Thermoreversible hydrogels X: Synthesis and swelling behavior of the (N‐isopropylacrylamide‐co‐sodium 2‐acrylamido‐2‐methylpropyl sulfonate) copolymeric hydrogels

A series of thermosensitive hydrogels were prepared from various molar ratios of N‐isopropylacrylamide (NIPAAm) and sodium‐2‐acrylamido‐2‐methylpropyl sulfonate (NaAMPS). Factors such as temperature and initial total monomer concentration and different pH solutions were investigated. Results indicated that the more the NaAMPS content in hydrogel system, the higher the swelling ratio and the gel transition temperature; the higher the initial monomer concentration, the lower the swelling ratio. The result also indicated that the NIPAAm/NaAMPS copolymeric hydrogels had different swelling ratios in various pH environments. The present gels showed a pH‐reversible property between pH 3 and pH 10 and thermoreversibility. The swelling ratios of copolymeric gels were lower in a strong alkaline environment because the gels were screened by counterions. Finally, the drug release behavior of these gels was also investigated in this article. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1760–1768, 2000     

Thermoreversible hydrogel. XVII. Investigation of the drug release behavior for [N‐isopropylacrylamide‐co‐trimethyl acrylamidopropyl ammonium iodide‐co‐3‐dimethyl (methacryloyloxyethyl) ammonium propane sulfonate] copolymeric hydrogels

A series of copolymeric hydrogels were prepared from various molar ratios of N‐isopropylacrylamide (NIPAAm), trimethyl acrylamidopropyl ammonium iodide (TMAAI), and 3‐dimethyl (methacryloyloxyethyl) ammonium propane sulfonate (DMAPS). Results showed that the swelling ratios of these copolymeric hydrogels increased with an increase of TMAAI content. The drug release behavior of the ionic thermosensitive hydrogels related to their ionicity and drug types. Results indicated that the release ratio of caffeine in the hydrogels was not affected by the ionicity of hydrogels, but increased with increasing of the swelling ratio. The anionic solute (phenol red) strongly interacted with cationic hydrogel (very large K_d), so the phenol red release ratio in cationic gels was very low. On the other hand, CV was adsorbed only on the skin layer of the cationic hydrogel because of the charge repulsion, and released rapidly. Therefore the release ratio was highest for cationic hydrogel to cationic drug. In addition, the partition coefficients (K_d) and the drug delivery behavior of the present gels were also investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1592–1598, 2002     

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     

Synthesis,Characterization, and drug release study of acrylamide‐co‐itaconic acid based smart hydrogel

A new kind of pH and temperature responsive poly(acrylamide‐co‐itaconic acid) hydrogel was prepared by free radical polymerization using ammonium persulfate as initiator and different comonomer ratios. The hydrogels were characterized in terms of chemical composition, swelling‐deswelling behavior, morphology, crystallographic behavior, and drug release properties. All the hydrogels showed high swelling ability in aqueous solutions, the maximum being at pH 7. Swelling decreased on either side of pH 7 (i.e., both in acidic and alkaline region) and increased with increase in temperature. The hydrogel with 10 mol% itaconic acid (IA) absorbed maximum water among the copolymer gels. The cellular structures of the hydrogels were clearly revealed by microscopic analysis and SEM pictures. Swelling of the gels in water followed non‐Fickian type of diffusion principle. The hydrogel was proved to be a controlled release vehicle, for example in drug delivery by using its smart properties. The hydrogel with 10 mol% IA also absorbed maximum amount of drug (ascorbic acid) under study. Incorporation of drug in hydrogel matrix was established from XRD peak analysis. POLYM. ENG. SCI., 55:113–122, 2015. © 2014 Society of Plastics Engineers     

Insight into hydrogels

The development and introduction of injectable biomaterials and the identification of methods through which materials may form in situ are currently the topics of interest in materials science, specifically in the field of biomaterials. Over the last few decades, hydrogels which refers to the swellable polymeric matrices have gained wide attention due to their excellent characteristics such as swelling in different media, pH and temperature sensitivity, and sensitivity to other stimuli. Nowadays, injectable hydrogels have widely been studied due to their excellent insitu gelation at body temperature. These injectable insitu gels serve as depot system which ensures the local and systemic drug and gene delivery. These insitu gels also protect the proteins and peptide drugs invivo from environmental effect. The current review is made to report latest extensive literature regarding hydrogels, their classification, synthesis methods, structure of hydrogel network, methods of crosslinking, environment-sensitive hydrogel system, drug loading, and release, hydrogels as biosensors and applications of hydrogels.     

