Synthesis and super-swelling behavior of a novel protein-based superabsorbent hydrogel

Summary In this work, we synthesize a novel protein-based superabsorbent hydrogel and study its swelling behavior. The crosslinking graft copolymerization of acrylic acid (AA) onto the hydrolyzed collagen as a protein backbone was carried out in a homogeneous medium. Potassium persulfate (KPS) as an initiator and N,N^′-methylene bisacrylamide (MBA) as a crosslinker were used. The product’s structure was established using FTIR spectroscopy. We were systematically optimized the certain variables of the graft copolymerization (i.e. the monomer, the initiator, and the crosslinker concentration) to achieve a hydrogel with maximum swelling capacity. Under this condition, maximum capacity of swelling in distilled water was found to be 920 g/g. Morphology of the optimized sample was examined by scanning electron microscopy (SEM). The swelling ratio in various salt solutions was also determined. Additionally, the swelling of superabsorbing hydrogels was measured in solutions with pH ranged from 1 to 13. The synthesized hydrogel exhibited a pH-responsiveness character so that a swelling-collapsing pulsatile behavior was recorded at pH 2 and 8.     

Radiation Synthesis of Polyampholytic and Reversible pH-Responsive Hydrogel and Its Application as Drug Delivery System

Graft copolymerization of acrylic acid (AA) and acrylamide (AAm) onto chitosan (CS) was carried out using gamma irradiation. Their swelling behavior was investigated. The hydrogels before and after alkaline hydrolysis were confirmed by FTIR spectroscopic studies. The hydrogels show ampholytic and reversible pH-responsiveness characteristics. The swelling variations were explained according to swelling theory based on the hydrogel chemical structure. The ability of the prepared copolymer to be used as gastric antibiotic delivery system was estimated using amoxicillin trihydrate as a model drug. Release of amoxicillin trihydrate from these investigated hydrogels was studied. For non-ionized drugs, such as amoxicilin trihydrate, the electrostatic polymer/ polymer interactions take place between the cationic groups from CS and the anionic ones from PAA resulting in entrapping the drug into the mesh space of the hydrogel. The non-ionized amoxicillin release was controlled by the swelling/eroding ratio.     

Synthesis and characterization of superabsorbent hydrogels composites based on polysuccinimide

A kind of novel superabsorbent hydrogel with high swelling ratio property that could be used for the development of water absorbing resin, soil water retention agent, and chemical sand‐fixing material was synthesized in this study. The hydrogels were prepared by the crosslinking reaction of polysuccinimide (PSI). The relationships between swelling ratio and volume of solvent as well as the concentration of crosslinking agent were investigated in detail. Several composites, such as starch, carrageenan, and polyacrylamide, were added into hydrogels to enhance the swelling ratio. It was found that the swelling ratio was significantly increased, which the maximum water absorbency was enhanced 2.46 times when the composite polyacrylamide (PAM) was added compared to the control. The effects of ionic strength and sensitivity of pH on hydrogels were also studied. The modified hydrogels products with swelling ratio less sensitivity to the salinity as well as relative high swelling ration in salinity system were also obtained by adding PAM. Through the Fourier transform infrared spectroscopy (FTIR) characterizations, the crosslinking reaction mechanism and the structure of composite were proposed. In addition, the transmission electron microscopy (TEM) examinations showed that some composite materials elevated the physical crosslinked and connected channels density substantially. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 550–557, 2006     

Synthesis and superswelling behavior of carboxymethylcellulose–poly(sodium acrylate‐co‐acrylamide) hydrogel

In this paper, attention is paid to synthesis and swelling behavior of a superabsorbent hydrogel based carboxymethylcellulose (CMC) and polyacrylonitrile (PAN). The physical mixture of CMC and PAN was hydrolyzed in NaOH solution to yield hydrogel, CMC–poly(NaAA‐co‐AAm). During alkaline hydrolysis, the nitrile groups of PAN were completely converted to a mixture of hydrophilic carboxamide and carboxylate groups followed by in situ crosslinking of the grafted PAN chains. A proposed mechanism for hydrogel formation was suggested and the structure of the product was established using FTIR spectroscopy. The reaction variables affecting the swelling capacity of the hydrogel were systematically optimized to achieve a hydrogel with swelling capacity as high as possible. Swelling measurements of the synthesized hydrogels in various chloride salt solutions indicated a swelling‐loss with increase in the ionic strength of the salt solutions. The pH of the various solutions also affected the swelling of the superabsorbent. Furthermore, the present hydrogels showed a pH‐reversible property. Finally, the swelling kinetics of synthesized hydrogels with various absorbent particle sizes was briefly examined. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of pH- and thermoresponsive Poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide-co-itaconic acid) hydrogels crosslinked with <Emphasis Type="Italic">N</Emphasis>-maleyl chitosan

