Synchrotron radiation X-ray diffraction and Raman spectroscopy study of l-asparagine monohydrate doped with Fe(III) at high pressure.

Crystals of l-asparagine monohydrate doped with Fe(III) were studied by Raman spectroscopy in a diamond anvil cell (DAC) in the spectral range from 100 to 3200 cm-1 and pressures up to 9.2 GPa. The behavior of external modes suggests conformational changes between 3.0 and 4.0 GPa mainly affecting the CH2 group. X-ray diffraction measurements with synchrotron radiation were performed in the angular range from 3 to 12 degrees (2θ) up to 9.3 GPa. The lattice parameters contract up to 9.3 GPa, with the exception of parameter b, which exhibits expansion from 7.2 GPa. The lattice parameters exhibit discontinuities between 3.0 and 4.0 GPa, this effect is compatible with conformational changes. Such modifications occur without a change in symmetry, at least up to 9.3 GPa. Under decompression, down to atmospheric pressure, the original Raman spectrum is recovered, showing that the conformational change and the other changes are all reversible.

Physical approach for a quantitative analysis of the phytosterols in free phytosterol-oil blends by X-ray Rietveld method.

This study investigates and compares the thermal phase transition and crystallization characteristics of a commercial food grade free phytosterol blend (FP) with a stigmasterol analytical standard (SS), the FP behavior in a food model system after its addition to high oleic sunflower oil (HOSO). The properties of the FP:HOSO blends were studied by differential scanning calorimetry, solid content, crystal morphology, and X-ray diffraction (XRD) measurements. The Rietveld method (RM) was applied associated with the XRD measurements to support phase analysis and the study of crystallinity degree. The materials were also characterized by means of chemical composition, such as fatty acids and triacylglycerol profiles, for HOSO, and phytosterol profile, for FP. Regarding phase behavior and crystallinity properties, FP has very similar characteristics to SS. The thermal behavior of FP:HOSO blends has two characteristic peaks, one from FP and the other from HOSO. The similarity reported in the literature between the diffraction pattern of FP and pure phytosterols is a positive characteristic for FP. A high FP concentration resulted in high supersaturation and thus the formation of small crystals. The incorporation of HOSO reduced of the large agglomeration of FP crystals and the dispersion crystalline aggregates (spherulites) of FP crystals. The application of RM in FP:HOSO blends to quantify the crystalline and amorphous phases was successfully used. The application has provided the expected value for these phases, according to the same experimental mass ratio of the blends, thereby validating the applicability of this approach in this type of material.