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.     

Phase separation in semidilute aqueous poly(N-isopropylacrylamide) solutions

The phase separation mechanism in semidilute aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions is investigated with small-angle neutron scattering (SANS). The nature of the phase transition is probed in static SANS measurements and with time-dependent SANS measurements after a temperature jump. The observed critical exponents of the phase transition describing the temperature dependence of the Ornstein-Zernike amplitude and correlation length are smaller than values from mean-field theory. Time-dependent SANS measurements show that the specific surface decreases with increasing time after a temperature jump above the phase transition. Thus, the formation of additional hydrogen bonds in the collapsed state is a kinetic effect: A certain fraction of water remains as bound water in the system. Moreover, H-D exchange reactions observed in PNIPAM have to be taken into account.     

Water flow in poly(N-isopropylacrylamide) gels

Friction between a polymer network of poly(N-isopropylacrylamide) gels and solvent water was investigated. The gel was mechanically constrained in a glass capillary at gelation, and hydrostatic pressure was directly applied to the cross section of the cylinder. The temperature dependence of the flow velocity was extensively measured in the vicinity of the transition temperature for gels with different lengths, l(0), at gelation. As the temperature increased, the friction slightly decreased at the transition point and increased rapidly in the collapsed phase. Although the flow velocity depended on l(0), the friction in the vicinity of the transition point was well scaled by l(0) based on the Hagen-Poiseuille equation for the flux of water flow in a capillary. The results suggested that the assumption that the gel is a bundle of microcapillaries was applicable to the water flow through the hydrogel, which was largely deformed not only by the pressure applied to the solvent but also by the shrinking force caused by the temperature increment. Macroscopic deformation did not affect the friction between the three-dimensional polymer network and water.     

Swelling and deswelling kinetics of poly(N-isopropylacrylamide) gels

Swelling and deswelling kinetics was investigated for three types of cylindrical poly(N-isopropylacrylamide) (PNIPA) gels differing in crosslink density. The temperature dependence curves of the volume of the gel specimens were different from one another. One of the gel specimens was considered as a critical gel showing the continuous volume phase transition. The volume change process of the specimens after a temperature jump was examined. In the deswelling processes with temperature jumps to temperatures higher than 35 degrees C, a phase separation was observed in the gel specimens and the volume change slowed down due to the homogenization after the phase separation. The value of the diffusion constant obtained without the phase separation decreased rapidly as temperature approaches the transition temperature. The rapid decrease for the critical gel indicates the emergence of the critical slowing-down. The value of the critical exponent for the correlation length suggests that the universality class for the volume phase transition of the critical PNIPA gel belongs to the class for the classical theory.     

Surface friction of thermoresponsive poly(N-isopropylacrylamide) gels in water

In this paper, we report the experimental results of surface friction between thermoresponsive poly(N-isopropylacrylamide) gels in water. The static friction force was found to depend on the waiting period prior to slider movement after contact between gel surfaces, which was a result of two relaxation mechanisms: the stress decay process due to macroscopic deformation under a normal load and the microscopic conformational change in the real contact area of polymer networks. The sliding velocity and the normal load dependence of the kinetic friction force were extensively measured. The results suggested that the following two mechanisms depended on the sliding velocity: the friction force generated by direct contact of the solid-like behavior and the viscous resistance of the liquid-like behavior. The strong temperature dependence of kinetic friction was observed, which was a result of a change in the balance between hydrophobic and hydrophilic interactions. The experimental results are discussed in terms of the multi-asperity contacts between the swollen gel/gel interfaces (solid friction, depending on the waiting period) and the viscous resistance and lubricating effect between the gel/water interfaces (fluid friction, depending on the sliding velocity).     

