Swelling behaviour of crosslinked hydrogels based on (2-hydroxyethyl methacrylate) with a zwitterionic comonomer (1-3-sulfopropyl-2-vinyl-pyridinium-betaine)

Copolymeric hydrogels were prepared by the chemically initiated free radical copolymerization in aqueous solution of mixtures of [1-(3-sulfopropyl)-2-vinyl-pyridinium-betaine] (SPV) and (2-hydroxyethyl methacrylate) (HEMA) in the presence of a crosslinking agent N,N′-methylene-bis-acrylamide (MBA). The hydrogels were swollen to equilibrium in water and aqueous KSCN at 298 K and their swelling behaviour has been investigated using gravimetric measurements. The effects of the concentration of KSCN and the mole fraction of SPV in the feed (F_s) have been noted and discussed. The main findings are:(a) In water, the water content (W₁) of copolymeric hydrogels is insensitive to SPV content at F_s ? 0.45. In contrast, W₁ decreases sharply with decreasing F_s within the range of 0 < F_s < 0.45. (b) In aq. KSCN, the degree of total swelling (W) exceeds the value in pure water, the enhancement in swelling being most marked at low values of [KSCN]. The content of water within the hydrogel increases with KSCN concentration in the swelling medium for low values of [KSCN], but thereafter falls with further increase in salt concentration. In contrast, the salt content within the swollen hydrogel displays a continuous increase with increasing [KSCN]. All these results of item (b) are for copolymeric hydrogels within the full range of F_s (0 < F_s < 1). (c) at a fixed aq. KSCN concentration, both W and W₁ increase sharply with increasing F_s over the entire range of copolymer composition.     

Electrochemically initiated chain polymerization of pyrrole in aqueous media

The electrochemical quartz crystal microbalance has been employed to investigate the electropolymerization of pyrrole in a variety of aqueous electrolytes. In contrast to the generally accepted cation–radical coupling process for the electropolymerization of pyrrole, an electrochemically initiated chain polymerization, featuring a high polymerization rate and involving little charge transport, was found under specific conditions in the presence of ClO^?₄, BF^?₄, and PF^?₆ electrolytes. The more typical cation-radical coupling mechanism, characterized by a constant polymerization charge to mass deposited ratio, is observed in the presence of Cl^?, NO^?₃, dodecyl sulfate, copper phthalocyanine tetrasulfonate, β-cyclodextrin tetradecasulfate, and poly(styrene sulfonate). Electrochemical characterizations of polypyrrole films prepared in aqueous ClO^?₄ electrolytes reveal that the polymer formed via chain polymerization exhibits the ability to transport both cations and anions during electrochemical switching between redox states, while the polymer synthesized through cation-radical coupling is only capable of transporting a single ionic species.     

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.     

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.     

Synthesis and characterization of novel PEG-tethered PMAA hydrogels based on a PEG macromolecular azo initiator

A new route was proposed to synthesize polyethylene glycol-tethered polymethacrylic acid (viz., PEG-tethered PMAA or PEG-t-PMAA) hydrogels based on a macromolecular azo initiator (MAI), PEG-attached azo initiator. The preparation of the MAI was accomplished by coupling PEG with 2,2-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (AMHP) using 1,1-methylene bis-(4-isocyanato-cyclohexane) (H₁₂MDI) as bridging molecules. The structure and morphologies of the resulting hydrogels were characterized by FTIR and SEM. The pH and ionic strength responses were investigated by swelling measurements, depending on molecular weight (MW) of PEG, molar ratios of isocyanate-terminated PEG to AMHP and mass percentage of the as-prepared MAIs. The PEG-t-PMAA hydrogels synthesized by 100 wt% PEG1000-attached azo initiators and a molar ratio 2 of -NCO-terminated PEG to AMHP exhibit more remarkable pH and ionic strength response than any other hydrogels. The driving force of swelling is believed to be mainly due to the porosity and dissociation balance of PMAA gels as well as gel compositions, while the deswelling behavior may be correlated with the decrease in osmotic pressure caused by the so-called “charge screening effect“ of the cations. The PEG-t-PMAA hydrogels are expected to find specific applications in oral drug delivery and tissue engineering.     