Biodegradable cross-linker N-maleyl chitosan (N-MACH) was synthesized with chitosan (CS) and maleic anhydride (MA) by acylation. With N-MACH cross-linker, a series of cross-linked poly(N-isopropylacrylamide-co-itaconic acid) [P(NIPAAm-co-IA)] hydrogels were prepared, and their pH-and temperature-responsive behaviors, water contents, swelling/deswelling kinetics were investigated. By alternating the NIPAAm/IA weight ratios, hydrogels had the volume phase transition temperature (VPTT) changed from 33 to 38 °C, whereas cross-linking density did not affect the VPTT apparently. The water content of hydrogels was controlled by the monomer weight ratios of NIPAAm/IA, swelling media, and the cross-linking density. The results of the influence of pH value on the swelling behaviors showed that the minimum swelling ratios of the hydrogels appeared in neutral buffer solution, which was attributed to chemical composition of the hydrogels and the swelling media. In the swelling/deswelling kinetics, all the dried hydrogels exhibited fast swelling within 480 min and fast deswelling within 20 min, which was independent of the content of IA and cross-linker.     

Preparation and characterization of microporous sodium poly(aspartic acid) nanofibrous hydrogel

A novel biodegradable sodium poly(aspartic acid) (PASP) hydrogel with microporous structure was manufactured using electrospun polysuccinimide (PSI) nanofibers. PSI is the intermediate of sodium PASP and could be electospun into nanofibers easily. Firstly, PSI nanofibers were prepared from PSI/N, N-dimethylformamide solution. Then the PSI nanofibrous mats were crosslinked and hydrolyzed to obtain biodegradable microporous sodium PASP nanofibrous hydrogels. The chemical structures, morphologies and pore sizes of PSI nanofibrous mats and microporous sodium PASP nanofibrous hydrogels were investigated. Moreover, the properties of PSI electrospinning solutions, and the swelling ratio and biodegradability of sodium PASP hydrogels were also examined. The results showed that the swelling ratio of microporous sodium PASP nanofibrous hydrogels achieved to 21.0–24.3 g/g and were obviously higher than that of the sodium PASP casting film, reporting a swelling ratio of only 4.6 g/g. When the microporous sodium PASP nanofibrous hydrogel was immersed in water, it exhibited quick absorption and morphological robustness. The microporous sodium PASP nanofibrous hydrogel showed 83 wt% weight loss after 7 days of trypsin catalyzed biodegradation, and the SEM analysis demonstrated the significant morphology change of the microporous sodium PASP nanofibrous hydrogel during the biodegradation.     

Fabrication of 3D Polypyrrole/Graphene Oxide Composite Hydrogels with High Performance Swelling Properties

The polypyrrole (PPy)/graphene oxide (GO) composite hydrogels with hierarchical porous structures were fabricated by one-step self-assembly method. The static oxidation polymerization of pyrrole monomer in GO aqueous solution resulted in the formation of three-dimensional (3D) PPy/GO composite hydrogels, which consisted of one-dimensional PPy nanofibers and two-dimensional GO nanosheets. The as-prepared composite hydrogels exhibited shrinking–swelling behavior with cycles of suction and water-supplying. The effects of GO nanosheets content on the swelling properties were investigated. Results showed that the well-dispersed GO nanosheets in the hydrogel networks resulted in a significant improvement in water absorbencies of the hydrogels. PPy/GO composite hydrogels exhibited unobvious variation in the water absorbency even in saline solutions. Such excellent properties in water absorbencies endow the conducting 3D PPy/GO composite hydrogels with great potential applications in electrochemical sensors or controlled release.     

