Swelling of a N-isopropyl acrylamide hydrogel in two aqueous/organic two-phase systems

Hydrogels are crosslinked macromolecules (polymer networks) with segments of hydrophilic groups. Such polymer networks are able to swell as well as to shrink in liquid phases. This paper reports experimental results for the swelling behavior of a nonionic, synthetic hydrogel of N-isopropyl acrylamide in partially miscible aqueous solutions of a single organic solvent (1-butanol and methyl isobutyl ketone) at 298 K. The experimental results are correlated applying a thermodynamic model, which combines an expression for the Gibbs energy of a liquid phase with an equation for the Helmholtz energy of an elastic network.     

Thermodynamics of phase equilibrium for systems containing N-isopropyl acrylamide hydrogels

Hydrogels are crosslinked polymers of hydrophilic monomers. Hydrogels can swell and shrink in aqueous solutions. The swelling behavior of hydrogels and the encountered phase behavior are of interest in many areas, e.g., in biotechnology, membrane science and controlled drug release. This contribution presents the criteria for such phase equilibria and a previously developed thermodynamic model for correlating/predicting the swelling and shrinking of hydrogels. The application of the method is demonstrated by describing the swelling equilibrium of some synthetic, non-ionic N-isopropyl acrylamide (N-IPAAm) hydrogels in aqueous solutions of sodium chloride at 298 K. Furthermore, new experimental results are presented for the degree of swelling of synthetic hydrogels that contain – besides the non-ionic monomer N-IPAAm – either a combination of a cationic comonomer (here, N-[3-(dimethylamino)propyl]methacrylamide (DMAPMA)) and an anionic comonomer (here, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS)) or a zwitterionic comonomer (here, [3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxide inner salt (MPSA)). These gels were equilibrated with aqueous solutions of sodium chloride at 298 K.     

Swelling behavior of amphiphilic hydrogels of copolymers of the vinyl ether of ethylene glycol and vinyl isobutyl ether,and their interaction with cationic surfactant

Amphiphilic hydrogels of copolymers of the vinyl ether of ethylene glycol and vinyl isobutyl ether were synthesized by -radiation-induced free radical polymerization. Hydrogels with certain copolymer compositions showed thermo-sensitive behavior in aqueous solutions. The swelling behavior of the hydrogels in cetylpyridinium bromide aqueous solution was studied. Increased swelling of the hydrogels was observed in the surfactant solutions. The increased swelling was more prominent for the hydrogels with a higher content of hydrophobic moiety in the copolymer composition, and with higher surfactant concentration. The reason for this phenomenon is discussed. Treatment of some hydrogels in the surfactant solutions resulted in higher swelling ability in distilled water with distinct thermo-induced contraction over a narrow temperature interval.     

多孔水凝胶研究进展

水凝胶是亲水性而又不溶于水的高分子聚合物材料,因其独特的吸水、保水和仿生特性而受到材料科学和生物医学工作者的关注。将多孔结构引入水凝胶可以极大地提高其溶胀率、溶胀速率和刺激敏感性。本文结合作者实验室开展的波聚合法制备多孔水凝胶的研究工作,较全面地介绍了国内外多孔水凝胶材料的研究现状及其在生物医药领域的应用,并对其发展前景进行了展望。     

Alginate/Polyoxyethylene and Alginate/Gelatin Hydrogels: Preparation,Characterization, and Application in Tissue Engineering

Hydrogels are attractive biomaterials for three-dimensional cell culture and tissue engineering applications. The preparation of hydrogels using alginate and gelatin provides cross-linked hydrophilic polymers that can swell but do not dissolve in water. In this work, we first reinforced pure alginate by using polyoxyethylene as a supporting material. In an alginate/PEO sample that contains 20 % polyoxyethylene, we obtained a stable hydrogel for cell culture experiments. We also prepared a stable alginate/gelatin hydrogel by cross-linking a periodate-oxidized alginate with another functional component such as gelatin. The hydrogels were found to have a high fluid uptake. In this work, preparation, characterization, swelling, and surface properties of these scaffold materials were described. Lyophilized scaffolds obtained from hydrogels were used for cell viability experiments, and the results were presented in detail.     