Inhibitory Effects of Hydrogels on the Adhesion,Germination, and Development of Zoospores Originating from Laminaria angustata

The inhibition of germination and development of zoospores originating from Laminaria angustata originated on various kinds of hydrogels is studied. The effects of the water content of the gel (the degree of swelling), the electrical nature (neutral, positive charge, negative charge), the charge density, the counterions of hydrogels on the inhibition of zoospore germination and development of gametophytes are phenomenologically investigated. Among the gels investigated, poly(acrylic acid) (PAA) gel showed a dramatic inhibition to germination, and might serve as a novel, environmentally safe inhibitor of zoospore adhesion.     

Preparation and characterization of biodegradable gelatin-PAAm-based IPN hydrogels for controlled release of maleic acid to improve the solubility of phosphate fertilizers

In this study, interpenetrating polymer network (IPN) hydrogel systems including maleic acid (MA) were constituted to improve the solubility of phosphate fertilizers. A series of full and semi-IPN hydrogels were prepared from various gelatin/polyacrylamide mixtures by using two different cross-linkers. The effects of polymer composition on the morphological structures and swelling behaviors of the hydrogels were investigated. The swelling values of all hydrogels were found to be in between 435% and 830%. MA release from load0ed hydrogels was followed and it was determined that MA-loaded hydrogels efficiently decreased pH and improved the solubility of Ca₃(PO₄)₂ in releasing medium.     

Microstructured Polyacrylamide Hydrogels Prepared Via Inverse Microemulsion Polymerization

The synthesis by a two-stage polymerization process of microstructured polyacrylamide hydrogels with large swelling capacity and improved mechanical properties is reported. First, crosslinked polyacrylamide particles of nanosize scale are made by inverse microemulsion polymerization. These particles are then dried and redispersed in an aqueous solution of acrylamide and polymerized in the presence of a crosslinking agent. The microstructured hydrogels, in contrast to transparent conventional polyacrylamide hydrogels, are translucid due to the presence of the dispersed particles. The swelling capacity of these hydrogels increases as the particle content increases and their Young and elastic moduli (at equilibrium swelling) diminish only slightly. Mechanical tests disclose that the microstructured hydrogels have larger Young moduli than conventional hydrogels with an identical degree of swelling. Copyright 2001 Academic Press.     

Swelling equilibrium of poly(acrylamide) gels in aqueous salt and polymer solutions

The influence of some single salts (NaCl, KCl, Na₂HPO₄ and K₂HPO₄) and poly(ethylene glycol) (PEG) on the swelling of aqueous poly(arcylamide)-gels was studied at 25°C in more than 600 experiments. The chlorides and phosphates cause a different behavior at high salt concentrations: The polyacrylamide gels swell in aqueous solutions of sodium and potassium chloride whereas they shrink when chloride ions are substituted by hydrogen phosphate ions. These differences are due to differences in the interactions of chloride and hydrogen phosphate ions with the network groups. In aqueous solutions of poly(ethylene glycol) the gels shrink continuously with increasing polymer concentration. At constant PEG mass fraction in the liquid phase, the swelling of the gel decreases with increasing molecular weight of PEG. The experimental results (degree of swelling, partitioning of solutes to the coexisting phases) are correlated by combining a model for the Gibbs excess energy for aqueous systems of polymers and electrolytes with a modification of the phantom-network theory. The correlation gives a good agreement with the experimental data for the degree of swelling, whereas in most cases, there is only a qualitative agreement for the partitioning of the solutes.     

Siloxane-functionalized calix[4]pyrrole: synthesis, characterization and modification of silica-based solid supports

A siloxane-functionalized calix[4]pyrrole derivative was synthesized starting from the corresponding alcohol-functionalized calix[4]pyrrole. Structural elucidation was carried out by using NMR spectroscopy, mass spectrometry and X-ray diffraction analysis. The use of this siloxane-functionalized calix[4]pyrrole for modification of various silica solid supports (silica gel 60, fume silica, and SiO₂ nanopowder) was studied. Characterization of the modified silica solid supports was achieved by FTIR, TGA, and elemental analysis. It was also shown that the production of silica nanoparticles is possible via a sol-gel reaction of siloxane-functionalized calix[4]pyrrole and tetraethoxysilane (TEOS). Calix[4]pyrrole modified silica solid supports were found to sense chloride anions of Azure A dye.     

