Glycine phases formed from frozen aqueous solutions: Revisited

Glycine phases formed when aqueous solutions were frozen and subsequently heated under different conditions were studied by Raman scattering, x-ray diffraction, and differential scanning calorimetry (DSC) techniques. Crystallization of ice I(h) was observed in all the cases. On cooling at the rates of 0.5 K∕min and 5 K∕min, glassy glycine was formed as an intermediate phase which lived about 1 min or less only, and then transformed into β-polymorph of glycine. Quench cooling of glycine solutions (15% w∕w) in liquid nitrogen resulted in the formation of a mixture of crystalline water ice I(h) and a glassy glycine, which could be preserved at cryogenic temperatures (80 K) for an indefinitely long time. This mixture remained also quite stable for some time after heating above the cryogenic temperature. Subsequent heating under various conditions resulted in the transformation of the glycine glass into an unknown crystalline phase (glycine "X-phase") at 209-216 K, which at 218-226 K transformed into β-polymorph of glycine. The "X-phase" was characterized by Raman spectroscopy; it could be obtained in noticeable amounts using a special preparation technique and tentatively characterized by x-ray powder diffraction (P2, a = 6.648 A?, b = 25.867 A?, c = 5.610 A?, β = 113.12[ordinal indicator, masculine]); the formation of "X-phase" from the glycine glassy phase and its transformation into β-polymorph were followed by DSC. Raman scattering technique with its power for unambiguous identification of the crystalline and glassy polymorphs without limitation on the crystallite size helped us to follow the phase transformations during quenching, heating, and annealing. The experimental findings are considered in relation to the problem of control of glycine polymorphism on crystallization.     

Photochromic Transformations of Spiro Compounds: 2. The Kinetics of Photocoloration under Continuous Irradiation

The kinetics of photocoloration of spiro compounds under continuous UV irradiation were analyzed. Using spirooxazine as an example, it was shown that the shape of the kinetic curve of spirooxazine absorbance in the course of photocoloration is the most sensitive to the photocoloration quantum yield and the molar decadic absorption coefficient of the colored form in the visible spectral region. The photocoloration rate was found to increase with increasing temperature as a result of the temperature dependence of the photocoloration quantum yield. The activation energies for photocoloration E _col and for thermal bleaching E _bleach were determined for a series of spiropyrans, and it was found that E _col < E _bleach.