Betulin-3,28-diphosphate. Physico-Chemical Properties and In Vitro Biological Activity Experiments.

Betulin-3,28-diphosphate (BDP) obtained by phosphorylation of betulin using POCl3 has two main structural forms-BDP-1 and BDP-2-which differ in ethanol solubility, melting point, FTIR spectra, thermoanalytical characteristics and biological activity. Betulin-3,28-diphosphate and its sodium salt (Na-BDP) were characterized using 13C and 31P-NMR spectra, powder XRD experiments, as well as differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) methods. The exo-effects at 193 ± 8 °C for ethanol soluble BDP-1 samples (-19.7 ± 0.2 kJ∙mol-1) were about three times less than for ethanol insoluble BDP-2 samples f (-70.5 ± 0.7 kJ∙mol-1). The DSC curves of Na-BDP-1 and Na-BDP-2 characterized the endo-effects having a maximum at 95⁻112 °C. Water-soluble Na-BDP-1 was obtained as needle-like crystals, unlike poorly crystalline Na-BDP-2, whereas BDP-1 and BDP-2 aged with time and were isolated as amorphous substances. In vitro experiments on rats showed that compared to the control, Na-BDP-1 increased catalase and SOD activity and improved energy metabolism more effectively than Na-BDP-2.

Valence-Tautomeric Interconversion in a Bis(dioxolene)cobalt Complex with Iminopyridine Functionalized by a TEMPO Moiety. Phase Transition Coupled with Monocrystal Destruction.

Iminopyridine modified by TEMPO nitroxide was utilized for the synthesis of an octahedral bis(o-semiquinonato)cobalt complex. Variable-temperature magnetic susceptibility measurements detect a valence tautomeric transformation in the temperature range 200-300 K. A reproducible hysteresis loop of about 40 K width is observed on the magnetic moment temperature dependence in the transition region. Differential scanning calorimetry measurements confirm different temperatures of phase transitions accompanying a valence-tautomeric transformation upon heating and cooling. Attempts to study the structural changes associated with the valence-tautomeric transformation by single-crystal X-ray diffraction failed because of the crystal destruction taking place upon cooling from 220 K. The powder X-ray diffraction pattern indicated an essential change of the unit cell upon cooling from 240 K.

Structure and Thermal Expansion of Calcium-Thorium Apatite, [Ca4]F[Ca2Th4]T[(SiO4)6]O2.

Thorium silicate apatite with the formula [Ca3.84Th0.16]F[Ca2.79Th3.21]T(SiO4)6O2 · x(H) was synthesized by solid-state reaction, and its structure refined in P63/m from powder X-ray diffraction (XRD) data using the Rietveld method (a = 9.50172(9) Å, c = 6.98302(8) Å, V = 545.98(1) Å(3); R-Bragg = 2.102%). It was found that thorium partitions strongly to the tunnel (T) 6h position rather than the framework (F) 4f site. Fourier transform infrared spectroscopy revealed only SiO4 tetrahedron, with SiO5 and SiO6 groups, sometimes observed in siliceous apatites absent, at least to the limit of detection of this technique. Thermal expansion of the thorium apatite determined by high-temperature XRD from 298-1173 K found Δa (0.87%) dilation to exceed Δc (0.73%) with increasing temperature consistent with other silicate apatites.

Crystal-chemical and morphological interpretation of the biocompatibility of compounds in a Ca-Na-Bi-fluorapatite system.

This work is devoted to the study of the features of isomorphism in compounds of a Ca-Na-Bi-P-O-F system with a crystalline structure of the mineral apatite, as well as its effect on the biocompatibility of substances in relation to human cells in an in vitro model. A Ca10-2xBixNax(PO4)6F2 system (x = 0, 1, 2, 3, 4, and 5) is characterized by continuous isomorphism, which follows from the minimum deviations of the unit cell parameters from the Vegard and Rötgers rules. The refinement of the crystal structure showed that the cations are unevenly distributed between the 4f and 6h positions of the crystal structure of apatite: the bismuth ions are predominantly localized in the 6h position, while the sodium ions are concentrated in the 4f position. A standard MTT test of the biocompatibility of compounds with x = 1, 2, 3, and 4, and at x = 1 showed an anomaly in the form of an increased relative cell growth rate. This paper discusses the possible crystal-chemical and morphological reasons for this phenomenon.

New iodine-apatites: synthesis and crystal structure.

The paper describes methods for the preparation of compounds with an apatite structure containing only iodine atoms in the "halogen" position. The crystal structure of the compounds was refined by the Rietveld method. The resulting apatites have a structure with a space group P63/m and have the following unit cell parameters: Ba4 f 1.78(2)Ba6 h 2.75(2)(PO4)3I0.04(2) (a = 10.18609(34) Å, c = 7.71113(30) Å, V = 692.889(54) Å3, R = 5.448 %), Pb4 f 1.82(2)Pb6 h 2.75(2)(PO4)3I0.13(2) (a = 9.87882(18) Å, c = 7.43222(16) Å, V = 628.144(26) Å3, R = 8.533 %), Pb4 f 1.90(2)Pb6 h 2.68(2)(PO4)3I0.16(2) (a = 9.87058(48) Å, c = 7.41255(46) Å, V = 625.437(72) Å3, R = 5.433 %). The study of the crystal structure showed a relatively low efficiency of the binding of iodine in the apatite matrix.