Structural parameters of polyacrylamide hydrogels obtained by the Equilibrium Swelling Theory

In this paper, the synthesis and structural characterization of a series of polyacrylamide hydrogels with different degrees of reticulation are reported. Although the Equilibrium Swelling Theory was recognized as a simple and reliable tool for the determination of structural hydrogels network parameters like equilibrium degree of swelling, cross-link ratio and mesh size, this is the first application of this methodology for polyacrylamide hydrogels. By changing the total monomer content in the synthesis solution (%T) from 5 to 30%, at a fixed value of cross-linker content in the total monomer amount (%C) of 5%, the final parameter obtained, the mesh size, can be tuned from 2 to 0.3 nm. It was also possible to change the mesh size (0.19-0.35) by varying %C from 5 to 12% (at %T = 20%). Scanning Electron Microscopy images for the most different formulations are shown and corroborate data obtained from the theory.     

Characterization of low molecular-weight gelator methyl-4,6-O-(p-nitrobenzylidene)-α-d-glucopyranoside hydrogels and water diffusion in their networks

This paper focuses on the thermal properties, the microstructure, and the molecular dynamics of water in the hydrogels (1.5, 2, 3, 4, and 5% [g mL⁻¹]) formed by sugar-based low molecular-weight gelator methyl-4,6-O-(p-nitrobenzylidene)-α-d-glucopyranoside. The energy needed to break the non-covalent interactions such as the hydrophobic, dipole-dipole, and π-π stacking interactions responsible for the gel formation was calculated to be 43 kJ mol⁻¹. The microstructure of the 4% [g mL⁻¹] hydrogel shows a characteristic fibril structure of the gel network with individual gel fibers, the junction points of thicker fibers, and pores occupied by water. The single mode diffusion of water molecules inside the gel network was detected irrespective of the diffusion time Δ (8-75 ms) and hydrogel concentration. For Δ of 10 ms the water diffusion is almost free and characterized by the diffusion coefficient in the range from 2.17×10⁻⁹ to 1.84×10⁻⁹ m² s⁻¹ for studied hydrogels. For larger Δ values, so-called restricted diffusions are observed and manifested in the linear decreases of the diffusion coefficient with diffusing time Δ, as shown for 5% gel. Only the one average proton spin-lattice relaxation time T₁ of water was determined for the studied hydrogels, irrespective of gelator concentration.     

Uranyl ion uptake capacity of poly (N-isopropylacrylamide/maleic acid) copolymeric hydrogels prepared by gamma rays

The effect of gel composition, absorbed dose and pH of the solution on the uranyl ion uptake capacity of N-isopropylacrylamide/maleic acid copolymeric hydrogels containing 0–3 mol% of maleic acid at 48 kGy have been investigated. Uranyl uptake capacity of hydrogels are found to increase from 18.5 to 94.8 mg [UO₂²⁺]/g dry gel as the mole % of maleic acid content in the gel structure increased from 0 to 3. The percent swelling, equilibrium swelling and diffusion coefficient values have been evaluated for poly(N-isopropylacrylamide/maleic acid) hydrogels at 500 ppm of uranyl nitrate solution.     

Radiation induced synthesis and swelling characterization of thermo-responsive N-isopropylacrylamide-co-ionic hydrogels

Two-component thermo-responsive hydrogels poly(N-isopropylacrylamide)-co-vinylbenzyltrimethylammonium chloride (NIPA-co-VBT) and poly(N-isopropylacrylamide)-co-p-sodium styrene sulphonate (NIPA-co-SSS) were prepared by using high energy gamma radiation. The gels were characterized by Fourier transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and sol-gel analysis. The presence of ionic monomers in NIPA leads to lower gel content. Introduction of ionic components in the matrix enhanced swelling extent but caused slower volume transition. The swelling studies in alcohol indicated that swelling extent was function of polarity of the swelling medium and all gels followed the order water > methanol > ethanol > iso-propanol. In mixed co-solvents (water-alcohol), they exhibit complex reentrant behavior. The co-polymer gels containing VBT swelled faster and to higher extent than those containing SSS. The dynamic swelling studies indicated that diffusion of water in PNIPA gel shifts from Fickian for PNIPA to anomalous for NIPA-co-ionic gels also the mean swelling time (MST) decreases for gels containing ionic monomers.     

