslinker, ammonium persulfate (APS) as initiator, acrylic acid (AA) as monomer, neutralization percent (NU), and collagen/kaolin weight ratio were used as important factors. From the analysis of variance of the test results, the most effective factor controlling equilibrium swelling capacity was obtained and maximum water absorbency of the optimized final product was found to be 674 g/g. The surface morphology of the gel was examined using scanning electron microscopy. Furthermore in this research, swollen gel strength of composite SAPs already swollen under realistic conditions (saline solution absorbency under load) was determined.     

Grafting of acrylamide onto kappa-carrageenan via γ-irradiation: Optimization and swelling behavior

The Taguchi method, a robust experimental design for optimization, was used for the synthesis of a superabsorbent hydrogel network using γ-rays as an initiator, energy source and crosslinker at the same time. Nine different samples of superabsorbent hydrogels were prepared in various conditions from kappa-carrageenan (κC) and acrylamide by γ-irradiation at room temperature. Considering the results of nine trials and according to analysis of variance (ANOVA), a new experimental condition with the concentrations of κC and acrylamide 1.5 g and 0.028 mol (2 g in total volume of 50 mL H₂O), respectively, as well as γ-ray at the optimum total dose (7 kGy) was proposed. After preparing the desired hydrogels according to optimum condition, the swelling behavior of hydrogels in different media was investigated.     

Preparation and characterization of poly(acrylic acid)‐iron rich smectite superabsorbent composites

A novel poly(acrylic acid)‐iron rich smectite (IRS) superabsorbent composite was synthesized by graft copolymerization reaction of acrylic acid (AA) in the presence of N,N‐methylenebisacrylamide (MBA) as a crosslinker. IRS was used to strengthen the hydrogel products in the polymerization process. Water absorbencies for these superabsorbent composites in water and saline solutions were investigated. IRS caused a reduced equilibrium swelling as low as 8–26%. However, grafted IRS particles resulted in improved gel strength as high as 66% compared to the IRS‐free sample. IRS modified superabsorbent hydrogel composites exhibited higher thermal stability compared to the IRS‐free sample. The pH dependent reversible swelling behavior of hydrogels was also investigated. It is found that the swelling process is pH dependent and reversible for synthesized superabsorbent. Superabsorbent hydrogel composites were characterized by thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). FTIR spectroscopy was confirmed grafting of acrylic chains onto the surface of IRS particles. From the standpoint of these results, these strengthened and thermostabilized hydrogels may be considered as good candidates for a controlled release study and agricultural applications. Copyright © 2007 John Wiley & Sons, Ltd.     

E-beam radiation synthesis of xanthan-gum/carboxymethylcellulose superabsorbent hydrogels with incorporated graphene oxide

In this study the electron beam (e-beam) radiation synthesis in “paste-like condition” and characterization of the network structure of acrylic acid (AA) sodium salt/xanthan gum (XG)/carboxymethylcellulose (CMC) superabsorbent hydrogels incorporating graphene oxide (GO) was investigated. The effects of the AA concentration on gel fraction, sol-gel analysis, swelling degree and network parameters, as well as the relationship between these parameters and radiation dose was also established.

Gel fraction exceeds 90%, and the p₀/q₀ ratio shows a moderate degradation process. The swelling kinetic data were used to determine, first the swelling degree, second the diffusion characteristics, and third the average molecular weight between crosslinks (Mc), as well as. The diffusion data revealed a Fickian mechanism transport, for each hydrogel compositions. The network parameters (Mc and ξ) increased with absorbed dose, while cross-linking density and the radiation-chemical yields were decreased.     

Superabsorbent hydrogels based on cellulose for smart swelling and controllable delivery

Novel superabsorbent hydrogels were prepared successfully from carboxymethylcellulose sodium (CMC) and cellulose in the NaOH/urea aqueous system by using epichlorohydrin (ECH) as cross-linker. The structure and morphology of the hydrogels were characterized by FT-IR spectroscope, thermogravimetric analysis and scanning electron microscope. The results revealed that the CMC contributed to the enhanced size of pore, whereas cellulose as a strong backbone in the hydrogel to support it for keeping its appearance. Their equilibrium swelling ratio in distilled water and different physiological fluids were evaluated, indicating the maximum swelling ratio in water reached an exciting level of 1000 as the hydrogels still keeping a steady appearance. Moreover, the hydrogels exhibited smart swelling and shrinking in NaCl or CaCl₂ aqueous solution, as well as the release behavior of bovine serum albumin (BSA) that could be controlled by changing CMC content. The cellulose-based hydrogels are promising for the applications in the biomaterials area.     

