Hydrogels In Aqueous Solutions Research Articles

Equilibrium swelling of N-isopropyl acrylamide based ionic hydrogels in aqueous solutions of organic solvents: Comparison of experiment with theory

A series of polyelectrolyte hydrogels were synthesized by copolymerization of N-isopropyl acrylamide with the ionic monomer sodium methacrylate. The swelling behavior and the effect of electric charge on the composition-induced collapse of the resulting ionic hydrogels were investigated in aqueous solutions of five single organic solvents (acetone, ethanol, acetic acid, butanol and methyl isobutyl ketone) at 298 K. The experimental results of some hydrogels were 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. The model was also successfully used to predict the swelling equilibrium of the other hydrogels in aqueous, organic solutions.

Swelling behavior of poly{N‐[3‐(dimethylaminopropyl)] methacrylamide‐co‐acrylamide} hydrogels in aqueous solutions of surfactants

AbstractTemperature sensitive poly{N‐[3‐(dimethylaminopropyl)]methacrylamide‐co‐acrylamide} [P(DMAPMA‐co‐AAm)] hydrogels were prepared by the free‐radical crosslinking copolymerization of corresponding monomers in water with N,N‐methylenebisacrylamide as the crosslinker, ammonium persulfate as the initiator, and N,N,N′,N′‐tetramethylethylenediamine as the activator. The swelling equilibrium of the P(DMAPMA‐co‐AAm) hydrogels was investigated as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate and the cationic surfactant dodecyltrimethylammonium bromide. In pure water, regardless of the amount of N,N‐methylenebisacrylamide, the P(DMAPMA‐co‐AAm) hydrogels showed a discontinuous phase transition between 30 and 36 °C. However, the transition temperature changed from discontinuous to continuous with the addition of surfactants; this was ascribed to the conversion of nonionic P(DMAPMA‐co‐AAm) hydrogels into polyelectrolyte hydrogels due to the binding of surfactants through hydrophobic interactions. Additionally, the concentrations of free sodium dodecyl sulfate and dodecyltrimethylammonium bromide ions were measured at different temperatures by conductometry, and it was found that the electric conductivity of the P(DMAPMA‐co‐AAm)–surfactant systems depended strongly on the swelling ratio; most notably, it changed drastically near the phase‐transition temperature of the P(DMAPMA‐co‐AAm) hydrogel. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1645–1652, 2006

Swelling of N-isopropyl acrylamide hydrogels in aqueous solutions of sodium chloride

Hydrogels are three-dimensional networks of hydrophilic polymer chains. Hydrogels can absorb/desorb water and hydrophilic solutes. This behavior is called swelling/shrinking, as it is accompanied by a volume change. The amounts of absorbed substances depend on the structure of the hydrogel and the composition of the coexisting liquid phase. This paper deals with experimental investigations of the swelling behavior of nonionic, chemically crosslinked, synthetic hydrogels of N-isopropyl acrylamide. The swelling equilibrium of some hydrogels in aqueous solutions of sodium chloride was investigated at 298 K. The experimental results are presented, discussed and correlated/predicted with a thermodynamic model which combines an expression for the Gibbs energy of a liquid phase with an expression for the Helmholtz energy of an elastic network.

Swelling of nonionic N-isopropyl acrylamide hydrogels in aqueous solutions of (acetic acid or pyridine)

Gels are crosslinked macromolecules (polymer networks). The crosslinking results in an elastic behavior of the polymer network. When the segments of the network contain hydrophilic groups, the gels are called “hydrogels”. Hydrogels respond to their surroundings by a volume change, i.e. they swell or shrink. This paper reports new experimental results for the swelling behavior of some nonionic, synthetic hydrogels of N-isopropyl acrylamide in aqueous solutions of a single organic solvent (acetic acid and pyridine) 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.

