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.     

Synthesis of thermoresponsive polystyrene-based comb-type grafted poly(N-isopropylacrylamide)

Narrowly distributed polystyrene-g-p(N-isopropylacrylamide) (PSt-g-PNIPAM) was prepared by atom transfer radical polymerization (ATRP) of N-isopropylacrylamide using the brominated polystyrene as macroinitiator and CuCl combined with hexamethyltriethylenetetramine as catalyst. Fourier transform infrared (FT-IR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy confirmed the structure of PSt-g-PNIPAM. The gel permeation chromatography (GPC) showed that the graft copoly- mer had a single distribution peak with molecular weight, Mn (g/mol) of 19815 g/mol (using polystyrene as the standard). Differential scanning calorimetry (DSC) revealed that due to both effects of hydro- phobic isopropyl groups and hydrogen bonds in the amide group, the glass transition temperature (Tg) of PSt-g-PNIPAM enhanced 16.0 ℃ compared to the Tg of the polystyrene.     

Tailoring thermoresponsive nanostructured poly(N-isopropylacrylamide) hydrogels made with poly(acrylamide) nanoparticles

The thermoresponsive behavior and mechanical properties of nanostructured hydrogels, which consist of poly(acrylamide) nanoparticles embedded in a cross-linked poly(N-isopropylacrylamide) hydrogel matrix, are reported here. Nanostructured hydrogels exhibit a tuned volume phase transition temperature (T _VPT), which varies with nanoparticle content in the range from 32 up to 39–40 °C. Moreover, larger equilibrium water uptake, faster swelling and de-swelling rates, and larger equilibrium swelling at 25 °C were obtained with nanostructured hydrogels compared with those of conventional ones. Elastic and Young’s moduli were larger than those of conventional hydrogels at similar swelling ratios. The tuned T _VPT and the de-swelling rate were predicted with a modified Flory–Rehner equation coupled with a mixing rule that considers the contribution of both polymers. These behaviors are explained by a combination of hydrophilic/hydrophobic interactions and by the controlled inhomogeneities (nanoparticles) introduced by the method of synthesis.     

Structural properties of thermoresponsive poly(N-isopropylacrylamide)-poly(ethyleneglycol) microgels

We present investigations of the structural properties of thermoresponsive poly(N-isopropylacrylamide) (PNiPAM) microgels dispersed in an aqueous solvent. In this particular work poly(ethyleneglycol) (PEG) units flanked with acrylate groups are employed as cross-linkers, providing an architecture designed to resist protein fouling. Dynamic light scattering (DLS), static light scattering (SLS), and small angle neutron scattering (SANS) are employed to study the microgels as a function of temperature over the range 10 °C ≤ T ≤ 40 °C. DLS and SLS measurements are simultaneously performed and, respectively, allow determination of the particle hydrodynamic radius, R(h), and radius of gyration, R(g), at each temperature. The thermal variation of these magnitudes reveals the microgel deswelling at the PNiPAM lower critical solution temperature (LCST). However, the hydrodynamic radius displays a second transition to larger radii at temperatures T ≤ 20 °C. This feature is atypical in standard PNiPAM microgels and suggests a structural reconfiguration within the polymer network at those temperatures. To better understand this behavior we perform neutron scattering measurements at different temperatures. In striking contrast to the scattering profile of soft sphere microgels, the SANS profiles for T ≤ LCST of our PNiPAM-PEG suspensions indicate that the particles exhibit structural properties characteristic of star polymer configurations. The star polymer radius of gyration and correlation length gradually decrease with increasing temperature despite maintenance of the star polymer configuration. At temperatures above the LCST, the scattered SANS intensity is typical of soft sphere systems.     

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.     