Probing Viscosity of Co-Polymer Hydrogel and HeLa Cell Using Fluorescent Gold Nanoclusters: Fluorescence Correlation Spectroscopy and Anisotropy Decay

Fluorescence dynamics of gold nanoclusters (Au₉ and Au₂₅) are studied in the complex and crowded environment of a triblock co-polymer (F127) hydrogel and inside cervical cancer cell, HeLa. In the hydrogel, spherical micelles of F127 remain immobilized with a hydrophobic core (PPO) and a hydrophilic corona (PEO) region. The fluorescence anisotropy decay suggests that the timescale of rotational relaxation in the hydrogel is similar to that in bulk water (viscosity ∼1 cP). From fluorescence correlation spectroscopy (FCS) it is inferred that the local viscosity in the hydrogel is 12 cP for Au₉ and 18 cP for Au₂₃. These results indicate that gold nanoclusters (AuNCs) localize in the corona region of the hydrogel. Evidently, frictions against rotation and translation are different inside the gel. It is suggested that rotation of the AuNCs senses the immediate water-like “void” region while translation motion involves in-and-out movement of the AuNCs at the periphery of the gel. Finally, the gold nanoclusters are used for cell imaging and estimation of intracellular viscosity of HeLa cells.     

Photo cross-linked biodegradable hydrogels for enhanced vancomycin loading and sustained release

A series of biodegradable hydrogels based on dextran and poly（L-glutamic acid） were fabricated for effective vancomycin loading and release. The preparation of hydrogels was simply achieved by photo cross-linking of methacrylated dextran and poly（L-glutamic acid）-g-hydroxyethyl methacrylate （PGH） in the presence of photoinitiator 12959. The structures of hydrogels were characterized by FTIR and SEM. The swelling and enzymatic degradation behaviors of hydrogels were examined to be dependent on the poly（L-glutamic acid） content in the hydrogels. The higher content of poly（L-glutamic acid） in the gel, the higher swelling ratio and quicker degradation were observed. More interestingly, the hydrogel with higher PGH ratio showed higher vancomycin （VCM） loading content, which might be due to the electrostatic interaction between carboxylate groups in hydrogel and ammonium group of VCM. In vitro drug release from the VCM-loaded hydrogels in aqueous solution exhibited sustained release of VCM up to 72 h, while the in vitro antibacterial test based on the VCM-loaded hydrogel showed an efficient Methicillin-Resistant S. aureus （MRSA） inhibition extending out to 7 days. These results demonstrated that the biodegradable hydrogels which formed by in situ photo-cross linking would be promising as scaffolds or coatings for local antibacterial drug release in tissue engineering.     

Optical and morphological characterization of polyacrylamide hydrogel and liquid crystal systems

In this work, the thermotropic liquid crystal MBBA (N-(4-methoxybenzilidene)-4-butylaniline), entrapped on hydrogels, based on cross-linked polyacrylamide (PAAm), was studied. The liquid crystalline phases of system were characterized by polarized optical microscopy (POM), refractive index, optical transmittance, scanning electron microscopy (SEM) and water loss. It was verified the presence of birefringence on hydrogel + liquid crystal. The dynamic of formation of such birefringence finished 40 days after the hydrogel synthesis. The effective birefringence Δn, i.e., the difference on refractive index of polyacrylamide hydrogel to refractive index of hydrogel + liquid crystal (Δn₁) and the difference on refractive index of liquid crystal (MBBA) to refractive index of hydrogel + liquid crystal (Δn₂) are dependent of content of acrylamide (AAm) and MBBA on hydrogel. The increase on Δn₁ and Δn₂ with the polyacrylamide content on hydrogel was attributed to decreasing of the mobility liquid crystal inside the hydrogel. Also, an increase on MBBA concentration in the polymeric matrix provides a reduction in the values of optical transmittance in the system. The morphology observed by SEM shows that hydrogel + liquid crystal is more compact that PAAm hydrogels. The presence of MBBA causes an increase in hydrophobicity. The water loss speed is favored by the increase in the amount of MBBA present in the hydrogels.     