Swelling and Adsorption Properties of Hydrophobic Poly[(N‐(3‐(dimethylamino)propyl)methacrylamide)‐co‐(lauryl acrylate)] Hydrogels in Aqueous Solutions of Surfactants

AbstractSummary: The swelling and adsorption behavior of a series of hydrophobic poly[(N‐(3‐(dimethylamino)propyl)methacrylamide)‐co‐(lauryl acrylate)] [P(DMAPMA‐co‐LA)] hydrogels was studied as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). Between 0 and 41.7 mol‐% of lauryl acrylate (LA) were used as a hydrophobic comonomer in the hydrogel synthesis. In SDS solutions, the equilibrium swelling ratio of the hydrogels decreased with increasing temperature. At SDS concentrations below 0.0083 M, the hydrogels exhibited an almost linear swelling behavior. However, for SDS concentrations above 0.0083 M, non‐linear swelling behavior was observed in the range 28–36 °C. In contrast to the SDS solutions, in all DTAB solutions the equilibrium swelling ratio of the hydrogels increased with increasing temperature and a positive temperature sensitive property was shown for all P(DMAPMA‐co‐LA) hydrogels. The adsorption capacities of the hydrogels in aqueous solutions of SDS and DTAB were determined via surface tension measurements. An increase in the LA content in the hydrogel caused an increase in the amount of adsorbed surfactant molecules in both media.Effect of the DTAB concentration on the adsorption capacities of P(DMAPMA‐co‐LA) hydrogels.magnified imageEffect of the DTAB concentration on the adsorption capacities of P(DMAPMA‐co‐LA) hydrogels.

Nitrocinnamate-Functionalized Gelatin: Synthesis and “Smart” Hydrogel Formation via Photo-Cross-Linking

Gelatin having p-nitrocinnamate pendant groups (Gel-NC) was prepared via an efficient one-pot synthesis, yield >87%. (1)H NMR data indicated that 1 mol of gelatin was modified with 18 +/- 6 mol of the photosensitive group. Upon exposure to low-intensity 365 nm UV light and in the absence of photoinitiators or catalysts, Gel-NC cross-linked within minutes into a gelatin-based hydrogel as monitored by UV-vis spectroscopy. The degree of swelling of this biodegradable hydrogel in aqueous solutions responded to changes in Gel-NC concentration levels, the ionic strength of the aqueous solutions, and photo-cross-linking time. Topography changes associated with phase transition resulting from "photocleavage" of the hydrogel network with 254 nm UV light were studied with AFM. Both Gel-NC and its hydrogel expressed low toxicity to human neonatal fibroblast cells. In addition, gelatin-based microgels were prepared via the photo-cross-linking of Gel-NC within inverse micelles.

Rheometric Study of the Gelation of Chitosan in Aqueous Solution without Cross-Linking Agent

A new process of formation of chitosan physical hydrogels in aqueous solution, without any organic solvent or cross-linking additive, was studied. The three conditions required for the physical gelation were an initial polymer concentration over C*, a critical value of the balance between hydrophilic and hydrophobic interactions, and a physicochemical perturbation responsible for a bidimensional percolating mechanism. The time necessary to reach the gel point was determined by rheometry, and gelations were compared according to different initial conditions. Thus, we investigated the influence of the polymer concentration and the degree of acetylation (DA) of chitosan on gelation. The number of junctions per unit volume at the gel point varied with the initial polymer concentration, i.e., the initial number of chain entanglements per unit volume or the number of gel precursors. The time to reach the gel point decreased with both higher DAs and concentrations. For a chitosan of DA = 36.7%, a second critical initial concentration close to 1.8% (w/w) was observed. Above this concentration, the decrease of the time to reach the gel point was higher and fewer additional junctions had to be formed to induce gelation. To optimize these physical hydrogels, to be used for cartilage regeneration, their final rheological properties were studied as a function of their degree of acetylation and their polymer concentration. Our results allowed us to define the most appropriate gel for the targeted application corresponding to a final concentration of chitosan in the gel of near 1.5% (w/w) and a DA close to 40%.

Swelling of N-isopropyl acrylamide hydrogels in aqueous solutions of poly(ethylene glycol)

Hydrogels are three-dimensional networks of hydrophilic polymer chains with properties between liquids and solids. One of the most interesting features is their capability to absorb liquids. This feature is called swelling. The amount of absorbed substances depends on the structure of the gel and the composition of the coexisting liquid phase. This paper reports experimental investigations of the swelling behavior of non-ionic, synthetic hydrogels of N-isopropyl acrylamide. The swelling equilibrium of two hydrogels in aqueous solutions of poly(ethylene glycol) with different average molecular weights was investigated at 298 K. The equilibrium properties and the compositions of the coexisting phases (gel phase and surrounding liquid solution) are correlated/predicted with a thermodynamic model which combines an expression for the Gibbs energy of a liquid with an expression for the Helmholtz energy of an elastic network.