Structural characterization of nanoparticles from thermoresponsive poly(N-isopropylacrylamide)-DNA conjugate

Poly(N-isopropylacrylamide) (PNIPAAm) grafted with single-stranded (ss) DNA conjugate (PNIPAAm-g-DNA) self-assembles above its lower critical solution temperature to form colloidal particles. When the ssDNA within the particle hybridizes with its complementary DNA, the particles aggregate above a certain threshold of salt concentration with drastically increased turbidity in solution. Detailed structural information of the particle was obtained mainly by small-angle X-ray scattering. The influence of copolymer composition on the morphology of particle and non-crosslinking aggregation was examined. The particle consists of hydrophobic PNIPAAm core surrounded by hydrophilic DNA strands. The increase in DNA fraction brought about a significant decrease in core size, whereas the shell thickness little changed and corresponded to the length of DNA. A structural model with a sticky potential was applied to the analysis of particle aggregate. This analysis provided that the particles aggregate while the coronal layers interpenetrate each other. The interaction between the particles was quantified in terms of the sticky potential and showed a trend to be influenced by the particle size rather than the graft density of DNA strands on the particle.     

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.     

Phase transition behavior of unimolecular micelles with thermoresponsive poly(N-isopropylacrylamide) coronas

This paper describes the double phase transition behavior of a thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) brush at the surface of a hydrophobic core. Reversible addition-fragmentation transfer (RAFT) polymerization of N-isopropylacrylamide (NIPAM) was conducted by using a hyperbranched polyester (Boltorn H40) based macroRAFT agent. The resultant multiarm star block copolymer (H40-PNIPAM) exists as unimolecular micelles with hydrophobic H40 as the core, densely grafted PNIPAM brush as the shell. A combination of laser light scattering (LLS) and microdifferential scanning calorimetry (micro-DSC) studies of H40-PNIPAM in aqueous solution reveals double phase transitions of the PNIPAM corona, which is in contrast to the fact that free PNIPAM homopolymer in aqueous solution exhibits a lower critical solution temperature (LCST) at approximately 32 degrees C. The first phase transition takes place in the broad temperature range 20-30 degrees C, which can be tentatively ascribed to the n-cluster-induced collapse of the inner region of the PNIPAM brush close to the H40 core; the second phase transition occurs above 30 degrees C, which can be ascribed to the outer region of PNIPAM brush. Employing the RAFT chain extension technique, the inner and outer part of PNIPAM brush were then selectively labeled with pyrene derivatives, respectively; temperature-dependent excimer fluorescence measurements further support the conclusion that the inner part of PNIPAM brush collapses first at lower temperatures, followed by the collapse of the outer part at higher temperatures.     

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.     

Thermoreversible gelation of isotactic-rich poly(N-isopropylacrylamide) in water

We report the experimentally determined phase diagram for an aqueous solution of isotactic-rich poly(N-isopropylacrylamide) (PNiPAM) composed of the sol-gel transition curve and the cloud-point curve. The meso diad content of isotactic-rich PNiPAM is 64%, and it is soluble in water at low temperatures, but undergoes a sol-to-gel transition with increasing temperature in the investigated concentration range of 1.8 wt. %-6.0 wt. %. With a further increase in temperature, the system becomes turbid. The gel formation and clouding behavior are thermally reversible. This is the first observation of thermoreversible gelation under the cloud-point temperature for an aqueous solution of PNiPAM. On the basis of the determined phase diagram, we carried out light scattering experiments to characterize the sol-gel transition behavior as a function of temperature.     

Thermal analyses of poly(N-isopropylacrylamide) in aqueous solutions and in nanocomposite gels

The coil-to-globule transition of poly(N-isopropylacrylamide) (PNIPA) prepared by free-radical redox polymerization in aqueous solutions and its nanocomposite (NC) gels were investigated by differential scanning calorimetery. The lower critical solution temperatures (LCST) of aqueous solutions of PNIPA of different molecular weights were not significantly affected by molecular weight (M _w: 0.19?×?10⁶?4.29?×?10⁶?g?×?mol^?1) or polymer concentration (1?10?wt%), although the enthalpy of transition increased with molecular weight, at M _w (<1.2?×?10⁶ g?×?mol^?1). The glass-transition temperature of PNIPA in the dried state also remained constant (138?°C), regardless of molecular weight. On the other hand, the enthalpy of the coil-to-globule transition of PNIPA in NC gels consisting of a PNIPA/clay network decreased with increasing clay concentration (C _clay), while the onset temperature (≡LCST) was almost constant, regardless of C _clay. The PNIPA chains in NC gels could be classified into the following three types: P-1, which exhibits a normal LCST transition, similar to that of linear PNIPA; P-2, exhibiting restricted transition at higher temperatures as a result of interactions with the clay; and P-3, which does not undergo that transition because of stronger restrictions. It was found that the proportion of P-3 increases with increasing C _clay. However, some P-1 and P-2 was still observed, even in NC gels with high C _clay. That the transition to the hydrophobic globular state was restricted by interactions with the clay was confirmed by measurements on PNIPA after removal of the clay from NC gels.     

