Closed-loop sol-gel transition of PEG-PEC aqueous solution

We are reporting an unusual closed-loop phase behavior of poly(ethylene glycol)-beta-poly(ethyl-2-cyanoacrylate) (PEG-PEC) aqueous solutions. As the temperature increased from 0 to 60 degrees C, the aqueous polymer solution (12 wt %) underwent sol-to-gel and gel-to-syneresis transitions. However, the polymer aqueous solution persisted as a sol phase below 4.0 wt % as well as above 16 wt % in the same temperature range, thus forming a closed-loop gel domain in the phase diagram. The closed-loop gel domain is suggested to be a result of the balance between the aggregation and the stabilization of micelles in specific temperature and concentration ranges.     

Phase behavior and modeling of the poly(methyl methacrylate)–CO2–methyl methacrylate system

Cloud-point data for the system poly(methyl methacrylate) (PMMA)–CO₂–methyl methacrylate (MMA) are measured in the temperature range of 26 to 170°C, to pressures as high as 2500 bar, and with cosolvent concentrations of 10.4, 28.9, and 48.4 wt.%. PMMA does not dissolve in pure CO₂ to 255°C and 2550 bar. The cloud-point curve for the PMMA–CO₂–10.4 wt.% MMA system exhibits a negative slope that reaches 2500 bar at 105°C. With 28.9 wt.% MMA the cloud-point curve remains relatively flat at ∼900 bar for temperatures between 25 and 170°C. With 48.4 wt.% MMA the cloud-point curve exhibits a positive slope that extends to 20°C and ∼100 bar. Pressure-composition isotherms are also reported for the CO₂–MMA system at 40.0, 80.0, 105.5°C. This system exhibits type-I phase behavior with a continuous mixture–critical curve. The Peng–Robinson (PR) and SAFT equations of state model the CO₂–MMA data reasonably well without any binary interaction parameters, although the PR equation provides a better representation of the mixture-critical region. It is not possible to obtain even a qualitative fit of the PMMA–MMA–CO₂ data with the SAFT equation of state. The SAFT model qualitatively shows that the cloud-point pressure decreases with increasing MMA concentration and that the cloud-point curve exhibits a positive slope for very high concentrations of MMA in solution.     

Gel-sol transition in gellan aqueous solutions

Gel-sol transition of sodium type gellan solutions with and without salts is studied by dynamic viscoelastic measurements and differential scanning calorimetry (DSC). Mechanical spectra show that gellan aqueous solutions behave as an entangled polymer solution in the concentration range around 2 wt.-% at temperatures >15°C and as a weak gel below this temperature. Concentrated solutions (> 3 wt.-%) show a true gel behavior below 30°C. The two step transition is observed for 2∼3 wt.-% gellan aqueous solutions in thermal scanning rheological (TSR) measurements; the transition at a higher temperature is attributed to a coil-helix transition whilst the transition at a lower temperature is attributed to sol-gel transition. The transition observed in dilute solutions of gellan is attributed to the coil-helix transition whilst the sol-gel transition occurs simultaneously with coil-helix transition in more concentrated solutions (>3 wt.-%). The sol-gel transition temperature shifts to higher temperatures with increasing concentration of the added salts. Junction zones formed in the presence of divalent cations are far more heat resistant than those with monovalent cations judging from both DSC and TSR, however, the possibility of the formation of junction zones by covalent bonds or by ionic bonds is excluded.     

Unperturbed volume transition of thermosensitive poly-(N-isopropylacrylamide) microgel particles embedded in a hydrogel matrix

The thermoresponsive behavior of poly-(N-isopropylacrylamide) (PNiPAM) microgels embedded in a covalently cross-linked polyacrylamide hydrogel matrix was investigated using ultraviolet-visible (UV-vis) spectroscopy, small-angle neutron scattering (SANS), and confocal laser scanning microscopy. The hydrogel synthesis was performed at two different temperatures, below and above the volume phase transition temperature of PNiPAM, resulting in highly swollen or fully collapsed PNiPAM microgel particles during the incorporation step. UV-vis spectroscopy experiments verify that the incorporation of thermosensitive microgels leads to temperature-sensitive optical properties of the composite materials. SANS measurements at different temperatures show that the thermosensitive swelling behavior of the PNiPAM microgels is fully retained in the composite material. Volume and structure criteria of the embedded microgel particles are compared to those of the free microgels in acrylamide solution. To visualize the temperature responsive behavior of larger PNiPAM particles, confocal fluorescence microscopy images of PNiPAM beads, of 40-microm size, were taken at two different temperatures. The micrographs also demonstrate the retained temperature sensitivity of the embedded microgels.     