Hydrophobically modified alginate hydrogels as protein carriers with specific controlled release properties

Amphiphilic derivatives of sodium alginate, prepared by chemical covalent binding of long alkyl chains onto the polysaccharide backbone via ester functions, form strong hydrogels in aqueous solutions. The shear-thinning and thixotropic behaviors of these hydrogels have been exploited to prepare particles (millimetric beads or microparticles) by dispersion in sodium chloride solutions. This all-aqueous procedure was used for the encapsulation of model proteins, such as bovine serum albumin (BSA) and human hemoglobin (Hb), or of a vaccine protein ( Helicobacter pylori ( H. pylori) urease). In all cases, the encapsulation yields were very high (70–100%). No release of model proteins was observed in water within several days, in contrast with protein-loaded calcium alginate particles, which exhibit an important release within only a few hours. The controlled release of proteins can, however, be achieved by inducing the dissociation of the physical hydrophobic network. This dissociation has been obtained either by addition of surfactants, acting as disrupting agents of intermolecular hydrophobic junctions, or of esterases such as lipases, which hydrolyze the ester bond between alkyl chains and the polysaccharide backbone. The level of immunization against H. pylori infection in mice, induced by encapsulated urease administrated by either systemic or mucosal routes, was also assessed.

Synthesis of persulfate containing poly ( N-vinyl-2-pyrrolidone) (PVP) hydrogels in aqueous solutions by γ-induced radiation

The effect of 60Co γ-irradiation on aqueous solutions of poly( N-vinyl-2-pyrrolidone) (PVP) in the presence of persulfate anion has been investigated. The gelation dose of PVP and persulfate containing PVP aqueous solutions has been determined. At low concentrations of persulfate (1.00–3.50%), gelation percentages exhibited a decreasing trend by increasing persulfate content in aqueous solutions of the polymer. The gelation doses of persulfate containing polymer solutions were calculated by the Charlesby–Pinner equation. It was observed that the gelation dose values were shifted to higher values by increasing persulfate concentration in solution. The ratio of the chain scission and crosslinking yields ( G( s)/ G( x)) was also determined. The results showed that the G( s)/ G( x) ratios were smaller than one for PVP aqueous solution system, whereas those obtained for persulfate containing PVP aqueous solutions were higher than unity. The results implied that the chain scission of polymer is more effective than crosslinking in the presence of persulfate. Mechanism of the crosslinking and/or degradation and structure–property relationship of PVP and PVP/persulfate hydrogel systems were investigated by Fourier transformation infeared and thermal analysis (differential scanning calorimetry, thermal gravimetric analysis and differential thermai analysis) methods.

Supramolecular assemblies of nucleoside phosphocholine amphiphiles.

A family of new uridine phosphocholine amphiphiles that were prepared using a convenient four-step synthetic route is described. Physicochemical studies (differential scanning calorimetry, small-angle X-ray scattering, UV-vis and circular dichroism spectroscopies, light microscopy, transmission electronic microscopy, and scanning electron microscopy) show that these amphiphiles spontaneously assemble into supramolecular structures including vesicles, fibers, hydrogels, and organogels. In aqueous solution, the amphiphiles possessing saturated alkyl chains self-assemble into DNA-like helical fibers in the crystalline state below T(m) and compact bilayers above the melting temperature (T(m)). The transition from bilayers to fibers is thermally reversible. Above a threshold concentration (>6% w/w), a hydrogel is formed due to an entangled network of the fibers. A therapeutic agent such as DNA can be entrapped within the hydrogel structure. In addition to forming bilayer vesicles and hydrogels in aqueous solution, these nucleoside amphiphiles also form organogels in cyclohexane above T(m). Scanning electron microscopy shows a continuous multilamellar phase in the organogels.