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.     

Surface instabilities in ultrathin, cross-linked poly(N-isopropylacrylamide) coatings

Near-the-surface instabilities with a cusplike morphology were observed in ultrathin photo-cross-linked poly(N-isopropylacrylamide) coatings upon swelling in water. The characteristic wavelength of the instability was approximately 25 times the dry thickness and scaled linearly with coating thickness between 30 and 1200 nm. Above 1200 nm, slippage of the coating along the confining substrate led to reticulated patterns with a much larger wavelength. To help interpret the origin of the instability, the coatings were also exposed to a solvent slightly worse than water (acetone) and a solvent slightly better than water (isopropanol). In all cases, the characteristic wavelength scaled linearly with respect to the swelling induced by each solvent. Both water and isopropanol produced well-defined cusps or folds in the gel surface, while acetone produced semiordered blisters that grew into one another. The features produced in acetone may be a consequence of swelling being close to the threshold value for the loss of planar stability. Through the use of a first-order linear perturbation of the Flory-Rehner model, it is shown that the emergence of a characteristic wavelength is consistent with an inhomogeneous distribution of solvent that results from diffusion of solvent into a dry coating.     

Importance of bound water in hydration-dehydration behavior of hydroxylated poly(N-isopropylacrylamide)

In this study, a differential scanning calorimetric analysis was performed to investigate the role of water existing around the polymer chains on their thermoresponsive behaviors using the novel functional temperature-sensitive copolymer, poly(N-isopropylacrylamide-co-2-hydroxyisopropylacrylamide) (poly(NIPAAm-co-HIPAAm)). The HIPAAm comonomers were incorporated into the polymeric chains as hydrophilic parameters, and then the hydration states of poly(NIPAAm-co-HIPAAm) with various HIPAAm compositions were examined. Bound water, which is affected by the polymeric chains to some extent, was produced by adding the copolymers to the water, and the temperature due to the melting of the bound water decreased as the HIPAAm content increased. On the basis of this result, we considered that the interaction between the bound water and the polymeric chains is reinforced by the increasing HIPAAm composition. In addition, the cloud points of the copolymers shifted to a higher temperature, and the endothermic enthalpy for the phase transition decreased with increasing the HIPAAm content, suggesting that the number of water molecules disassociated from the polymeric chains decreased. Based on these results, we postulate that the changes in the interaction between the thermosensitive polymer and bound water exert a strong influence on its phase transition and/or separation, such as the cloud point or dehydration behavior.     

Temperature-induced aggregation of poly(N-isopropylacrylamide)-stabilized CdS quantum dots in water

Water-soluble nanosized semiconductor CdS particles (quantum dots, QDs) were synthesized with a protective layer of covalently grafting linear thermally sensitive poly(N-isopropylacrylamide) chains. Reversible association and dissociation of these CdS particles can be induced via an alteration of the solution temperature. The formation and fragmentation of the QD aggregates of the CdS particles were systematically investigated by laser light scattering (LLS) and confirmed by transmission electron microscopy (TEM). There exists a hysteresis during one heating-and-cooling cycle. The CdS particles stabilized with shorter PNIPAM chains (Mn=15,000 g/mol) can associate to form larger and denser spherical aggregates with a much higher aggregation number than those grafted with longer PNIPAM chains (Mn=31,000 g/mol) in the heating process. The dissociation (fragmentation) in the cooling process has two stages: initially, the aggregates dissociate as the temperature decreases, and then, the fragmentation stops over a wider temperature range before complete dissociation. We attribute such a two-stage fragmentation to a balanced effect of inter- and intrachain hydrogen bonding as well as the hydrophobic interaction between PNIPAM chains and CdS 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.