Temperature-dependent intermolecular force measurement of poly(N-isopropylacrylamide) grafted surface with protein

We have investigated the temperature dependence of the intermolecular force between poly(N-isopropylacrylamide) (PNiPAM) grafted surface and bovine serum albumin (BSA) in phosphate buffer (pH 7.4) using atomic force microscopy at the nanonewton scale. These observations show that the interaction force is nearly zero below the phase transition temperature of PNiPAM and that it increases steeply during the phase transition. Since the PNiPAM chains are grafted onto the aminosilane (gamma-aminopropyltriethoxysilane)-treated silicon wafer, we measured the force-distance curve of BSA-immobilized tips for the bare and the aminosilane-treated silicon wafer. These surfaces show no temperature dependence and their values are different from those of the PNiPAM-grafted surfaces at 30 degrees C. The results indicate that the measured adhesion force is between the PNiPAM-grafted surface and the BSA-immobilized tip. Our studies on the intermolecular force between other surfaces (CH(3)- and COOH-terminated self-assembled monolayers) and the BSA-immobilized tip indicate that the variation in the intermolecular force between the PNiPAM surface and BSA with temperature can be attributed to the changes in the properties of the PNiPAM chains. From consideration of the PNiPAM phase transition mechanism, it is speculated that the intermolecular force between the PNiPAM-grafted surface and BSA would be affected by changes in the arrangement of the bound water molecules around the PNiPAM chain and by changes in the conformation (i.e., in the chain mobility) of the PNiPAM chain during the phase transition.     

Compound formation and glassy solidification in the system gelatin-water

Calorimetric investigations of the system gelatin-water lead to the conclusion that the state diagram is of the eutectic type. At the invariant eutectic temperature ice, nearly pure water and an intermediate compound with an over-all concentration of 67 % by wt gelatin coexist. The liquidus and the solidus curves have been determined up to temperatures very close to the melting point of pure gelatin at 510 K. The glassy solidification curve, which has been measured between a solution of 40% by wt and pure gelatin, is situated below but very close to the solidus. From the change of the cooling rate different non-equilibrium states can be verified leading to a second, morphologically caused glass transition, which does not correspond to the initial over-all composition of the homogeneous phase. The phase behaviour is discussed with respect to the model proposed for collagen fibrils by Hosemann et al.Dedicated to Prof. Dr. Robert Kosfeld on occasion of his 60th birthday.     

Simultaneous cloud-point extraction of nine cations from water samples and their determination by flame atomic absorption spectrometry.

The cloud-point methodology was successfully employed for the preconcentration of heavy metal cations at trace levels from aqueous samples prior to flame atomic absorption spectrometry (FAAS). Cations were taken into a complex with 8-quinolinol in an aqueous non-ionic surfactant, Triton X-114, medium and concentrated in the surfactant rich phase by bringing the solution to the cloud-point temperature. The preconcentration of only 100 mL of the solution with 1% Triton X-114 and 10(-3) M 8-quinolinol at pH 7.0 gave a preconcentration factor higher than 100 for most cations. Under these conditions, the detection limits of the cloud-point extraction-FAAS system were 0.8 - 15 microg/L.     

Microemulsions of triglyceride and non-ionic surfactant — effect of temperature and aqueous phase composition

The phase behavior of soybean oil, polyoxyethylene (40) sorbitol hexaoleate and water—ethanol was investigated. Regions of water-in-oil (W/O) microemulsions were determined and were found to be strongly dependent on temperature and water:alcohol ratios. At a water:ethanol ratio of 80/20 (wt.%), an oil:surfactant ratio of 2/3 and a temperature of 25°C, the microemulsion region extended continuously from the oil—surfactant axis to the phase diagram center. However, at the hydrophilic—lipophilic balance (HLB) temperature (20–22°C) and a water:ethanol ratio of 80/20 or 75/25 (wt.%), a single-phase area separated from the original microemulsion region. Conductivity measurements and dynamic light scattering intensifies at 25°C indicated that association structures were formed with increasing aqueous phase concentrations above 15 wt.%. At 20°C, the single-phase scattering intensifies increased sharply with increasing aqueous phase concentrations (38–46 wt.%) and a plateau in the conductivity was detected.