Radiation Synthesis of Superabsorbent Hydrogels Based on Chitosan and Acrylic Acid for Controlled Drug Release

Superabsorbent hydrogels based on the natural polymer chitosan and acrylic acid (CS/AAc) was prepared using ⁶⁰Co gamma radiation as a source of initiation and crosslinking. The factors, which affect the preparation of CS/AAc hydrogels such as irradiation dose, CS/AAc ratios, and acrylic acid monomer concentrations, to get the best optimum conditions, were investigated. The kinetic studies of the swelling of CS/AAc hydrogel showed that it follows a Fickian type of water diffusion. The Fickian constant value ‘n’ was more than 0.5 with a high swelling capacity of 300 g/g as superabsorbent hydrogel. In addition, the suitability of CS/AAc hydrogel as carrier material for the drug Chlortetracycline-HCl has been investigated by adsorption isotherm studies. The performance of drug release from hydrogel systems, influenced by acrylic acid ratio and the effect of pH of the medium was studied.     

Evaluation of the degree of cross-linking of cellulose-based superabsorbent hydrogels: a comparison between different techniques

Three different techniques have been applied to the evaluation of the degree of cross-linking of superabsorbent cellulose-based hydrogels obtained from water solutions of carboxymethylcellulose sodium salt (CMCNa) and hydroxyethylcellulose (HEC), chemically cross-linked with divinyl sulfone. These polyelectrolyte hydrogels are biodegradable and have the same sorption capacity as acrylate-based superabsorbents on the market. A ¹³C solid state NMR analysis was carried out on dry samples of hydrogel to obtain the degree of cross-linking, an important parameter that affects the swelling and mechanical properties of a hydrogel. Dynamic mechanical analysis was performed during the hydrogel cross-linking using a parallel plate rheometer under oscillatory deformations in order to monitor the evolution of the hydrogel viscoelastic properties during the synthesis. The value of |G*| and the slope of the stress-deformation ratio plots from uniaxial compression tests were used to evaluate the elastically effective degree of cross-linking according to classical rubber elasticity theory. Moreover, a dynamic mechanical analysis was carried out on cross-linked hydrogels at different degrees of swelling in order to investigate the influence of the swelling on the mechanical properties and the application of rubber elasticity theory to swollen hydrogels.     

Control of the structure of polyacrylamide hydrogel

It has been shown via the example of three types of polyacrylamide hydrogels synthesized through the usual radical copolymerization of acrylamide and N,N′-methylene-bisacrylamide, the copolymerization of these monomers in the presence of a chain-transfer agent, and the pseudoliving copolymerization in the presence of a reversible-chain-transfer agent that one of the factors determining the microstructure of crosslinked polymer systems is the molecular-mass distribution of the copolymer forming at the initial step of the process. The closer the M _w/M _n ratio of the copolymer is to unity, the lower the contribution of larger pores in the total number of hydrogel pores.     

Adsorption of Apollo reactive dyes on poly(N,N dimethylamino ethylmethacrylate) hydrogels

Poly(N,N-dimethylamino ethylmethacrylate) [P(DMAEMA)] hydrogels were prepared by irradiating the ternary mixtures of dimethylamino ethylmethacrylate (DMAEMA)/ethyleneglycol dimethacrylate (EGDMA)/water (H₂O) by γ-rays at ambient temperature. The swelling of four types of DMAEMA hydrogels in distilled water is higher than the swelling of these hydrogels in dye solutions. The value of equilibrium swelling of P(DMAEMA)1 hydrogel was 338% at pH 7.0 in distilled water, while it was 325% and 326% at pH 7.0 in Apollofix Red (AR) and Apollofix Yellow (AY) solutions, respectively. The adsorption capacity of P(DMAEMA)1 hydrogel was found to increase from 85 to 131 mg for AR g⁻¹ dry gel and from 58 to 111 mg for AY g⁻¹ dry gel with decreasing pH of the dye solutions.     