Swelling of poly(N-isopropylacrylamide) gels in water-aprotic solvent mixtures

The swelling volume of poly(N-isopropylacrylamide) (PIPAAm) gel in aprotic solvents (acetonitrile (AcN)-, tetrahydrofuran (THF)-, 1,4-dioxane (DO)- and dimethylsulfoxide (DMSO))-water mixtures was measured at 25°C. The gel swollen in water shrank first and then reswelled with addition of the aprotic solvents. At an intermediate mole fraction (XDMSO) range of DMSO-water mixtures, the gel demonstrated a reentrant swelling phenomenon the hydrated gel shrank first on addition of a small amount of solvent, showed a typical wide reentrant transition, and gradually reswelled in the range near pure solvent. On the other hand, the gels in AcN-, THF-, and DO-water mixtures demonstrated a reentrant-convex swelling phenomenon: the gels reswelled after a reentrant phase transition in low Xorg (XAcN, XTHF and XDO), showed a maximum swelling in the intermediate Xorg region, and shrank again gradually in the high Xorg region. Such a swelling behavior of the gel was interpreted by correlating with solution properties of the aqueous aprotic solvent mixtures.The strength of hydrogen bonding around amide groups of the homopolymer was examined in pure solvents (water, THF, and DMSO) and in all proportion of aqueous THF to observe the relation with swelling behavior of gel by spectrum analysis of the amide I and II bands of Fourier Transform Infrared Spectroscopy (FT-IR). The swelling properties of gels in solvents and the aqueous mixtures were well correlated with the peak shifts of amide groups of the homopolymer.     

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.     

Fluorescence studies on volume phase transition in poly(acrylamide) and poly(N-isopropylacrylamide) gels

The changes in microenvironments during the volume phase transition of poly(acrylamide) and poly(N-isopropylacrylamide) gels induced by pH change or the change in solvent composition were studied by using dansyl or pyrenyl fluorescent probes.     

Electron-beam initiated crosslinking in poly(N-isopropylacrylamide) aqueous solution

The reactions between the OH, H and e_aq⁻ transients of water radiolysis and a linear poly(N-isopropylacrylamide) were identified by the spectral and kinetic properties of intermediates. The radical responsible for crosslink formation is the isopropyl-centered radical that forms mainly in OH radical attack on the polymer. Below pH 3 this radical undergoes reversible protonation with pK_a≈2.1. The radical decay is composed of fast and slow parts. The initial fast decay is attributed to intramolecular reactions of radicals on the same chain (loop formation), the following slow decay to competition between further intramolecular and intermolecular (H-type crosslinks) termination processes. The differences in the network formation during irradiation of aqueous monomer and polymer solutions are discussed.     

Dynamic surface properties of poly(N-isopropylacrylamide) solutions

The dynamic surface elasticity of aqueous solutions of poly(N-isopropylacrylamide) (pNIPAM) has been measured by the oscillating barrier and capillary wave methods as a function of time and concentration. While the real and imaginary parts of the surface elasticity almost did not change with the concentration, their kinetic dependencies proved to be nonmonotonic. Simultaneous measurements of the film thickness and adsorbed amount by null-ellipsometry showed that the pNIPAM adsorption can be divided into two steps corresponding to the formation of a concentrated narrow region close to the air phase and a region of tails and loops protruding into the bulk liquid. The local maximum of the elasticity can be observed in the course of the first step when the adsorbed macromolecules do not form long loops and tails. The results are in agreement with recent data on the nonequilibrium surface properties of solutions of other nonionic homopolymers and the theory of dilational surface viscoelasticity.     

Temperature-responsive photoluminescence of quinoline-labeled poly(N-isopropylacrylamide) in aqueous solution

The pH- and temperature-responsive optical properties of a quinoline-labeled poly(N-isopropylacrylamide) copolymer are explored in aqueous solution and compared to the respective behavior of a similar quinoline-labeled poly(N,N-dimethylacrylamide) copolymer. These copolymers, P(NIPAM-co-SDPQ) and P(DMAM-co-SDPQ), were prepared through free radical copolymerization of 2,4-diphenyl-6-(4-vinylphenyl)quinoline (SDPQ) with the thermosensitive N-isopropylacrylamide (NIPAM) and the hydrophilic N,N-dimethylacrylamide (DMAM), respectively. Both copolymers exhibit the well-known pH-controlled optical response of quinoline unit in aqueous solution and the emitted color changes from blue to green upon decreasing pH. Nevertheless, a ～20 nm emission shift is observed upon heating the aqueous P(NIPAM-co-SDPQ) solution, regardless of pH, due to the formation of hydrophobic microdomains (Nile Red probing), as a consequence of the Lower Critical Solution Temperature (LCST) behavior of this copolymer in water. Interestingly, this LCST behavior also imposes the partial deprotonation of the otherwise protonated SDPQ unit at pH = 2 and the emission of the basic form appears upon increasing temperature, suggesting that the acid/base equilibrium of the quinoline unit is significantly temperature-controlled, when introduced in the thermosensitive poly(N-isopropylacrylamide) chain.     