Transmission electron microscopy results supported the finding that more particles are formed with increasing aqueous phase and form connected particles, resulting in constant conductance.     

Hydration and phase separation of temperature-sensitive water-soluble polymers

Collapse of a poly(N-isopropylacrylamide)(PNIPAM) chain upon heating and phase diagrams of aqueous PNIPAM solutions with very flat LCST phase separation line are theoretically studied on the basis of cooperative dehydration(simultaneous dissociation of bound water molecules in a group of correlated sequence),and compared with the experimental observation of temperature-induced coil-globule transition by light scattering methods.The transition becomes sharper with the cooperativity parameterσof hydration.Reentrant coil-globule-coil transition in mixed solvent of water and methanol is also studied from the viewpoint of competitive hydrogen bonds between polymer-water and polymer-methanol. The downward shift of the cloud-point curves(LCST cononsolvency) with the mole fraction of methanol due to the competition is calculated and compared with the experimental data.Aqueous solutions of hydophobically-modified PNIPAM carrying short alkyl chains at both chain ends(telechelic PNIPAM) are theoretically and experimentally studied.The LCST of these solutions is found to shift downward along the sol-gel transition curve as a result of end-chain association (association-induced phase separation),and separate from the coil-globule transition line.Associated structures in the solution,such as flower micelles,mesoglobules and higher fractal assembly,are studied by USANS with theoretical modeling of the scattering function.     

Unusual phase behavior in mixtures of poly(ethylene oxide) and ethyl alcohol

Poly(ethylene oxide) (PEO), soluble in both aqueous and organic solvents, is one of the most intriguing polymers. PEO solution properties have been extensively studied for decades; however, many of the studies have focused on specific properties, such as clustering, of PEO in aqueous solutions, and the behavior of PEO in organic solvents has not been adequately explored. The results presented here demonstrate that PEO crystallizes into a lamellar structure in ethyl alcohol after the mixture is quenched to room temperature from a temperature above the crystal melting point. Above the melting temperature, PEO completely dissolves in ethyl alcohol, and the mixture exhibits regular polymer solution thermodynamic behavior with an upper critical solution temperature (UCST) phase diagram. Remarkably, the UCST phase boundary is significantly below the melting temperature, and this indicates that the system undergoes a crystallization process before the phase separation can occur upon cooling and, therefore, possesses an unusual phase transition. The phase transition from the crystalline state to the miscible solution state is reversible upon heating or cooling and can be induced by the addition of a small amount of water. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 557–564, 2006     

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.     

Thermal gelation of cellulose in a NaOH/thiourea aqueous solution

Utilizing a novel solvent of cellulose, 6 wt % NaOH/5 wt % thiourea aqueous solution, for the first time, we prepared the thermally induced cellulose gel. We investigated the thermal gelation of cellulose solutions with rheometry and the structure of the gel with 13C NMR, wide-angle X-ray diffraction, environmental scanning electron microscopy, and atomic force microscopy. The cellulose solutions revealed an increase in both the storage modulus (G') and the loss modulus (G") with an increase in the temperature during gelation. The temperature at the turning point, where G' overrides G" because of the onset of gelation, decreased from 38.6 to 20.1 degrees C with an increase of cellulose concentration from 4 to 6 wt %. Given enough time, G' of all solutions can exceed G" at a certain temperature slightly lower than the gelation temperature, indicating that the occurrence of the gelation is also a function of time. Each of the assigned peaks of NMR of the cellulose gel is similar to that of the cellulose solution, suggesting that the gelation resulted from a physical cross-linking. The gels were composed of relatively stable network units with an average diameter of about 47 nm. At either a higher temperature (at 60 degrees C for 30 s) or a longer gelation time (at 30 degrees C for 157 s), the gel in the 5 wt % cellulose solution could form. A schematic gelation process was proposed to illustrate the sol-gel transition: the random self-association of the cellulose chains having the exposed hydroxyl in the aqueous solution promotes the physical cross-linking networks.     