Thermodynamics of aqueous solutions containing poly (N-isopropylacrylamide)

Hydrogels undergo reversible and discontinuous volume changes in response to variation of solution conditions such as solvent composition, temperature, salt concentration, and pH. In this contribution we focus our attention on the experimental and theoretical investigation of these swelling equilibria of aqueous cross-linked poly (N-isopropylacrylamide) solutions as well as on the connected demixing behavior of the linear polymer dissolved in water. For the experimental study of the (liquid + liquid) equilibrium an alternative method based on refractive index measurements is suggested. In order to calculate the swelling behavior a model combining an expression for the Gibbs free energy of mixing with an expression for the elastic network is applied. As a model for the Gibbs free energy of mixing the UNIQUAC-approach and the Koningsveld–Kleintjens model are used. For the elastic network contribution again two different theories, namely the phantom network theory and the affine network theory, were applied. Whereas the type of network theory has only a small influence on the calculation results, the Gibbs free energy of mixing has a large impact. Using the UNIQUAC-approach the swelling equilibria can be correlated close to the experimental data, however, this model predicts a homogeneous mixture for linear polymer chains in water. In contrast to this situation the Koningsveld–Kleintjens model does a good job in calculating the swelling equilibria as well as the demixing curve, however, the adjustable parameter must be changed slightly.     

Swelling behavior of chitosan hydrogels in ionic liquid-water binary systems

The swelling behavior of chitosan hydrogels in ionic liquid-water binary systems was studied using hydrophilic room-temperature ionic liquids (RTILs) to elucidate the swelling mechanism of chitosan hydrogels. No penetration of RTIL into a dry chitosan material was observed. Swelling was achieved by soaking in water-RTIL binary mixtures, with larger swelling observed at higher water contents. In one instance, the binary mixture was acidic and produced larger than expected swelling due to the dissociation of the amine groups in the chitosan. The equilibrium binary system content behavior of the chitosan hydrogels depended upon the amount of free water, which is a measure of the number of water molecules that do not interact with the ionic liquid. After evaporation of water, remnant RTIL remained in the chitosan network and hardness testing indicated a plasticization effect, suggesting that the RTIL molecularly mixed with the chitosan. Chitosan hydrogels containing only RTIL were prepared by dropping pure RTIL onto a fully preswollen hydrogel followed by water evaporation. This method may be a useful means for preparing air-stable swollen chitosan gels.     

Indole-3-acetic acid based tunable hydrogels for antibacterial,antifungal and antioxidant applications

Indole-3-acetic acid (IAA) based biopolymeric hydrogels with tunable anti-oxidant and anti-fungal character has been synthesized via condensation polymerization as pH-sensitive hydrophilic material.The present study focused on the synthesis of antifungal heterocyclic hydrogel using citric acid (CA), indole-3-acetic acid (IAA) and ethylene glycol (EG) by condensation polymerization. The hydrogels revealed a pH-sensitive swelling behavior, with increased swelling in acidic media, which in turn has decreased the swelling in the basic media.The hydrogel samples were tested for antifungal activity against Aspergillus fumigates, Rhizopusoryzae and Candida albicans at different concentrations (500, 1000, 1500, 2000 μg/well). Ketoconazole was used as positive control and DMSO as negative control for antifungal activity. Fungi were increasingly identified as major pathogens in various infections. Hydrogels with antifungal properties may constitute an important restriction to fungal infections. The biopolymeric hydrogels were characterized by Fourier transform infrared (FT-IR) spectroscopy, ¹H-NMR,¹³C-NMR, TGA, DSC followed by scanning electron microscopy (SEM). The increased antifungal activity was monitored in equimolar composition more than that of other compositions. The antioxidant activity of ICE with DPPH and NO radicals has been compared with rutin. Such antifungal hydrogels with antioxidant properties is recommended for medical applications such as bandages, catheters, drains and tubes to prevent infection.     