Hydrogels based on carboxymethyl cassava starch cross-linked with di- or polyfunctional carboxylic acids: Synthesis, water absorbent behavior and rheological characterizations

Carboxymethyl cassava starch (CMS) was synthesized and its hydrogels were prepared by cross-linking it with di- or polyfunctional carboxylic acids using glutaric (CASXGLU), suberic (CASXSUB), pimelic (CASXPIM) and butanetetracarboxylic acids (CASBTC) as the cross-linkers. The characterization of the CMS showed that its degree of substitution was 0.86, average molar mass (M_w) was 5.6 × 10⁶ g mol⁻¹ and the ¹³C NMR showed strong peak at δ = 180.42 ppm which was assigned to the CO carbon in the carboxymethyl group. The absorption under load (AUL) and free swelling capacity (FSC) studies showed that the hydrogels have fast swelling properties and that they reached equilibrium after 1 h. Furthermore, all the hydrogels were sensitive to the increasing salt concentrations and pH of the medium. Both AUL and FSC reduced in saline solution while their values increased in alkaline buffer solutions. The result indicate that the difunctional carboxylic acids produced hydrogels with stronger material functions compared with the polyfunctional carboxylic acid and the order of increases in both AUL and FSC was CASXBTC, CASXPIM, CASXSUB and CASXGLU.     

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.     

Partitioning of hexavalent chromium in temperature-sensitive,polyelectrolyte hydrogels

Partitioning data for hexavalent chromium (Cr(VI)) are presented for systems where thermally sensitive poly-N-isopropylacrylamide (NIPA)-based hydrogels are in contact with aqueous solutions of potassium dichromate (K₂Cr₂O₇). The poly-NIPA hydrogels contain 0–3% quatemized amine comonomer. Experimental results are given for the effect of gel charge, ionic strength and temperature on the partitioning of Cr(VI) into these NIPA-copolymer gels. At low ionic strength, the partition coefficient increases with the content of quatemized amine. The effect of rising temperature is to increase the partition coefficient. Swelling equilibria in aqueous K₂Cr₂O₇ solutions decrease with ionic strength and, at ionic strengths <0.1 M, are lower compared to swelling in aqueous sodium chloride solutions. Experimental partitioning data as a function of ionic strength and gel charge are compared with predictions based on two theoretical models for mixed electrolyte solutions. Predictions based on the cell model for polyelectrolyte solutions agree best with experimental results. Calculated results are in semi-quantitative agreement with experimental data for the effects of solution ionic strength and gel charge on Cr(VI) partitioning and in qualitative agreement for the effect of temperature.     

Synthesis and Properties of Polypyrrole/Chitosan Composite Hydrogels

Conducting polymer hydrogels consisting of polypyrrole (PPy) and chitosan (CS) are prepared by static polymerization of pyrrole using methyl orange (MO) as the dopant and Fe₂(SO₄)₃ as the oxidant in the CS aqueous solution. PPy/CS composite hydrogels not only have good electrical conductivities, but also exhibit excellent swelling/deswelling behaviors due to the participation of one-dimensional conducting PPy blocks in the hydrogel network. The effects of the amount of the oxidant and ionic strength on the physical properties of PPy/CS composite hydrogels are studied in detail. The results show that PPy/CS composite hydrogels have improved water absorbencies in saline solutions compared with the conventional polyelectrolyte hydrogel.     

Aminol initiated Prins cyclization for the synthesis of octahydro-1H-pyrano [3,4-c]pyridine and hexahydro-1H-furo[3,4-c]pyrrole derivatives

Various aldehydes undergo smooth coupling with a branched homoallylic alcohol appended N-tosyl amine (1 & 3) in the presence of 10 mol % BF₃·OEt₂ at room temperature to afford a novel class of 1,8-disubstituted octahydropyrano[3,4-c]pyridine and 1,6-disubstituted hexahydrofuro[3,4-c]pyrrole derivatives in good yields, respectively.     

Swelling behavior of gelatin‐ionic liquid functional polymers

In this work, hydrogels obtained by mixing gelatin with ionic liquids (ILs) are prepared. Two different ILs, [emim][EtSO₄] and [bmim][N(CN)₂], are used to prepare hydrogels with different amounts of starting water and phosphate buffer content, which are used after a maturation period. The percentage of swelling in water and phosphate buffer, swelling and diffusion parameters are investigated in thin‐film polymers (1 × 1 cm²; 1‐mm thick) with different maturation times and at temperatures ranging from 4 to 37 °C. [emim][EtSO₄] polymers show a moderate (100% weight increase) but quick swelling that reaches 80% of the equilibrium within 30 min. They are liquefied and dissolved at temperatures above 25 °C. [bmim][N(CN)₂] polymers with short maturation times exhibit a similar behavior to the former, but more mature hydrogels register a very small swelling, abnormal kinetics and are more resistant to higher temperatures. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys., 2013