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     

High‐Strength,Rapidly Self‐Recoverable,and Antifatigue Nano‐SiO2/Poly(Acrylamide–Lauryl Methacrylate) Composite Hydrogels

Creating load‐bearing hydrogels with superior mechanical strength and toughness is of vital importance for promoting the development of polymer hydrogels toward practical applications. Herein, a type of composite hydrogel is facilely fabricated employing simple and effective UV irradiation one‐pot method by introducing cheap and available nanosilica sol into hydrophobic association poly(acrylamide–lauryl methacrylate) (HAPAM gels). Composite hydrogels exhibit enhanced mechanical strength (compression stress reaching 4.4 MPa) and toughness (compression hysteresis energy achieved is 151.15 kJ m^?3) compared to HAPAM gels. Composite hydrogels also demonstrate rapid self‐recovery behavior (95.91% stress recovery and 92.19% hysteresis energy recovery after restoration for 15 min, respectively) and favorable fatigue‐resistant ability without the help of external stimuli at room temperature based on the cyclic loading–unloading compression measurements. The simple and effective design strategy may help the development of hydrogel materials toward practical applications for soft sensors, tissue engineering, and actuators.     

Electrical behavior of chitosan and poly(hydroxyethyl methacrylate) hydrogel in the contact system

Semi‐interpenetrating polymer networks (semi‐IPNs), as polymer hydrogels composed of chitosan and poly(hydroxyethyl methacrylate) (PHEMA), exhibiting electrical‐sensitive behavior, were prepared. The swelling behavior of the chitosan/PHEMA hydrogels was studied by immersing the gels in various concentrations of aqueous NaCl solution. The electrical responses of the semi‐IPN hydrogel, in applied electric fields, were also investigated. When the semi‐IPN hydrogels were swollen, where one electrode was placed in contact with the gel and the other fixed 30 mm apart from one, they exhibited bending behavior on the application of an electric field on a contact system. The electroresponsive behavior of the present semi‐IPN was also affected by the electrolyte concentration of the external solution. The semi‐IPN also showed various degrees of increased bending behavior depending on the electric stimulus. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 915–919, 2004     

Poly[2-(hydroxyethyl methacrylate)-co-(sulfobetaine)]s hydrogels: 1. Synthesis and swelling behaviors of the 2-(hydroxyethyl methacrylate)-co-2-(vinyl-1-pyridinium propane sulfonate) hydrogels

A series of the 2-hydroxyethyl methacrylate/2-vinyl-l-pyridinium propane sulfonate (HEMA/VPPS) copolymeric gels have been prepared from HEMA and zwitterionic monomer VPPS of various molar ratios. The influence of the amount of VPPS in copolymeric gels on their swelling behavior in water and various saline solutions at different temperatures was investigated. Results indicate that the PHEMA hydrogels exhibit an overshooting phenomenon in their dynamic swelling behavior. The maximum overshooting value decreases with increasing temperature. The same results are also shown for the lower VPPS content HEMA/VPPS copolymeric gels. In the equilibrium swelling ratio, the PHEMA hydrogel exhibits a minimum swelling ratio at 55 °C. Then, the minimum swelling ratio disappears gradually with increasing VPPS content in HEMA/VPPS copolymeric gels. In the saline solution, the swelling ratios of HEMA/VPPS copolymeric gels increase rapidly with increasing salt concentration, for salts with a smaller ratio of charge/radius.     