Swelling and drug releasing properties of poly(N-isopropylacrylamide) thermo-sensitive copolymer gels

A series of N-isopropylacrylamide (NIPAAm) copolymer gels with different hydrophilicities were prepared from NIPAAm, hydrophilic acrylamide (AAm) and hydrophobic butyl methacrylate (BMA). The swelling and thermo-responsive properties of PNIPAAm P (NIPAm-co-BMA) and P(NIPAm-co-AAm) copolymer hydrogels were investigated. The drug loading and releasing behaviors for two kinds of model drug with different hydrophilicities were studied. The result shows that the copolymer gels present negative thermo-sensitivities. The lower critical solution temperature (LCST), equilibrium swelling degree and the initial swelling rate increase as the hydrophilicity of gels increases when the temperature is below the LCST. With increasing gel hydrophilicity the loading ratio for sodium salicylate increases, while for salicylic acid, the reverse is observed. The initial drug releasing rate of sodium salicylate and salicylic acid also increase with increasing gel hydrophilicity. The initial drug releasing rate of sodium salicylate is significantly higher than that of salicylic acid. For salicylic acid which is less hydrophilic, the equilibrium releasing ratio at high temperature is lower than that at low temperature while for sodium salicylate which is more hydrophilic, the equilibrium releasing ratio at high temperature is almost the same as that at low temperature. Equilibrium releasing ratios of the three gels are significantly different from each other for salicylic acid when the temperature is below LCST while the equilibrium releasing ratios of the three gels are all 100% for sodium salicylate. __________ Translated from Journal of Central South University (Science and Technology), 2007, 38(5): 906–911 [译自: 中南大学学报(自然科学版)]     

Preparation of poly(N-isopropylacrylamide) emulsion gels and their drug release behaviors

Stimuli-sensitive drug delivery systems (DDSs) have attracted considerable attention in medical and pharmaceutical fields; thermosensitive DDS dealing with poly(N-isopropylacrylamide) (poly(NIPA)) have been widely studied. Novel NIPA emulsion gels, i.e., NIPA hydrogels containing distributed oil (oleyl alcohol) microdroplets, were synthesized by means of an emulsion-gelation method in which the polymerization of hydrogels in an aqueous phase in an oil-in-water (O/W) emulsion and the loading of a lipophilic drug (indomethacin) dissolved in an oil phase were accomplished simultaneously. The pulsatile (on-off) drug release from the NIPA emulsion gel loading indomethacin to a phosphate buffered saline (PBS) solution was successfully controlled by a temperature swing between 25 degrees C (release off) and 40 degrees C (release on). The mechanism of the pulsatile drug release was discussed in relation to the diffusion rate, distribution ratio, solvent exchange of NIPA hydrogels, and drug release from an NIPA organogel. The mechanism was as follows: the solvent exchange occurred within the NIPA emulsion gel (the NIPA gel-network absorbed oleyl alcohol with indomethacin) at temperatures above the LCST, and the diffusion rate of indomethacin through the solvent-exchanged gel was higher at 40 degrees C than at 25 degrees C.     

Effect of heating rate on thermo-induced aggregation of poly(ethylene oxide)-b-poly(N-isopropylacrylamide) in aqueous solutions

<正>The effects of heating rate on the aggregate behavior of poly(ethylene oxide)-b-poly(N-isopropylacrylamide) in aqueous solutions were investigated in detail by laser light scattering and TEM.By employing two separate heating protocols,step-by-step heating at5 K/step and one-step jump,to heat the sample from 15℃to the selected temperature, we found that the heating rate only showed significant effect on the aggregates above the cloud point.The aggregate formed by step-by-step heating exhibited a much larger size and a broader size distribution than those formed by one-step jump heating.Moreover,neither of the aggregates were ideal micellar structures as indicated by the size and the R_g/R_h values.On the contrary,at temperatures below the cloud point where the block copolymer formed core-shelled micelles,the heating rate showed negligible effect on the size and size distribution of the micelles.Since the system underwent a phase separation above the cloud point,the heating rate effect could be reasonably explained by the phase separation mechanisms:the nucleation-and-growth mechanism in the metastable region and the spinodal decomposition mechanism in the unstable region.     

