Aqueous Solubilities, Infinite Dilution Activity Coefficients and Octanol–Water Partition Coefficients of Tricyclic Analogs of Acyclovir

Solubilities of tricyclic analogs of acyclovir have been determined in water at 25, 35, and 45°C and in octanol, water-saturated octanol, and octanol-saturated water at 25°C. Octanol-water partition coefficients were determined at 25°C. Melting temperatures and molar enthalpies of fusion were measured. Activity coefficients in water, octanol, and in aqueous octanol solutions were determined and are discussed. The effect of hydrophilic and hydrophobic substituents in the tricyclic analogs on their thermodynamic properties are discussed. The standard Gibbs energy of transfer between the saturated phases were found to correlate with known values of the melting point of the solvents and the solubilities of the solute. For a number of the compounds examined, correlations between the minimum inhibitory concentration against the herpes simplex virus type 1 (HSV-1) and type 2 (HSV-2), varicella-zoster virus (VZV), thymidine kinase-deficient (TK^–) strains of VZV and were established. Detailed conclusions have been derived concerning the relationships between the structure and the thermodynamic parameters of the compounds examined.     

A thermochemical study of aqueous solutions of sodium diclophenac at 293.15–318.15 K

The enthalpies of solution and dilution of aqueous solutions of sodium diclophenac were measured at 293.15–318.15 K on an isoperibolic calorimeter. The content of the electrolyte determined by its solubility did not exceed 0.035–0.057 mol/kg solvent depending on temperature. The Pitzer model was used to obtain virial coefficients that allowed us to calculate a wide range of excess thermodynamic properties of both solution and its components.     

Polymorphism of paracetamol

The thermodynamic relationship between crystal modifications of paracetamol was studied by alternative methods. Temperature dependence of saturated vapor pressure for polymorphic modifications of the drug paracetamol (acetaminophen) was mea sured and thermodynamic functions of the sublimation process calculated. Solution calorimetry was carried out for the two modifications in the same solvent. Thermodynamic parameters for sublimation for form I (monoclinic) were found: ΔG _sub²⁹⁸=60.0 kJ mol⁻¹; ΔH _sub²⁹⁸=117.9±0.7 kJ mol⁻¹; ΔS _sub²⁹⁸=190±2 J mol⁻¹ K⁻¹. For the orthorhombic modification (form II), the saturated vapor pressure could only be studied at 391 K. Phase transition enthalpy at 298 K, ΔH _tr²⁹⁸(I→II)=2.0±0.4 kJ mol⁻¹, was derived as the difference between the solution enthalpies of the noted polymorphs in the same solution (methanol). Based on ΔH _tr²⁹⁸ (I→II), differences between temperature dependencies of heat capacities of both modifications and the vapor pressure value of form II at 391 K, the temperature dependence of saturated vapor pressure and thermodynamic sublimation parameters for modification II were also estimated (ΔG _sub²⁹⁸=56.1 kJ mol⁻¹; ΔH _sub²⁹⁸=115.9±0.9 kJ mol⁻¹; ΔS _sub²⁹⁸=200±3 J mol⁻¹ K⁻¹). The results indicate that the modifications are monotropically related, which is in contrast to findings recently reported found by classical thermochemical methods.     

Thermodynamics of sublimation,thermophysical and structural aspects of the molecular crystals of fenamates

A method of transfer with an inert carrier gas is used to obtain temperature dependences of pressure vapors. The thermodynamic functions of sublimation processes are calculated for seven molecular crystals that belong to the group of non-steroidal anti-inflammatory drugs: diclofenac, niflumic, flufenamic, tolfenamic, mefenamic, N-phenylanthranilic acids, and diphenylamine. Differential scanning calorimetry is applied to study the melting processes of the selected substances. Single crystal X-ray structural literature data are analyzed, and they are compared with the obtained thermodynamic and thermophysical parameters of sublimation and melting processes. A correlation between the values of the enthalpy of sublimation and the melting temperature under standard conditions is found. The effect of different substituents on the crystal lattice energy of this class of compounds is studied.     

Deformation and annealing textures of rolled nickel single crystals

Textural and structural analysis is conducted on nickel single crystals of unstable orientation in a compression deformed (=83%) and annealed state. The formation of different deformation textures (DT) on opposite surfaces of compressed crystals is established. The relief and band structure corresponds to two-component DT {110} 112, observed in the compression plane. Annealing (573°K) leads to the appearance of recrystallization grains on the two component DT side {110} 112. Orientationally, the first recrystallization grains correspond to the intersection of the peripheral portions of the texture maxima associated with both components of DT. On the side with DT {123} 212, indications of recrystallization were not observed. Application of the texture method with defocus allowed the comparison of the state of the lattice in the regions of the crystal having different orientations. The experimentally observed inhomogeneity of the development of the structure for primary recrystallization is explained by the inhomogeneity of the deformed structure and by orientational factors.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 45–50, June, 1986.     

Thermochemical study of aqueous solutions of lithium diclofenac at 293.15–318.15 K

The enthalpies of solution and dilution of aqueous solutions of lithium diclofenac (LiDC) are measured in the concentration range of 0.002–0.047m at 293.15, 298.15, 308.15, and 318.5 K using an isoperibolic calorimeter. The heat capacity of solid LiDC in the temperature range of 273.15–373.15 K is determined using a DSC 204 F1 Phoenix differential scanning calorimeter (NETZSCH, Germany). The virial coefficients of the enthalpy characteristics of a water-LiDC solution are derived in terms of the Pitzer model to calculate a wide range of thermodynamic properties of both the solution and its components. Changes in these characteristics as a function of concentration and temperature are discussed.