Gelation, Phase Separation, and Fibril Formation in Aqueous Hydroxypropylmethylcellulose Solutions.

The thermoresponsive behavior of a hydroxypropylmethylcellulose (HPMC) sample in aqueous solutions has been studied by a powerful combination of characterization tools, including rheology, turbidimetry, cryogenic transmission electron microscopy (cryoTEM), light scattering, small-angle neutron scattering (SANS), and small-angle X-ray scattering (SAXS). Consistent with prior literature, solutions with concentrations ranging from 0.3 to 3 wt % exhibit a sharp drop in the dynamic viscoelastic moduli G' and G″ upon heating near 57 °C. The drop in moduli is accompanied by an abrupt increase in turbidity. All the evidence is consistent with this corresponding to liquid-liquid phase separation, leading to polymer-rich droplets in a polymer-depleted matrix. Upon further heating, the moduli increase, and G' exceeds G″, corresponding to gelation. CryoTEM in dilute solutions reveals that HPMC forms fibrils at the same temperature range where the moduli increase. SANS and SAXS confirm the appearance of fibrils over a range of concentration, and that their average diameter is ca. 18 nm; thus gelation is attributable to formation of a sample-spanning network of fibrils. These results are compared in detail with the closely related and well-studied methylcellulose (MC). The HPMC fibrils are generally shorter, more flexible, and contain more water than with MC, and the resulting gel at high temperatures has a much lower modulus. In addition to the differences in fibril structure, the key distinction between HPMC and MC is that the former undergoes liquid-liquid phase separation prior to forming fibrils and associated gelation, whereas the latter forms fibrils first. These results and their interpretation are compared with the prior literature, in light of the relatively recent discovery of the propensity of MC and HPMC to self-assemble into fibrils on heating.

Fibrillar structure of methylcellulose hydrogels.

It is well established that aqueous solutions of methylcellulose (MC) can form hydrogels on heating, with the rheological gel point closely correlated to the appearance of optical turbidity. However, the detailed gelation mechanism and the resulting gel structure remain poorly understood. Herein the fibrillar structure of aqueous MC gels was precisely quantified with a powerful combination of (real space) cryogenic transmission electron microscopy (cryo-TEM) and (reciprocal space) small-angle neutron scattering (SANS) techniques. The cryo-TEM images reveal that MC chains with a molecular weight of 300 000 g/mol associate into fibrils upon heating, with a remarkably uniform diameter of 15 ± 2 nm over a range of concentrations. Vitrified gels also exhibit heterogeneity in the fibril density on the length scale of hundreds of nanometers, consistent with the observed optical turbidity of MC hydrogels. The SANS curves of gels exhibit no characteristic peaks or plateaus over a broad range of wavevector, q, from 0.001-0.2 Å(-1). The major feature is a change in slope from I ∼ q(-1.7) in the intermediate q range (0.001 - 0.01 Å(-1)) to I ∼ q(-4) above q ≈ 0.015 Å(-1). The fibrillar nature of the gel structure was confirmed by fitting the SANS data consistently with a model based on the form factor for flexible cylinders with a polydisperse radius. This model was found to capture the scattering features quantitatively for MC gels varying in concentration from 0.09-1.3 wt %. In agreement with the microscopy results, the flexible cylinder model indicated fibril diameters of 14 ± 1 nm for samples at elevated temperatures. This combination of complementary experimental techniques provides a comprehensive nanoscale depiction of fibrillar morphology for MC gels, which correlates very well with macro-scale rheological behavior and optical turbidity previously observed for such systems.

Influence of temperature on low-power upconversion in rubbery polymer blends.

The upconverting properties of a dye cocktail composed of palladium(II) octaethylporphyrin (PdOEP, triplet sensitizer) and 9,10-diphenylanthracene (DPA, triplet acceptor/annihilator) were investigated as a function of temperature in several low glass transition temperature (T(g)) polymer hosts including an ethyleneoxide-epichlorohydrin copolymer (EO-EPI) and the polyurethanes Texin 270, Texin 285, and Tecoflex EG-80A. Selective excitation of PdOEP at 544 nm in the presence of DPA in these materials resulted in anti-Stokes blue emission from DPA, a consequence of sensitized triplet-triplet annihilation (TTA) photochemistry, confirmed by the quadratic dependence of the upconverted fluorescence intensity with respect to incident light power. The upconversion process was completely suppressed by cooling a PdOEP/DPA blend film to below the T(g) of the respective polymer. However, the blue emission was clearly visible by the naked eye upon heating these films to room temperature (290 K). Subsequently, the upconverted emission intensity increased with increasing temperature and was found to be completely reversible upon several heating and cooling cycles provided the temperature remained below 400 K. Heating samples above this temperature resulted in unrecoverable failure of the material to produce upconverted photons. The phosphorescence intensity decay of PdOEP in the polymer host, Tecoflex EG-80A, adequately fits to a sum of two exponential functions as well as the Kohlrausch-Williams-Watts (KWW) stretched exponential model. Increasing the temperature of the film increases the complexity and heterogeneity of the system as evidenced by the lower beta values obtained from the KWW model as the temperature increases.

Melt-processed all-polymer distributed Bragg reflector laser.

We have assembled and studied melt-processed all-polymer lasers comprising distributed Bragg reflectors that were fabricated in large sheets using a co-extrusion process and define the cavities for dye-doped compression-molded polymer gain core sheets. Distributed Bragg reflector (DBR) resonators consisting of 128 alternating poly(styrene) (PS) and poly(methyl methacrylate) (PMMA) layers were produced by multilayer co-extrusion. Gain media were fabricated by compression-molding thermoplastic host poly notmers doped with organic laser dyes. Both processing methods can be used in high-throughput roll-to-roll manufacturing. Optically pumped DBR lasers assembled from these components display single and multimode lasing in the reflection band of the resonators, with a slope efficiency of nearly 19% and lasing thresholds as low as 90microJ/cm(2). The lasing wavelength can be controlled via the layer thickness of the DBR resonator films, and variation of the laser dye. Studies of threshold and efficiency are in agreement with models for end-pumped lasers.

Linear and Nonlinear Rheological Behavior of Fibrillar Methylcellulose Hydrogels.

Cryogenic transmission electron microscopy and small-angle neutron scattering recently have revealed that the well-known thermoreversible gelation of methylcellulose (MC) in water is due to the formation of fibrils, with a diameter of 15 ± 2 nm. Here we report that both the linear and nonlinear viscoelastic response of MC solutions and gels can be described by a filament-based mechanical model. In particular, large-amplitude oscillatory shear experiments show that aqueous MC materials transition from shear thinning to shear thickening behavior at the gelation temperature. The critical stress at which MC gels depart from the linear viscoelastic regime and begin to stiffen is well predicted from the filament model over a concentration range of 0.18-2.0 wt %. These predictions are based on fibril densities and persistence lengths obtained experimentally from neutron scattering, combined with cross-link spacings inferred from the gel modulus via the same model.

Integration of nanoassembly functions for an effective delivery cascade for cancer drugs.

A "cluster-bomb"-like lipid-dendrimer nanoassembly synergizes the functions of its components and thereby efficiently accomplishes the drug delivery cascade for high efficacy in treating cancer. The nanoassembly successfully circulates in the blood and accumulates in the tumor. Once in the tumor, it releases small dendrimers that act like "bomblets", enabling tumor penetration, cell internalization, and drug release.