High performances of dual network PVA hydrogel modified by PVP using borax as the structure-forming accelerator

A dual network hydrogel made up of polyvinylalcohol (PVA) crosslinked by borax and polyvinylpyrrolidone (PVP) was prepared by means of freezing-thawing circles. Here PVP was incorporated by linking with PVA to form a network structure, while the introduction of borax played the role of crosslinking PVA chains to accelerate the formation of a dual network structure in PVA/PVP composite hydrogel, thus endowing the hydrogel with high mechanical properties. The effects of both PVP and borax on the hydrogels were evaluated by comparing the two systems of PVA/PVP/borax and PVA/borax hydrogels. In the former system, adding 4.0% PVP not only increased the water content and the storage modulus but also enhanced the mechanical strength of the final hydrogel. But an overdose of PVP just as more than 4.0% tended to undermine the structure of hydrogels, and thus deteriorated hydrogels’ properties because of the weakened secondary interaction between PVP and PVA. Likewise, increasing borax could promote the gel crosslinking degree, thus making gels show a decrease in water content and swelling ratio, meanwhile shrinking the pores inside the hydrogels and finally enhancing the mechanical strength of hydrogels prominently. The developed hydrogel with high performances holds great potential for applications in biomedical and industrial fields.     

通过RAFT聚合方法合成具有高强度和高溶胀率的纳米水凝胶

为了得到具有高强度和高溶胀率的纳米水凝胶(NCgels),N-异丙基丙烯酰胺通过可逆加成断裂链转移(RAFT)聚合的方法,插层在含有质量分数为0.25%～15%的可扩展的有机化的蒙脱土(Clay-S)层间并交联。结果表明,与传统水凝胶相比,该水凝胶的强度和溶胀性能得到了很大提高,并且对温度的变化具有较快的响应速率。以质量分数为5%的蒙脱土,链转移剂的质量分数为0.5%制备的纳米水凝胶为例,该水凝胶在20℃的溶胀率为450,而传统水凝胶在相同温度时的溶胀率仅为20;该水凝胶在1min内失去75%的水,在4min内失去约90%的水,而传统水凝胶在15min内仅失去66%左右的水。     

Polyampholytic hydrogels: Poly(N-isopropylacrylamide)-based stimuli-responsive networks with poly(ethyleneimine)

Polyampholytic hydrogels are crosslinked networks composed of positively and negatively charged repeat units that show entirely different properties from their originate polyelectrolyte polymers. Here we report a series of stimuli-responsive polyampholytic hydrogels designed with poly(N-isopropylacrylamide-co-sodium acrylate)/poly(ethyleneimine) [poly(NIPAM-co-SA)/PEI] through the interpenetrating network method. The polyampholytic IPN hydrogel containing 0.5 g PEI showed a higher swelling capacity than the remaining PEI-formulated hydrogels. These gels demonstrated a relatively higher swellability at pH 5 or 6. The interaction of various surfactants and polymer solutions was evaluated at different concentrations. Both the non-ionic (Tween 80) and anionic (sodium dodecyl sulfate, SDS) surfactants promoted their swelling properties, while the cationic (dodecylpyridinium chloride, DPC) surfactant drastically reduced the swelling nature of the polyampholytic semi-IPN hydrogels. Because of more physical attractions between the polyampholytic IPN gels and DPC, it showed a greater thermal stability. The surfactant interactions were eventually studied using scanning electron microscopy. Further, the effect of different salts on the swelling properties of the polyampholytic IPN hydrogels has been demonstrated in detail.     

From Supramolecular Hydrogels to Multifunctional Carriers for Biologically Active Substances

Supramolecular hydrogels are 3D, elastic, water-swelled materials that are held together by reversible, non-covalent interactions, such as hydrogen bonds, hydrophobic, ionic, host–guest interactions, and metal–ligand coordination. These interactions determine the hydrogels’ unique properties: mechanical strength; stretchability; injectability; ability to self-heal; shear-thinning; and sensitivity to stimuli, e.g., pH, temperature, the presence of ions, and other chemical substances. For this reason, supramolecular hydrogels have attracted considerable attention as carriers for active substance delivery systems. In this paper, we focused on the various types of non-covalent interactions. The hydrogen bonds, hydrophobic, ionic, coordination, and host–guest interactions between hydrogel components have been described. We also provided an overview of the recent studies on supramolecular hydrogel applications, such as cancer therapy, anti-inflammatory gels, antimicrobial activity, controlled gene drug delivery, and tissue engineering.     