Molecular motion and 1H NMR relaxation of aqueous poly(N-isopropylacrylamide) solution under high pressure

In order to obtain useful information about the molecular motion and structure of poly(N-isopropylacrylamide) (PNiPAM) in aqueous solution, proton spin-lattice relaxation times, proton spin-spin relaxation times, and volume changes were measured at pressures from 1 to 400 kg/cm² as a function of temperature. We found that the molecular motion and the structure of water and PNiPAM in PNiPAM/water solution transitionally change at gelation temperature (31°C). The effect of pressure on such transitional changes is studied. It is suggested that application of pressure to the system prevents the gelation.     

Investigation of sol-gel transition in pluronic F127/D2O solutions using a combination of small-angle neutron scattering and monte carlo simulation

Physical gelation in the concentrated Pluronic F127/D2O solution has been studied by a combination of small-angle neutron scattering (SANS) and Monte Carlo simulation. A 15% F127/D2O solution exhibits a sol-gel transition at low temperature and a gel-sol transition at the higher temperature, as evidenced by SANS and Monte Carlo simulation studies. Our SANS and simulation results also suggest that the sol-gel transition is dominated by the formation of a percolated polymer network, while the gel-sol transition is determined by the loss of bound solvent. Furthermore, different diffusion behaviors of different bound solvents and free solvent are observed. We expect that this approach can be further extended to study phase behaviors of other systems with similar sol-gel phase diagrams.     

Collapse transition in thin films of poly(methoxydiethylenglycol acrylate)

The thermal behavior of poly(methoxydiethylenglycol acrylate) (PMDEGA) is studied in thin hydrogel films on solid supports and is compared with the behavior in aqueous solution. The PMDEGA hydrogel film thickness is varied from 2 to 422?nm. Initially, these films are homogenous, as measured with optical microscopy, atomic force microscopy, X-ray reflectivity, and grazing-incidence small-angle X-ray scattering (GISAXS). However, they tend to de-wet when stored under ambient conditions. Along the surface normal, no long-ranged correlations between substrate and film surface are detected with GISAXS, due to the high mobility of the polymer at room temperature. The swelling of the hydrogel films as a function of the water vapor pressure and the temperature are probed for saturated water vapor pressures between 2,380 and 3,170?Pa. While the swelling capability is found to increase with water vapor pressure, swelling in dependence on the temperature revealed a collapse phase transition of a lower critical solution temperature type. The transition temperature decreases from 40.6?°C to 36.6?°C with increasing film thickness, but is independent of the thickness for very thin films below a thickness of 40?nm. The observed transition temperature range compares well with the cloud points observed in dilute (0.1?wt.%) and semi-dilute (5?wt.%) solution which decrease from 45?°C to 39?°C with increasing concentration.     

Thermally induced sign change of Soret coefficient for dilute and semidilute solutions of poly(N-isopropylacrylamide) in ethanol

We studied the thermal diffusion behavior of poly(N-isopropylacrylamide) (PNiPAM) in ethanol in a temperature range from T = 14.0 degrees C to T = 40.0 degrees C by means of thermal diffusion forced Rayleigh scattering. The obtained Soret coefficient S(T) of PNiPAM was positive for lower temperatures (T < 34 degrees C), while S(T) showed a negative value for higher temperatures (T > 34 degrees C). This means PNiPAM molecules move to the cold side for temperatures T < 34 degrees C, whereas they move to the warm side for T > 34 degrees C. This is the first nonaqueous polymeric system for which a sign change with temperature has been observed. We performed static and dynamic light scattering experiments in the same temperature range. The second virial coefficient determined from dilute solutions by static light scattering (SLS) was positive in the comparable temperature range. The results of SLS for the semidilute solution showed a strong repulsion among PNiPAM chains which was enhanced by increasing temperature. These results imply that the observed thermally induced sign change of S(T) does not depend on the intermolecular interactions among PNiPAM chains.     

