Thermal analysis of the system triamterene-d-mannitol

Thermal analysis (DSC and HSM), and equilibrium solubility determinations were carried out to elucidate the mechanism of interaction at the solid state in the binary system triamterene-D-mannitol. Physical mixtures (5–90% w/w triamterene) and solid dispersions (5 up to 40% w/w triamterene) were prepared and studied. From DSC and HSM results, the thermal changes were associated with the variations in composition of the binary mixture, being more pronounced in the range 20–50% w/w. The binary phase diagram was proposed, although the exact position of the eutectic was uncertain. This is in accordance with a partial dissolution process detected by HSM. A linear increase in the solubility of triamterene with increasing aqueous mannitol concentration was obtained. The thermodynamic parameters of the solution properties were calculated, with an activation energy value of 96.081 kJ/mole. The solubilization increase was associated with complexation processes and hydrogen bonding formation. Dedicated to Professor Lisa Heller-Kallai on the occasion of her 65^th birthday     

Multiscale analysis of water uptake and erosion in biodegradable polyarylates

The role of hydration in degradation and erosion of materials, especially biomaterials used in scaffolds and implants, was investigated by studying the distribution of water at length scales from 0.1 nm to 0.1 mm using Raman spectroscopy, small-angle neutron scattering (SANS), Raman confocal imaging, and scanning electron microscopy (SEM). The measurements were demonstrated using l-tyrosine derived polyarylates. Bound- and free- water were characterized using their respective signatures in the Raman spectra. In the presence of deuterium oxide (D₂O), H-D exchange occurred at the amide carbonyl but was not detected at the ester carbonyl. Water appeared to be present in the polymer even in regions where there was little evidence for NH to ND exchange. SANS showed that water is not uniformly dispersed in the polymer matrix. The distribution of water can be described as mass fractals in polymers with low water content (∼5 wt%), and surface fractals in polymers with larger water content (15-60 wt%). These fluctuations in the density of water distribution are presumed to be the precursors of the ∼20 μm water pockets seen by Raman confocal imaging, and also give rise to the 10-50 μm porous network seen in SEM. The surfaces of these polymers appeared to resist erosion while the core of the films continued to erode to form a porous structure. This could be due to differences in either the density of the polymer or the solvent environment in the bulk vs. the surface, or a combination of these two factors. There was no correlation between the rate of degradation and the amount of water uptake in these polymers, and this suggests that it is the bound water and not the total amount of water that contributes to hydrolytic degradation.     

Model films of cellulose: I. Method development and initial results

This report presents a new method for the preparation of thin cellulosefilms. NMMO (N-methylmorpholine-N-oxide) was used to dissolve cellulose andaddition of DMSO (dimethyl sulfoxide) was used to control viscosity of thecellulose solution. A thin layer of the cellulose solution is spin-coated ontoasilicon oxide wafer and the cellulose is precipitated in deionised water. Thecellulose film is anchored onto the silicon oxide wafer by a saturated polymerlayer. Among many different polymers tested, PVAm (polyvinylamine) and G-PAM(glyoxalated-polyacrylamide) worked well. The preparation of cellulose modelfilms described in this paper resulted in films with thicknesses in the range20–270 nm and the thickness can be controlled by alteringtheconcentration of cellulose solution by addition of different amounts of DMSO.The films were cleaned in deionised water and were found to be free fromsolvents by ESCA analysis and contact angle measurements. The molecular weightdistribution of the cellulose surface material shows that there is only minorbreakdown of the cellulose chains, mainly by cleavage of the longest molecularmass fraction and without creation of low molecular mass oligomers of glucose.     

Supercritical fluid chromatography/Fourier transform infrared microspectrometry

The feasibility of supercritical fluid chromatography/Fourier transform-infrared (SFC/FT-IR) microspectrometry is presented. In this approach to SFC/FT-IR, the chromatographic eluates are aspirated from the restrictor directly onto the surface of a moving window which then passes into the beam focus of an infrared microscope. Because the mobile phase is gaseous at ambient conditions, elimination of the mobile phase is easily accomplished. Detection limits in all interfaces between a chromatograph and an FT-IR spectrometer in which the mobile phase is eliminated are determined in large part by the area over which the sample is deposited. We have shown that SFC eluates can be condensed at ambient temperature into spots of 100 to 200μm in diameter. The microscope interface therefore serves to increase the sensitivity of the SFC/FT-IR measurements of these spots and detection limits in the low nanogram range are possible. Preliminary results obtained before any real attempts were made to optimize the deposition process indicate that identifiable spectra can be obtained in real time at the 50 ng level for chromatographic separations performed with a 100μm i.d. wall coated open tubular column. Reproducible reconstructed chromatograms are obtained as each deposited eluate travels through the beam focus of the microscope. The concentration profile of deposited peaks was determined by IR measurements performed at 50 μm increments over the width of the peak to ascertain the deposition size. The results described in this paper, while not yet optimized, indicate the great potential of SFC/FT-IR microspectrometry.     

Influence of the sample-probe coupling on the resolution of transmitted near-field optical image

Numerical simulation of photon scanning tunneling microscopy is presented to study the near-field distribution in the vicinity a dielectric surface with one-dimensional sub-wavelength structures. Multiple scattering between the probe tip and the sample has been taken into account implicitly by matching electromagnetic boundary conditions at interfaces. The near-field intensity in transmission mode through two ridges on surface has been modeled in order to analyze the resolution of the system. The effects on the signal by the sample-tip coupling, the polarization of the incident light, and the angle of incidence are investigated. We find that the capability to recognize the feature will be improved when the tip–object interaction is strong.     

Synthesis and characterization of dispersions of ZnCrO4 prepared in AOT stabilized water/heptane microemulsion

Dispersions of zinc chromate (ZnCrO₄) were prepared in H₂O/AOT (sodium bis(2-ethylhexyl sulfosuccinate))/n-heptane water-in-oil (W/O) microemulsion medium with various water pool sizes and precursor concentration both without and with sonication. The formation of ZnCrO₄ in the microemulsion was verified by XRD and FTIR measurements. The absorbance of the dispersions formed in different water pool sizes was studied. Their dimension in the microemulsion medium was determined by the dynamic light scattering method. Enthalpy of formation of ZnCrO₄ in W/O microemulsion medium was measured by isothermal titration calorimetry (ITC). The dimension and morphology of the formed ZnCrO₄ colloidal particles examined by transmission electron microscopy (TEM) were strongly dependent on the water pool size, precursor concentration and sonication.