Preparation and characterization of biocompatible spongy cryogels of poly(vinyl alcohol)–gelatin and study of water sorption behaviour

Porous biocompatible spongy hydrogels of poly(vinyl alcohol) (PVA)–gelatin were prepared by the freezing–thawing method and characterized by infrared and differential scanning calorimetry. The prepared so‐called ‘cryogels’ were evaluated for their water‐uptake potential and the influence of various factors, such as the chemical architecture of the spongy hydrogels, pH and the temperature of the swelling bath, on the degree of water sorption by the cryogels was investigated. It was found that the water sorption capacity constantly decreased with increasing concentration of PVA while initially an increase and thereafter a decrease in swelling was obtained with increasing amounts of gelatin in the cryogel. The water sorption capacity decreased with an increase in the number of freeze–thaw cycles. The hydrogels were also swollen in salt solutions and various simulated biological fluids and a fall in swelling ratio was noticed. The effect of the drying temperature of the cryogel on its water sorption capacity was also investigated, and a decrease in swelling was obtained with increasing temperature of drying. The biocompatibility of the prepared materials was assessed by in vitro methods of blood‐clot formation, platelet adhesion, and per cent haemolysis. It was noticed that with increasing concentration of PVA and gelatin the biocompatibility increased, while a reduced biocompatibility was noted with an increasing number of freeze–thaw cycles. Copyright © 2005 Society of Chemical Industry     

Ultrasonic monitoring of the network formation in superabsorbent cellulose based hydrogels

Biodegradable hydrogels are finding increasing interest in the academic and industrial field due to their high swelling capacity and the potential for many novel applications enabled by their biodegradability. The monitoring of the hydrogel cross-linking process is a crucial step for predicting hydrogel performances in terms of degree of swelling and viscoelastic properties.In this work, the chemical cross-linking of cellulose based hydrogels has been monitored during synthesis in water by means of ultrasonic wave propagation and low frequency dynamic mechanical analysis (DMA). The effect of the cross-linker concentration on the hydrogel acoustic behaviour has been also analysed and correlated with the different elastic response developed by the macromolecular hydrogel.The results demonstrate the reliability of the ultrasonic wave propagation in the following network formation process of a superabsorbent hydrogel, being capable of following the limited changes in the physical properties of the reacting solution.     

A promising porous polymer-nanoclay hydrogel nanocomposite as water reservoir material: synthesis and kinetic study

A porous hydrogel nanocopmposite based on biodegradable salep and montmorillonite (MMT) was synthesized by in-situ free radical graft polymerization of salep chains with acrylic acid (AA) monomers. The chemical structure and morphological properties of the prepared hydrogels was evaluated by FTIR spectroscopy, X-ray diffraction and SEM techniques. The effect of reaction variables such as crosslinker, initiator, monomer and clay contents on equilibrium water absorption capacity and swelling kinetic of hydrogel were investigated and optimized. Swelling behavior of the hydrogels in various pH and saline solutions was also studied. Incorporation of MMT into hydrogel matrix caused the formation of porous hydrogel network. These porous structures resulted in higher water uptake capacity and swelling rate in hydrogel nanocomposite in comparison to neat hydrogel sample. Moreover, hydrogel nanocomposite sample exhibited proper salt and pH-sensitive behavior. High swelling capacity and rate, porosity, salt and pH sensitivity make hydrogel nanocomposite a profitable candidate in agricultural and horticultural applications, such as water reservoir system.     

Swelling of pH‐sensitive chitosan–poly(vinyl alcohol) hydrogels

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     

Temperature and pH sensitive hydrogels composed of chitosan and poly(ethylene glycol)

Summary Chitosan based semi-interpenetrating polymer network (semi-IPN) hydrogels containing different amounts of poly(ethylene glycol) (PEG) were prepared. The crosslinking of the hydrogels was achieved by using a naturally occurring nontoxic cross-linking agent genipin. The swelling behaviour of these hydrogels was studied by immersing the films in deionized water at 25, 37 and 45 °C and in media of different pHs at 37 °C. Swelling was found to be dependent on temperature, pH of the medium and the amount of PEG in the gel. States of water in the hydrogels swollen in deionized water at 37 °C were determined using Differential Scanning Calorimetry (DSC). The equilibrium water content and the amount of freezing water in the swollen hydrogels increased with the increase in PEG concentration in the gels.     