Thermoresponsive behavior of poly(n-isopropylacrylamide) hydrogels containing gold nanostructures

We report the changes in the structure and thermoresponsive behavior of poly(N-isopropylacrylamide) (PNIPAm) hydrogels when gold nanostructures are synthesized in situ within the hydrogel matrix. Cross-linked PNIPAm hydrogels were synthesized using NIPAm and 0.00-3.50% (w/w versus NIPAm) of N,N'-methylenebisacrylamide (MBAm) and/or N,N'-cystaminebisacrylamide (CBAm) as cross-linking agents. The hydrogels were soaked in potassium tetrachloroaurate to introduce gold ions. The hydrogels containing Au3+ were then immersed in a sodium borohydride solution to reduce the gold ions. Infrared spectroscopy, UV-visible spectroscopy, and equilibrium swelling were used to examine the structural/physical differences between gels of different compositions; UV-visible spectroscopy and mass measurements were used to observe the kinetics and thermodynamics of the hydrogel volume phase transition. These studies revealed several differences in the physical characteristics and thermoresponsive behavior of hydrogels based on cross-linker identity and the presence or absence of gold nanostructures. Hydrogels with gold nanostructures and high CBAm and low MBAm content have equilibrium swelling masses 3-20 times their native analogues. In comparison, gold-containing hydrogels with high MBAm and low CBAm content have swelling masses that are equal to their native analogues. Additionally, the gold-containing PNIPAm hydrogels cross-linked with only CBAm have a deswelling temperature of approximately 40 degrees C, approximately 8 degrees C above the samples cross-linked with only MBAm. Varying the CBAm content and introducing gold enables tuning of the deswelling temperature.     

Birefringent hydrogels based on PAAm and lyotropic liquid crystal: Optical, morphological and hydrophilic characterization

In this work, hydrogels of polyacrylamide (or PAAm) with confined lyotropic liquid crystal (potassium laurate-decanol-water, KL-DeOH-H₂O) (or LLC) were synthesized. The hydrogels were characterized by polarized optical microscopy (POM), refractometry, optical transmission, scanning electron microscopy (SEM) and small angle X-ray scattering (SAXS). Besides these techniques, the hydrophilicity of hydrogels was characterized by the degree of swelling. Based on POM, it was observed that the texture of the birefringent hydrogels obtained depends on their cross-linking density, and that it is formed soon after hydrogel synthesis. Refractometry results indicated an behavior antagonist to that obtained for the system constituted by thermotropic liquid crystal inserted into the PAAm lattice in relation to the dependence of Δn on the AAm concentration and the optical transmittance. SEM micrographs show that birefringent hydrogels present rougher surface when compared to the surface of PAAm hydrogels. For the same AAm concentrations, it was observed that the hydrogels with confined LLC present larger swelling values (Q) when compared to those of PAAm hydrogels. The loss of water by birefringent hydrogels is twofold slower than that of PAAm hydrogels. Hydrogels formed by PAAm and lyotropic liquid crystal synthesized in this work can be potentially used in optical devices.     

Modeling of Swelling Behaviors of Acrylamide-Based Polymeric Hydrogels by Intelligent System

Hydrogels based on acrylamide (AAm) were synthesized by free radical polymerization in an aqueous solution using N,N’-methylenebisacrylamide (MBAAm) as crosslinker. To obtain anionic hydrogels, 2-acrylamido-2-methylpropanesulfonic acid sodium salt (AMPS) and acrylic acid (AAc) were used as comonomers. The swelling behaviors of all hydrogel systems were modeled using an artificial neural network (ANN) and compared with a multivariable least squares regression (MLSR) model and phenomenal model. The predictions from the ANN model, which associated input parameters, including the amounts of crosslinker (MBA) and comonomer, and swelling values with time, produce results that show excellent correlation with experimental data. The parameters of swelling kinetics and water diffusion mechanisms of the hydrogels were calculated using the obtained experimental data. Model analysis indicated that the ANN models could accurately describe complex swelling behaviors of highly swellable hydrogels.     