Phase separation dynamics of aqueous solutions of thermoresponsive polymers studied by a laser T-jump technique

Poly(N-isopropylacrylamide) and poly(vinyl methyl ether) are well-known thermoresponsive polymers. The aqueous solutions of these polymers exhibit a phase transition followed by phase separation with LCST approximately 305-310 K. In the present study, the dynamic behavior of the phase separation was analyzed by a laser T-jump method. Two different T-jump methodologies were employed: the first was a dye-photosensitized T-jump technique (indirect heating) using 532 nm laser pulses, while the other was a direct heating T-jump technique using 1.2 mum laser pulses. Both methods gave similar results. The time constants (tau) of the phase separation were systematically determined for 1-10 wt % aqueous solutions of the polymers, and a hydrodynamic radius (R) dependence for tau was clearly observed. The values of tau increased linearly with increasing square of R. The present behavior is interpretable in the framework of Tanaka's model for the volume phase transition of a gel, since each of the polymer chains are entangled in the present sample solutions, which can be regarded as approximating to a gel in solution.     

Thermally induced phase transition of carborane-functionalized aliphatic polyester dendrimers in aqueous media

Three recently reported aliphatic polyester dendrimers of generations 3, 4, and 5, having 4, 8, and 16 carborane cages within their interior, respectively, were found to exhibit thermally induced, reversible precipitation in aqueous solution. The cloud-point temperatures for these molecules were observed to be between 40 and 80 degrees C, depending on the dendrimer generation. The three dendrimers investigated have a hydroxyl-to-carborane ratio of 8:1, which provides the ideal balance between the hydrophobic interior and the hydrophilic exterior to enable the thermally induced phase transition to occur. It was found that repeated heating/cooling cycles resulted in a decreasing cloud-point temperature and increased dendrimer solubility. Additionally, the effect of pH on the cloud point was investigated, indicating no significant changes as long as the dendrimers remained stable. Size-exclusion chromatography indicated that dendrimer degradation was occurring at pH above 7.0.     

Microviscosity in poly(ethylene oxide)‐polypropylene oxide‐poly(ethylene oxide) block copolymers probed by fluorescence depolarization kinetics

Triblock copolymers [poly(ethylene oxide) (PEO) and polypropylene oxide (PPO)], Pluronic F127 with 100 PEO blocks on each end, and 65 blocks of PPO in the center were examined in aqueous solution. The “sol” and “gel” phase diagram was determined as a function of concentration and temperature. For further study, the concentration was fixed at 20 wt %, and the temperature dependence of the dynamic viscosity differed from the temperature dependence of fluorescence emission spectra and the microviscosity probed by the fluorescence depolarization kinetics of rhodamine 123 dye, which was dissolved in the continuous hydrophilic phase. The depolarization measurements used single‐photon counting after two‐photon excitation with a Ti‐sapphire femtosecond laser. Although the viscoelastic modulus increased by an order of magnitude when the sol‐to‐gel transition was crossed, the microviscosity of the hydrophilic continuous medium showed only minor changes. At different temperatures the fluorescence lifetime was the same with a single‐exponential time constant, but the fluorescence depolarization displayed a double‐exponential decay. After comparison with fluorescence depolarization of the dye in PPO melt and PEO whose molecular weight and aqueous concentrations were varied, the relative proportions of faster and slower components of the fluorescence depolarization were tentatively attributed to varying ratios of the dye in free solution and associated with micelles. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2883–2888, 2002     

Aggregation behavior of polypropylene oxide with electric charges at both ends in aqueous solution

The aggregation behavior of polypropylene oxide (PPO) with positive charges at both ends was investigated in aqueous solution by means of the measurements of solution turbidity, dynamic light-scattering, differential scanning calorimetry, and dye solubilization. The positive charges were produced by protonation of terminal NH(2) groups attached to the polymer composed of 33 PO units. It was found that the aggregation behavior is quite sensitive to temperature. At low temperature, the polymer dissolves in water as a unimer. When temperature is increased, the unimer solution undergoes a phase separation to give a turbid solution. Further increase in temperature produces a transparent micellar solution. The aggregation of the polymer molecules must be induced by the dehydration of PPO chain caused by temperature increase. According to the analysis of heat absorptions associated with the melting of the solid mixture and the phase separation of the unimer solution, it is suggested that approximately 10% dehydration of PPO chain causes the phase separation. The temperature-composition phase diagram of aqueous mixture of this polymer was constructed on the basis of turbidity and DSC experiments, which reveals the aggregation behavior of this polymer in aqueous medium as a function of concentration and temperature.