Interaction of poly(N-isopropylacrylamide) with perfluorooctanoic acid in aqueous solution

Interaction of poly(N-isopropylacrylamide) (PNIPAAM) with perfluorooctanoic acid (PFOA) was explored in aqueous solution. Increasing concentrations of PFOA were observed first to depress slightly the lower critical solution temperature (LCST) then to elevate it at concentrations greater than ca. 2.5 mM. At concentrations >ca. 3.5 mM, the LCST transition could not be detected by either microcalorimetry or cloud point measurements. PNIPAAM appeared to promote the micellization of PFOA. Pinacyanol dye experiments were ambiguous, but the aggregation concentration reported by surface tension measurements was clearly depressed upon addition of PNIPAAM.     

Gelation mechanism of poly(N-isopropylacrylamide)-clay nanocomposite hydrogels synthesized by photopolymerization

The gelation process of poly-(N-isopropylacrylamide)-clay nanocomposite hydrogels (PNIPAAm-clay NC gels) was investigated by dynamic and static light scattering (DLS and SLS), as well as by fluorescence correlation spectroscopy (FCS). The photopolymerization method chosen for the radical polymerizing system ensured that, when the irradiation is removed, the reaction stopped immediately. Experiments showed that shortly before the gelation threshold is reached, no changes in the DLS autocorrelation functions appear, while the monomer conversion can be observed by 1H NMR spectroscopy. These results correspond to the formation of microparticles, in which the PNIPAAm chains are closely attached to the clay platelets. During the further polymerization process, clay clusters are developed before the sol-gel threshold is reached. FCS measurements were performed to obtain information on the motion of the clay platelets inside the NC gel. The DLS method gives only an average of the motions in the gel. In a time window between 10 micros and 1 s, the clay sheets labeled with Rhodamine B show no characteristic motions.     

Rheological properties of poly(ethylene glycol) solutions and gels

By the interaction of a water–glycol solution of poly(ethylene glycol) (PEG) with calcium chloride dihydrate, a gel was produced. It was determined that, below a certain shear rate, this gel is a Newtonian fluid; however, above a certain shear rate, which depends on the gel viscosity, the properties of this gel are anomalous: the gel flow instantaneously completely stops. The viscosity of the gels was found to exponentially increase with increasing concentration of the cross-linking metal at constant PEG concentration. The density of the gels linearly increases with increasing concentration of the cross-linking metal at constant PEG concentration.     

Thermal property changes of poly(N-isopropylacrylamide) microgel particles and block copolymers

Investigation of the thermo-reversible properties of different poly(N-isopropyl acrylamide) samples, including microgels and block copolymers, with a combination of methods such as electron microscopy, dynamic light scattering, analytical ultracentrifugation, electrophoresis and ultrasound resonator technology allows comprehensive characterisation of the phase transition. By the combination of methods, it was possible to show that the precipitated polymer phase contains at 40 °C between 40 and 50 vol.% of water. Besides free bulk water, there is also bound water that strongly adheres to the N-isopropyl acrylamide units (about 25 vol.%). Ultrasound resonator technology, which is a non-sizing characterisation method, revealed for the microgel particles two more temperatures (at about 35 and between 40 °C and 50 °C depending on the chemical nature) where characteristic changes in the ultrasound attenuation take place. Moreover, the experimental data suggest that the phase transition temperature is related to surface charge density of the precipitated particles.     

Effect of ionization on the temperature- and pressure-induced phase transitions of poly(N-isopropylacrylamide) gels

The ionization effects on the pressure-induced phase transition of weakly charged poly(N-isopropylacrylamide-co-acrylic acid) (PNIPA-AAc) gels have been investigated by small-angle neutron scattering. At low temperature, T, and pressure, P, the structure factor of PNIPA-AAc gels was well represented by a Lorentzian (L) function, which was similar to noncharged PNIPA gels. However, at high Ps, the contribution of inhomogeneities became large and a squared-Lorentzian term had to be added in addition to the L term. At high Ts, on the other hand, a scattering maximum appeared, indicating microphase separation. This scattering maximum was suppressed by increasing P up to P approximately 100 MPa and then reincreased at higher Ps. The following facts were disclosed: (1) The peak position and height were very sensitive to P, which is mainly ascribed to strong pressure dependence of hydrophobic interaction, (2) ionization leads to microphase separation at elevated temperatures, (3) the re-entrant phase behavior is commonly observed in the P-T plane due to the parabolic variation of the polymer-solvent interaction with P, and (4) the pressure and temperature dependence of the structure factor was reproduced with the Rabin-Panyukov theory and was interpreted with a convexity of hydrophobic interaction with respect to pressure.