Synthesis and characterization of biodegradable hydrogels based on photopolymerizable acrylate-terminated CL-PEG-CL macromers with supramolecular assemblies of α-cyclodextrins

A series of polypseudorotaxanes were synthesized from α-cyclodextrins (α-CDs) threaded onto photopolymerizable CL-PEG-CL oligomers bearing acrylate terminals. The corresponding supramolecular structured hydrogels were prepared from these polypseudorotaxanes in a mixed solvent of H₂O and DMSO via in situ photopolymerization under UV irradiation. The structure and properties of the gels were characterized by FTIR, TGA-DTG and WAXD. The results show that α-CDs are threaded and immobilized onto the network chains of the hydrogel with crosslinking junctions as stoppers topologically, and the feed molar ratio of α-CDs to the macromers affects the hydrogel structure and the water distribution in the hydrogel. These supramolecular structured hydrogels may be good candidates for biomaterial applications.     

Large strain behaviour of nanostructured polyelectrolyte hydrogels

The mechanical properties of nanostructured polyelectrolyte hydrogels have been investigated targeting specifically the nonlinear deformation regime at large strains and the fracture properties. The hydrogels were synthesized using a thiol-ene cross-linking chemistry of polyacrylic acid precursor chains previously functionalized with double bonds. Some polymers were also grafted with C₁₂ side chains able to form hydrophobic clusters in water. The large strain deformation of these nanostructured gels was tested in uniaxial compression by performing loading/unloading cycles at different strain rates and up to different maximum strains. All hydrogels displayed a pronounced strain hardening before fracture and a strain dependent hysteresis but the magnitude of these effects depended on the details of the composition. The most pronounced strain hardening was observed for the unmodified hydrogels in pure water while the largest hysteresis was found for the gels containing the highest concentration of nanoclusters. These dissipative processes barely influence the mechanical behaviour at small strains where the gel remains very elastic but become important at large strains and improve the resistance to fracture of the gels.     

Electroresponsive and spinnable hydrogels from xanthan gum and gelatin enhanced by Fe3+ ions coordination

Polyelectrolyte hydrogels with spinnability and electroresponsive were prepared from xanthan gum (XG) and gelatin. Oscillatory rheological measurements were utilized to explore mechanical properties and thermal stability of the resultant XG-Gelatin5 hydrogels. The XG-Gelatin5 hydrogels possessed higher strength and larger critical strain than these of the XG hydrogels, demonstrating existence of synergistic interactions. The XG-Gelatin5 hydrogels were stable in temperature range of 20–60°C, and gradually release drug with controlled manner in neutral and acid medium at 37°C. The self-recoverable and thixotropic XG-Gelatin5 hydrogels were extruded to form hydrogel fibers, and the dried hydrogel fibers rapidly bend towards cathode under applied voltage. Long hydrogel fibers were harvested with enhancement by Fe³⁺ ions, and were weaved and braided to obtain hydrogel fiber constructs. The XG-Gelatin5 hydrogel fibers with electroresponsive and controlled drug release possess potential applications in biomaterials, tissue engineering, and drug carrier fields.     

Removal of anionic dyes from aqueous solution using poly [N-vinyl pyrrolidone/2-(methacryloyloxyethyl) trimethyl ammonium chloride] superswelling hydrogels

Summary A superswelling poly [N-vinyl pyrrolidone/2-(methacryloyloxyethyl)trimethyl ammonium chloride], poly(NVP/METAC) hydrogels were prepared by free radical polymerization using ethylene glycol dimethacrylate as crosslinker. The hydrogels were characterized by FT-IR spectroscopy and their surface morphology was determined using Scanning Electron Microscope (SEM). The influence of feed composition of both the monomers and crosslinker on equilibrium swelling and dye adsorption properties of the hydrogels were examined. The equilibrium swelling ratio and binding ratio of the hydrogel/dye systems greatly depends on the METAC and crosslinker concentration in the gels. The effects of pH of the medium and initial dye concentration on the adsorption were also studied. The binding ratio of the hydrogel/dye system increases in the following order: OR-II>RO-14>RO-13.     