Solute retention and the states of water in polyethylene glycol and poly(vinyl alcohol) gels

The states of water sorbed in a cross-linked polyethylene glycol (PEG) gel, TSKgel Ether-250, and cross-linked poly(vinyl alcohol) (PVA) gels of different pore sizes, TSKgel Toyopearl HW-40S, 50S, 55S and 75S, were investigated by means of differential scanning calorimetry (DSC). It was found that there were three types of water in these hydrogels, non-freezing water, freezable bound water and free water. The amount of water that functions as the stationary phase in the column packed with the each gel was also estimated by a liquid chromatographic method. The estimated amount of the stationary phase water is in good agreement with the sum of the amount of non-freezing water and that of freezable bound water for HW-40S, 50S and 55S, while it agrees with the amount of only non-freezing water for HW-75S and Ether-250. This means that the stationary phase water consists of non-freezing water and freezable bound water for HW-40S, 50S and 55S, while only non-freezing water functions as the stationary phase in HW-75S and Ether-250 gels. This result can be attributed to the difference in the structure of the gels; the PVA gels containing PVA at relatively high concentrations, HW-40S, 50S and 55S, have a homogeneous gel phase, whereas HW-75S and Ether-250 have a heterogeneous gel phase consisting hydrated polymer domains and macropores with relatively hydrophobic surface. The freezable bound water in Toyopearl HW-40S, 50S and 55S can be regarded as a component of a homogeneous PVA solution phase, while that in HW-75S and Ether-250 may be water isolated in small pores of the hydrophobic domains. The results obtained by the investigation on the retention selectivity of these hydrogels in aqueous solutions supported our postulated view on the structures of the hydrogels.

Correlation and Prediction of Swelling Behavior of N-isopropyl- acrylamide Based Hydrogels in Aqueous Solution of Acetone

Correlation and Prediction of Swelling Behavior of N-isopropyl- acrylamide Based Hydrogels in Aqueous Solution of Acetone

Effect of chemistry and morphology on the biofunctionality of self-assembling diblock copolypeptide hydrogels.

Amphiphilic, diblock copolypeptides of hydrophilic lysine or glutamic acid and hydrophobic leucine or valine have been observed to self-assemble into rigid hydrogels in aqueous solution at neutral pH and very low volume fraction of polymer, > or =0.5 wt % polypeptide. Laser scanning confocal microscopy and ultra small angle neutron scattering revealed a heterogeneous microstructure with distinct domains of hydrogel matrix and pure water pores. In situ nanoscale characterization, using cryogenic transmission electron microscopy, revealed a porous, interconnected membranous network of assembled polypeptides. At concentrations of polypeptide below gelation, diblocks containing lysine were cytotoxic to cells, whereas those containing glutamic acid were noncytotoxic. At higher polypeptide concentrations, within rigid gel scaffolds, both lysine and glutamic acid based diblocks were noncytotoxic but did not support cell attachment/proliferation. The cationic chemistry observed as cytotoxic in the fluid state was essentially inert in the intact, rigid hydrogel state.

Comparative Behavior of Poly(ethylene glycol) Hydrogels and Poly(ethylene glycol) Aqueous Biphasic Systems

The properties of covalently cross-linked poly(ethylene glycol) (PEG) hydrogels have been studied. The degrees of expansion of the hydrogels in aqueous solutions containing different types of salt and the expansion with respect to temperature have been examined. The apparent polarity of the hydrogels in these differing environments has been measured using Reichardt's betaine dye. The uptake of hydrophobic solutes with respect to temperature and salt concentration has also been examined. We attempt to relate these observations to a consideration of the PEG molecular conformation and hydrogen-bonding ability in aqueous solution. Hydrogel expansion, apparent polarity, and solute uptake all appear to be continuous functions of temperature and salt concentration without any discontinuity typical of critical phenomena. It is suggested that phase formation in aqueous biphasic systems and miscibility gaps in PEG solutions in general result from molecular collapse and the loss of H-bonding ability, followed by the...

Temperature dependent swelling behavior of ionic poly(N-isopropylacrylamide) gels in PEG solutions

The swelling behavior of poly(N-isopropylacrylamide) (PNIPA) hydrogels in aqueous solution of poly(ethy1ene glycol) (PEG) and the partition parameter of PEG between the gel and the external solution were investigated. The molecular weight of PEG, the ionic group content of the hydrogels and the swelling temperature were taken as the independent variables. Several types of volume phase transitions such as swelling, deswelling and reentrant phase transitions were observed depending on the external parameters. The results were explained in terms of the theory of equilibrium swelling.