Partially hydrolyzed kappa carrageenan—polyacrylonitrile as a novel biopolymer‐based superabsorbent hydrogel: Synthesis,characterization, and swelling behaviors

In this paper, synthesis and swelling behavior of a novel superabsorbent hydrogel based on kappa carrageenan (κC) and polyacrylonitrile (PAN) was investigated. To achieve partially hydrolyzed κC‐PAN hydrogel, physical mixture of κC and PAN was hydrolyzed by NaOH solution. During alkaline hydrolysis, the nitrile groups of PAN are converted to a mixture of hydrophilic carboxamide and carboxylate groups follow by in situ crosslinking of the grafted PAN chains. The reaction variables affecting on the swelling capacity of the hydrogel were systematically optimized to achieve a hydrogel with swelling capacity as high as possible. Under the optimized conditions concluded, super swelling hydrogel with the ability of water absorption up to 3260 g/g (water/dry hydrogel powder) has been prepared. Swelling measurements of the synthesized hydrogels was carried out in various salt solutions and solutions with different pH. The results indicate that the hydrogels have good pH sensitivity and pH‐reversible property between pH 2 and pH 8. POLYM. ENG. SCI. 46:1778–1786, 2006. © 2006 Society of Plastics Engineers.     

The effect of PEG(400)DA crosslinking agent on swelling behaviour of acrylamide-maleic acid hydrogels

Summary Acrylamide (AAm)-maleic acid (MA) hydrogels with different monomer ratios were prepared in an aqueous solution by radical polymerization using a new crosslinking agent, polyethyleneglycol (400) diacrylate (PEG (400) DA) and also using N, N’-methylenebisacrylamide (NMBA) for comparison purpose. The hydrogels were characterized by acid group content and FTIR spectroscopy. Their swelling and deswelling behavior were studied as a function of maleic acid content, pH and crosslinking agent. Incorporation of MA in hydrogels significantly increased their swelling ability and their equilibrium degree of swelling (EDS) values changed between 100–269 g water/g polymer in water while AAm polymers swollen less (22–23 g water/g polymer). The AAm hydrogels showed Fickian type diffusion but the all AAm-MA hydrogels showed non-Fickian type behavior. Their swelling degree increased with the increase of pH of the external medium and an instantaneous increase was observed near a pH value of 7.0. The use of PEG (400) DA instead of NMBA as a crosslinking agent also increased the swelling rate and capacity of the gel. The swelling constant (K) and the diffusion coefficient (D) of hydrogels were also increased. The swelling-deswelling cycles in acidic-basic solutions showed that they could be used as pH responsive gels without any decrease in swelling capacity.     

Polymer Hydrogels: A Review

This review encompasses definitions, classification, main properties, and application of polymer hydrogels. Raw materials and preparation techniques of polymer hydrogels were described. The factors that affect absorption capacity and swelling properties of polymer hydrogels were reviewed. PHG materials are defined as a viscoelastic network structure, swellable and not soluble in water with high absorbent capacity, which may reach 1000 g/g of their dried weight to be termed “superabsorbent polymer hydrogels”. PHGs have the ability to release absorbed fluids under certain circumstances.     

改性聚天冬氨酸复合水凝胶的制备及性能

以聚琥珀酰亚胺（PSI）、丙烯酸（AA）和丙烯酰胺（AM）为原料,KH550和KH570为联合交联剂,采用水溶液聚合法合成了聚天冬氨酸/聚（丙烯酸-丙烯酰胺）复合水凝胶［KPAsp/P（AA-AM）］;探讨了交联剂用量、原料配比对KPAsp/P（AA-AM）复合水凝胶溶胀性能的影响;采用FTIR和TG对水凝胶进行了表征。结果表明当v（KH550）∶v（KH570）=1∶1和n（PSI）∶n（AA）∶n（AM）=1∶3∶1时,所合成的复合水凝胶溶胀性能最佳,溶胀度达到395。通过吸水动力学研究表明,共聚链的引入改变了水凝胶的吸水行为。研究了复合水凝胶对阿莫西林的控释性能,结果表明,复合水凝胶的载药量可达29.98mg/g;在37℃、pH=1.8的NaCl溶液中,负载了阿莫西林的复合水凝胶在2h对药物的释放率达到57%,24h左右达到85%。     