新型半纤维素基磁性水凝胶的制备及性能

采用H₂O₂-Vc氧化还原体系引发半纤维素衍生物,以表面修饰的Fe₃O₄粒子作为磁性组分,利用接枝共聚方法制备了新型半纤维素基磁性水凝胶. 分别用傅里叶变换红外(FTIR)光谱、X射线光电子能谱(XPS)和扫描电子显微镜(SEM)对水凝胶的结构及形貌进行了表征,利用X射线衍射(XRD)和振动样品磁强计(VSM)对水凝胶的晶型结构及磁性能进行了分析,发现Fe₃O₄粒子均匀分散在凝胶网络中,半纤维素基磁性水凝胶表现出良好的顺磁性. 考察了丙烯酸/半纤维素比例、Fe₃O₄粒子含量及交联剂用量对水凝胶溶胀性能的影响,并探讨了该水凝胶的溶胀机理,它在pH 8 缓冲溶液中的溶胀较好符合Fickian 和Schott 动力学模型. 通过SEM和溶胀性能分析表明,随着pH值的升高水凝胶的孔径增大,水凝胶的溶胀率逐渐增大. 制备的水凝胶被用于溶菌酶吸附研究,结果表明磁性凝胶的吸附量大于非磁性水凝胶,水凝胶的吸附行为符合Freundlich 和Temkin 等温模型.     

Synthesis and Characterization of Hydrogels Based on Gamma Radiation Copolymerization of N‐isopropylacrylamide and Ethylene Glycol Dimethacrylate Monomers

Hydrogels based essentially on N‐isopropylacrylamide (NIPAAm) and different ratios of ethylene glycol dimethacrylate (EGDMA) monomer were synthesized by gamma radiation copolymerization. The thermal decomposition behavior of NIPAAm/EGDMA hydrogels was determined by thermogravimetric analysis (TGA). The effect of temperature and pH on the swelling behavior was also studied. The results showed that the ratio of EGDMA in the comonomer feeding solution has a great effect on the yield product, gel fraction and water content in the final hydrogel. In this regard, it was observed that the increase of EGDMA ratio decreased these properties. The TGA study showed that all the compositions of NIPAAm/EGDMA hydrogels displayed higher thermal stability than the hydrogel based on pure PNIPAAm hydrogel. The swelling kinetics in water showed that pure PNIPAAm and NIPAAm/EGDMA hydrogels reached equilibrium after 6 h. However, NIPAAm/EGDMA hydrogels show swelling in water lower than pure PNIPAAm. The results showed that the swelling character of pure PNIPAAm and NIPAAm/EGDMA hydrogels was affected by the change in temperature within the temperature range 25–40°C, and showed a reversible change in swelling in the pH range 4–7 depending on composition.     

Synthesis of cross-linked carboxymethyl cellulose and poly (2-acrylamido-2-methylpropane sulfonic acid) hydrogel for sustained drug release optimized by Box-Behnken Design

This research aims to fabricate and characterize chemically crosslinked CMC/PVP-co-poly (AMPS) based hydrogel for the sustained release of model drug metoprolol tartrate through the free radical polymerization technique. Box-Behnken Design was used to optimize CMC/PVP-co-poly (AMPS) hydrogel by varying the content of reactants such as; polymers (CMC and PVP), monomer (AMPS), and crosslinker (EGDMA). Carboxymethyl cellulose (CMC) was crosslinked chemically with AMPS with a constant ratio of PVP by the ethylene glycol dimethacrylate as the crosslinker in the presence of sodium hydrogen sulfite (SHS)/ammonium peroxodisulfate (APS) as initiators. After developing CMC-based hydrogels using different polymers, monomer, and crosslinker concentrations, this study encompassed dynamic swelling, sol–gel fraction, drug release and chemical characterizations such as FTIR, XRD, TGA, DSC, and SEM. In vitro drug release and swelling were performed at 1.2 and 6.8 pH to determine the sustained release pattern and pH-responsive behavior. These parameters depended on the crosslinker, polymer, and monomer ratios used in the formulation development. XRD, SEM, and FTIR showed the successful grafting of constituents resulting in the formation of a stable hydrogel. DSC and TGA confirmed the thermodynamic stability of the hydrogel. Hydrogel swelling was increased with an increase in the ratio of monomer; however, an increase in the ratio of polymer and crosslinker decreased the hydrogel swelling. In vitro gel fraction and drug release also depended on polymer, monomer, and crosslinker ratios. The fabricated CMC/PVP-co-poly (AMPS) hydrogels constituted a potential system for sustained drug delivery.