Electrochemistry and electrocatalysis with heme proteins in chitosan biopolymer films

Protein–chitosan (CS) films were made by casting a solution of proteins and CS on pyrolytic graphite electrodes. Myoglobin (Mb), hemoglobin (Hb), and horseradish peroxidase (HRP) incorporated in CS films gave a pair of stable, well-defined, and quasi-reversible cyclic voltammetric peaks at about −0.33 V vs saturated calomel electrode in pH 7 buffers, respectively, while catalase (Ct) in CS films showed a peak pair at about −0.46 V which was not stable. All these peaks are located at the potentials characteristic of heme Fe III/Fe II redox couples of the proteins. The electrochemical parameters such as formal potentials (E° ′) and apparent heterogeneous electron-transfer rate constants ( k s) were estimated by square-wave voltammetry with nonlinear regression analysis. Chitosan films contained considerable water and formed hydrogel in aqueous solution. Positions of the Soret absorbance band suggest that Mb and Hb in CS films keep their secondary structure similar to the native states in the medium pH range, while HRP and Ct retain their native conformation at least in the dry CS films. Scanning electron microscopy of the films demonstrated that interaction between the proteins and CS would make the morphology of dry protein–CS films very different from the CS films alone. Oxygen, trichloroacetic acid, nitrite, and hydrogen peroxide were catalytically reduced by all four proteins in CS films.

SWELLING PROPERTIES OF POLY(N-VINYLIMIDAZOLE) HYDROGELS

The swelling capacity of poly(N-vinylimidazole) hydrogels in aqueous solutions and organic solvents was measured as a function of polymer network structure. In pure water, the swelling capacity decreases monotonously upon increasing the crosslinker ratio and the total comonomers concentration in the polymerization feed mixture. In methanol a similar behaviour was observed while in ethanol, the swelling capacity shows an abrupt change from large values to 0.01 grams of water per gram of dry gel, that is to say, PVI experience swollen-collapsed transitions with small changes of the gel crosslinking degree. Molecular weight of chains between crosslinks, determined from swelling measurements in methanol, scales with the product of the crosslinker and total comonomers concentrations in the feed mixture to m1.14-0.05. The dependence of the polymer solvent interaction parameter on the polymer concentration inside the swollen gel was also determined for water and ethanol.

Stimuli response of polysoap hydrogels in aqueous solution and DC electric fields

Novel types of polysoap hydrogels based on hydrophobically-modified polyelectrolytes crosslinked with N, N-methylenebisacrylamide have been prepared by free radical polymerization at 70–80°C in aqueous solution with ammonium persulfate as initiator. Poly(diallylamine-co-N, N-dodecylmethyldiallylammonium bromide) (PDA-C12), poly( N-methyldiallyl-co-N, N-dodecylmethyldiallylammonium bromide) (PMDA-C12) both contain hydrophobic side chains with 12 carbon atoms. The swelling behavior of these polysoap hydrogels was studied by immersion of the gels in buffered solutions at various pHs and ionic strengths. It was found that the structure of the polysoap backbone influenced the pH-dependent swelling and deswelling. The swelling process is reversible after repeating cycles of swelling and deswelling induced by a change of pH in appropriate buffer solutions. SEM micrographs of polysoap gels indicate that the network structures are characterized by the presence of large open pores or small closed pores. The stimuli response of the polysoap gels in electric fields was also investigated. In a contact electric field, deswelling was observed at the anode side of the gels. In a non-contact electric field, the gels bend towards the anode. The gels can turn back to the original shape and bend toward the cathode with time when higher electric potentials are applied. These properties of the gels are related to both the change of osmotic pressure caused by mobile ions and by hydrophobic interactions.

Novel nucleotide-responsive hydrogels designed from copolymers of boronic acid and cationic units and their applications as a QCM resonator system to nucleotide sensing

Hydrogels comprised of boronic acid monomer (3), cationic monomer (4), and crosslinker monomer (5) were prepared by radical copolymerization. These hydrogels could efficiently bind nucleotides such as AMP and ATP by a cooperative action of the boronic acid-cis-diol complexation and the electrostatic interaction between the cationic unit and the phosphate group. The binding processes were conveniently monitored by the swelling and deswelling behaviors of these hydrogels in aqueous solution. For the hydrogel with the specific monomer composition an interesting charge inversion was observable: with increasing AMP or ATP concentration, the cation-rich hydrogel was gradually charge neutralized, once shrunken at the neutral stage, and then swollen again because of the anion-rich charge state. These nucleotide-induced swelling and deswelling phenomena were reproduced on the gold surface of a QCM resonator. Therefore, the present system is not only interesting to consider nucleotide-induced mechanochemical properties, but also applicable as a sensor to the nucleotide detection.