Cellulose-graft-polyacrylamide/hydroxyapatite composite hydrogel with possible application in removal of Cu (II) ions

Cellulose-graft-polyacrylamide/hydroxyapatite composite hydrogels of different weight ratios were prepared through a suspension polymerization method. Physical and chemical characteristics of the composite were investigated by Fourier transform infrared spectroscopy and scanning electron microscopy. The swelling behaviors of the composite hydrogels were investigated under varying conditions of time, temperature and pH. The optimized swelling capacity in standard conditions was found to be 5197% per gram of the hydrogel. The prepared hydrogel has the potential to be used for ion adsorption in water treatment. Such a possibility was examined through adsorption of copper (II) ions from an aqueous solution. The effects on adsorption of varying the time, pH, and initial concentration of copper (II) solution as well as some thermodynamic parameters were also investigated. The maximum adsorption capacity was found to be 175 mg per gram of composite hydrogel in dried state. The mechanism of adsorption was well presented using a pseudo-second-order kinetic model. Finally, the mercury-loaded hydrogel was regenerated without losing its original activity and stability.     

Swelling and Thermal Characteristics of Genipin Crosslinked Chitosan and Poly(vinyl pyrrolidone) Hydrogels

Summary Chitosan / poly(vinyl pyrrolidone) (PVP) were used to prepare semi-interpenetrating polymeric networks. The hydrogels were crosslinked using genipin, a non-toxic cross-linking agent extracted from the fruits of Gardenia jasminoides Ellis. Swelling properties of these hydrogels were studied in media of different pHs and temperatures. States of water in the swollen hydrogels at 25°C and pH 7 were determined using Differential Scanning Calorimetry (DSC). The swelling behaviour of the hydrogels was found to be dependent on the temperature and the pH of the swelling medium. The total water content in the hydrogels was found to increase with increasing PVP content.     

Swelling and Metal Ion Adsorption Characteristics of Radiation Synthesized Stimuli Responsive PAAm-KC Semi – IPN Hydrogels

The preparation of super absorbent hydrogels based on Kappa-carrageenan and polyacrylamide was carried out by electron beam irradiation technique. The gels were characterized for their temperature and pH responsive behavior by equilibrium swelling experiments and for their structure by FTIR, DSC, and SEM techniques. The effect of polymer composition, dose applied, pH, and temperature on swelling was evaluated. The suitability of these systems as matrix materials for the uptake of Cu²⁺ and Ni²⁺ ions from aqueous solutions was studied. The influence of gel structure and pH conditions on metal ion uptake capacity of gels were investigated. The metal ion uptake capacity has been correlated with the swelling ability of the gels.     

Dual-responsive shape memory hydrogels with self-healing and dual-responsive swelling behaviors

Shape memory hydrogels (SMHs) can fix the hydrogels in a provisional shape and restore the initial shape under external stimulation. Herein, a dual-responsive shape memory hydrogel with dual-responsive swelling and self-healing properties is presented in this work. The SMHs were fabricated by one-step emulsion copolymerization of acrylic acid (AAc), acrylamide (AAm) and stearyl methacrylate (SMA). Sodium alginate (SA) was introduced as an interpenetrating polymer in the network. With ionic cross-linking between -COO⁻ and Fe³⁺ or saline-reinforced hydrophobic association, the hydrogels can be fixed in a provisional shape, which can be restored by immersing the hydrogels in vitamin C solution or pure water, respectively. When the as-prepared hydrogels were immersed in FeCl₃ solutions, additional ionic cross-linking between Fe³⁺ and -COO⁻ could be formed, thus constructing the dual physically cross-linked (DPC) network, which endows the hydrogels with excellent fracture stress (2.6 MPa) and toughness (5.47 MJ/m³). Besides, the reversible physical cross-linkings endowed the hydrogel with outstanding self-healing capability. Furthermore, the pH and saline responsive swelling properties of the SMHs are additional fantastic properties. Therefore, we believe that this simple strategy provides a great opportunity for the preparation of SMHs with multiple intellectual performances.