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 Ih 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 Ih 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 Å, b = 25.867 Å, c = 5.610 Å, β = 113.12º); 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.
10 December 2015 in The Journal of Physical Chemistry B
The temperature dependences of α relaxation time of three glass-forming liquids (salol, -terphenyl, and α-picoline) were investigated by a depolarized light scattering technique. A detailed description of near , the temperature of the transition from the Arrhenius law at high temperatures to a non-Arrhenius behavior of at lower temperatures, was done. It was found that this transition is quite sharp. If the transition is described as switching from the Arrhenius law to the Vogel-Fulcher-Tammann law, it occurs within the temperature range of about 15 K or less. Most of the known expressions for cannot describe this sharp transition. Our analysis revealed that this transition can be described either as a discontinuous transition in the spirit of the frustration-limited domain theory [D. Kivelson, G. Tarjus, X. Zhao, and S. A. Kivelson, Phys. Rev. E 53, 751 (1996)], implying a phase transition, or by a phenomenological expression recently suggested [B. Schmidtke, N. Petzold, R. Kahlau, M. Hofmann, and E. A. Rössler, Phys. Rev. E 86, 041507 (2012)], where the activation energy includes the term depending exponentially on temperature.
The measurement of intracellular viscoelastic properties by Brillouin scattering is a rapidly developing field in biophysics and medicine. Here, the Brillouin spectroscopy is applied for a number of aqueous solutions of biorelevant molecules to reveal relations between the Brillouin line parameters (frequency and width) and viscosity or solute concentration. It is found that for the majority of the studied biorelevant molecules the solute concentration governs the Brillouin frequency in a universal manner. On the other hand, the relations between the macroscopic viscosity and Brillouin peak parameters are different for different solutes. We conclude that for biological fluids the viscosity evaluation from Brillouin data needs prior knowledge about the chemical composition. This result challenges the fidelity of the indirect experimental determinations of the cellular viscosity, when small molecule solutions are used for the calibration.
24 January 2011 in The Journal of Chemical Physics
The temperature dependence of selected low-wavenumber (< 200 cm−1) Raman bands was studied for the different crystalline phases (α-, β-, γ-) of glycine — the simplest possible “building block” of a biomolecule. The temperature dependence of the frequencies of vibrational modes deviates from the theoretical expectation based on the assumption of cubic anharmonicity. Although relatively small, this deviation was observed above 250 K for all the three polymorphs. This finding was discussed in relation to the “dynamical transition” phenomenon, observed in variety of biomolecules in the range 200–250 K. The similarity of the temperatures suggests, that the origin of the dynamical transition phenomenon can be related to intrinsic conformational states of biomolecules, while water serves rather as a plasticizer or a structure organizer.
6 July 2012 in The Journal of Physical Chemistry B