Thermodynamics of Swelling of Poly(NIPAM-co-NTBA-co-HEAAm) Hydrogels

In the present study, poly(N-Isopropylacrylacrylamide-co-N-tertiarybutylacrylamide-co-hydroxyethylcrylamide) (NIPAM-co-NTBA-co-HEAAm) hydrogels are prepared with variation of molar ratio of hydrophilic HEAAm and hydrophobic NTBA. The prepared hydrogels are characterized with elemental analysis and Fourier transform infrared (FTIR) spectroscopy. The thermodynamics of swelling properties of poly(NIPAM-co-NTBA-co-HEAAm) hydrogels have also been discussed. The experimental C/N ratios are comparable with the theoretical value. The enthalpy change of mixing ∆H_mix, entropy change of mixing ∆S_mix, free energy change of mixing ∆G_mix are determined for swelling of hydrogels at 25 °C. The value of total free energy of hydrogel swelling is found to be negative which confirms the lower critical solution temperature (LCST) exhibited in all hydrogels and the volume change transition shows the thermoresponsive behavior. The values of ∆S_mix increase and ∆G_mix decrease with increasing amount of hydrophobic NTBA content in the hydrogels. The values of free energy change of elasticity (∆G_el) are found to be increased with increasing the hydrophobic NTBA content followed by decrease in swelling percentage. Also, the transition temperature of the hydrogel is found to be decreased with increasing the hydrophobic NTBA.     

分子印迹智能水凝胶的研究进展

智能水凝胶可以响应外界环境(如温度、pH、溶剂、离子强度、电场、磁场、光、压力和特异分子等)的变化,发生可逆体积相变,从而具有控制释放的能力.将分子印迹技术引入智能水凝胶,制备分子印迹智能水凝胶,不仅可以保持其环境响应性,更赋予其对特异分子的识别性能,从而可以根据外界环境的变化控制其对特定分子记忆功能的开关,实现自动识别并结合或释放特定分子.它有望应用于药物控释、生物传感和免疫分析等领域.本文综述了分子印迹智能水凝胶的研究现状,讨论了其目前所面临的挑战,并展望了其发展前景.     

温度和pH双敏性PVME/CMCS水凝胶辐射交联制备及其性能

以聚甲基乙烯基醚(PVME)和羧甲基壳聚糖(CMCS)为原料, 采用电子束辐照交联方法制备聚甲基乙烯基醚/羧甲基壳聚糖(PVME/CMCS)水凝胶, 研究了温度、pH值、CMCS含量等对PVME/CMCS水凝胶溶胀度的影响, 同时以5-氟尿嘧啶(5-Fu)作模型药物, 初步探讨了凝胶药物释放性能. 结果表明, 辐射剂量在20—40 kGy时, 凝胶分数随辐射剂量的增加而快速增加, 辐射40 kGy以后趋于平衡. 在相同辐射剂量下, 随着体系中CMCS含量的增加, 凝胶分数反而减少. 该水凝胶具有一定的温度和pH敏感性, 其低临界溶解温度(LCST)在35 ℃左右, 并且在相同时间内和25及37 ℃下的溶胀反复可逆, 表现出较快的响应性. pH<3.0和pH>5.0时, 溶胀度较大; pH值为3.0~5.0时, 凝胶网络由于静电力收缩, 溶胀度较小. CMCS含量的增加和辐射剂量的减小均可提高凝胶载药量. 药物释放时间可通过改变体系中CMCS的含量和辐射剂量来调节.     

Organohydrogels with High-Speed Lubrication by Confining Polymer Chain Mobility by an Interpenetrated Heteronetwork

Hydrogels with pure hydrophilic network have received much attention due to their excellent low frictional behavior. However, the lubrication performance of hydrogels is not satisfied under high-speed condition due to the energy dissipation caused by adsorbed polymer chains as well as the failure of lubricating mechanisms accompanied by the transition of lubrication regime. In this work, interpenetrating double-network organohydrogels were constructed by combining hydrophilic and oleophilic polymer networks to modify the physiochemical properties of surface polymer chains, especially the chain mobility. The oleophilic polymer network spatially restricting the mobility of the swollen hydrophilic network in water, resulted in a low coefficient of friction (ca. 0.01) compared with conventional hydrogels at high speed (0.1 m s⁻¹). Meanwhile, the organohydrogels had superior wear resistance, with almost no wear observed on the sliding track after 5 k cycles of rubbing at high speed. The design concept of organohydrogels can be extended to a variety of low-wear, highly-lubricating materials.     