Recent Progress in Biopolymer-Based Hydrogel Materials for Biomedical Applications

Hydrogels from biopolymers are readily synthesized, can possess various characteristics for different applications, and have been widely used in biomedicine to help with patient treatments and outcomes. Polysaccharides, polypeptides, and nucleic acids can be produced into hydrogels, each for unique purposes depending on their qualities. Examples of polypeptide hydrogels include collagen, gelatin, and elastin, and polysaccharide hydrogels include alginate, cellulose, and glycosaminoglycan. Many different theories have been formulated to research hydrogels, which include Flory-Rehner theory, Rubber Elasticity Theory, and the calculation of porosity and pore size. All these theories take into consideration enthalpy, entropy, and other thermodynamic variables so that the structure and pore sizes of hydrogels can be formulated. Hydrogels can be fabricated in a straightforward process using a homogeneous mixture of different chemicals, depending on the intended purpose of the gel. Different types of hydrogels exist which include pH-sensitive gels, thermogels, electro-sensitive gels, and light-sensitive gels and each has its unique biomedical applications including structural capabilities, regenerative repair, or drug delivery. Major biopolymer-based hydrogels used for cell delivery include encapsulated skeletal muscle cells, osteochondral muscle cells, and stem cells being delivered to desired locations for tissue regeneration. Some examples of hydrogels used for drug and biomolecule delivery include insulin encapsulated hydrogels and hydrogels that encompass cancer drugs for desired controlled release. This review summarizes these newly developed biopolymer-based hydrogel materials that have been mainly made since 2015 and have shown to work and present more avenues for advanced medical applications.     

Synthesis and evaluation of sucrose‐containing polymeric hydrogels for oral drug delivery

Biodegradable and biocompatible copolymeric hydrogels based on sucrose acrylate, N‐vinyl‐2‐pyrrolidinone, and acrylic acid were designed and synthesized. Because of the growing importance of sugar‐based hydrogels as drug delivery systems, these new pH‐responsive sucrose‐containing copolymeric hydrogels were investigated for oral drug delivery. The sucrose acrylate monomer was synthesized and characterized. The copolymeric hydrogel was synthesized by free‐radical polymerization. Azobisisobutyronitrile (AIBN) was the free‐radical initiator employed and bismethyleneacrylamide (BIS) was the crosslinking agent used for hydrogel preparations. Homopolymeric vinyl pyrrolidone hydrogels were also prepared by the same technique. The hydrogels were characterized by differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy. Equilibrium swelling studies were carried out in enzyme‐free simulated gastric and intestinal fluids (SGF and SIF, respectively). These results indicate the pH‐responsive nature of the hydrogels. The gels swelled more in SIF than in SGF. A model drug, propranolol hydrochloride (PPH), was entrapped in these gels and the in vitro release profiles were established separately in both enzyme‐free SGF and enzyme‐free SIF. The drug release was found to be faster in SIF. About 93 and 99% of the entrapped drug was released over a period of 24 h in SGF and SIF, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2597–2604, 2002     

A comparative study of swelling properties of hydrogels based on poly(acrylamide‐co‐methyl methacrylate) containing physical and chemical crosslinks

Poly (acrylamide‐co‐methyl methacrylate) hydrogels of different ratios were prepared by using chemical and physical crosslinks to study the effect of nature of crosslinks on swelling behavior of hydrogels. The chemically crosslinked gels were prepared by using NN′‐methylene bis acrylamide, while physically crosslinked hydrogels were prepared by precipitation polymerization method, using dioxane as solvent. Detailed swelling kinetics such as swelling ratio, transport exponent n, diffusion coefficient D and the effect of pH on equilibrium swelling studies. The study revealed that the nature of crosslinks alter the swelling characteristics of the hydrogel. In chemically crosslinked hydrogels the water transport is Fickian in nature, while in the case of the physically crosslinked hydrogels the water transport mechanism is anomalous indicating major change in relaxation mechanism due to nature of crosslinks. The results also indicate that with increasing acrylamide content the swelling ratio of the hydrogels were also increased, but the transport exponent n remains nearly constant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 779–786, 2003