Facile Tailoring of Structures for Controlled Release of Paracetamol from Sustainable Lignin Derived Platforms

Nowadays, sustainable materials are receiving significant attention due to the fact that they will be crucial for the development of the next generation of products and devices. In the present work, hydrogels have been successfully synthesized using lignin which is non-valorized biopolymer from the paper industry. Hydrogels were prepared via crosslinking with Poly(ethylene) glycol diglycidyl ether (PEGDGE). Different crosslinker ratios were used to determine their influence on the structural and chemical properties of the resulting hydrogels. It has been found that pore size was reduced by increasing crosslinker amount. The greater crosslinking density increased the swelling capacity of the hydrogels due to the presence of more hydrophilic groups in the hydrogel network. Paracetamol release test showed higher drug diffusion for hydrogels produced with a ratio lignin:PEGDGE 1:1. The obtained results demonstrate that the proposed approach is a promising route to utilize lignocellulose waste for producing porous materials for advanced biomedical applications in the pharmacy industry.     

Light-induced water swelling/shrinking recovery of hydrogels based on chemically cross-linked poly (vinyl alcohol)

Photoresponsive hydrogels with high performance are of considerable interest because of their wide application. In this paper, a kind of smart poly (vinyl alcohol) (PVA) hydrogel is obtained using 4, 4′-azodibenzoic acid as cross-link agent. The hydrogels have the ability of swelling and shrinking reversibly under irradiation by ultraviolet or visible light because azobenzene groups show trans–cis isomerization under suitable light wavenumber. Under UV irradiation, azobenzene takes the cis structure which leads to volume decreases; macroscopically, shrinking can be observed. Under visible light irradiation, the volume recovers, and swelling can be observed macroscopically. Hydrogels have excellent swelling/shrinking recovery properties even after 12 cycles. The procedure achieves loop control of the transformation from light energy to mechanical energy.     

Characterization and Evaluation of Acrylic Acid Co-2-acrylamido-2-methylpropane-1-sulfonic Acid Hydrogels for Uranium Recovery

Crosslinked 2-acrylamido-2-methyl-1-propane sulfonic acid -co- acrylic acid (AMPS/AA) hydrogels were synthesized by radical polymerization in the presence of N,N′-methylenebisacrylamide (MBA) as the crosslinking agent using potassium persulfate (KPS) as initiator. Hydrogels with different compositions and crosslinker concentrations were prepared. The structures of hydrogels were characterized by FTIR analysis. Thermal stabilities of the hydrogels were investigated using TGA and DSC analysis. Swelling kinetics and the equilibrium water content (EWC) of the hydrogels were studied. The swelling behavior of these hydrogels was investigated at different pHs at room temperature. Also the swelling behavior of these hydrogels was investigated at different ionic strength. The ability of the prepared hydrogels to bind uranium(VI) was tested under noncompetitive conditions by batch equilibrium procedure. Experimental work using uranyl nitrate hexahydrate bought from the local market was carried out in the safeguards destructive analysis laboratory (KMP-I) in the National Center for Nuclear Safety and Radiation Control.     

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.     

Hydrophilic silicone hydrogels with interpenetrating network structure for extended delivery of ophthalmic drugs

In the current work, hydrophilic silicone hydrogels were prepared for extended drug delivery applications. The preparation method was based on sequential interpenetrating network synthesis. A hydrophilic network was prepared by radical copolymerization of hydrophilic monomers 2‐hydroxyethyl methacrylate and poly(ethylene glycol) diacrylate. A hydrophobic silicone network was obtained by crosslinking polymerization of bifunctional methacrylated polydimethylsiloxanes macromonomer. The morphology of the silicone hydrogels was characterized by transmission electron microscopy. The result showed that the silicone hydrogels exhibited heterogeneous morphology. The properties of the silicone hydrogels such as equilibrium swelling ratio (ESR), mechanical property, oxygen permeability, contact angle, and protein repelling ability were investigated. Finally, the silicone hydrogels were loaded with timolol by pre‐soaking in drug solution to evaluate drug‐loading capacity and in vitro release behavior. The results showed that mechanical strength and oxygen permeability increased, and the ESR decreased with the increase of silicone component in the silicone hydrogels. The result of the contact angle measurement indicated that the silicone hydrogels possessed hydrophilic surfaces. The drug loading and in vitro releases were dependent on the composition of hydrophilic/hydrophobic phase of silicone hydrogels. Copyright © 2011 John Wiley & Sons, Ltd.