To determine the half-life for gemcitabine hydrochloride using microcalorimetry

The enthalpies of dissolution of gemcitabine hydrochloride in 0.9 % normal saline (medical) and citric acid solution were measured using a microcalorimeter at 309.65 K under atmospheric pressure. The differential enthalpy $ \left( {\Updelta_{\text{dif}} H_{\text{m}}^{{{\theta}}} } \right) $ and molar enthalpy $ \left( {\Updelta_{\text{sol}} H_{\text{m}}^{{{\theta}}} } \right) $ of dissolution were determined, respectively. The corresponding kinetic equation described the dissolution were elucidated to be da/dt = 10^?3.84(1 ? a)^0.92 and da/dt = 10^?3.80(1 ? a)^1.21. Besides, the half-life, $ \Updelta_{\text{sol}} H_{\text{m}}^{{{\theta}}} ,\;\Updelta_{\text{sol}} G_{\text{m}}^{{{\theta}}} $ and $ \Updelta_{\text{sol}} S_{\text{m}}^{{{\theta}}} $ of the dissolution were also obtained. Obviously, it will provide a simple and reliable method for the clinical application of gemcitabine hydrochloride.     

Computer-aided cooling curve thermal analysis of near eutectic Al–Si–Cu–Fe alloy

The effects of bismuth (Bi), antimony (Sb) and strontium (Sr) additions on the characteristic parameters of the evolution of aluminium dendrites in a near eutectic Al–11.3Si–2Cu–0.4Fe alloy during solidification at different cooling rates (0.6–2 °C) were investigated by computer-aided cooling curve thermal analysis (CA-CCTA). Nucleation temperature ( $ T_{\text{N}}^{{\alpha {\text{ - Al}}}} $ ) is defined with a new approach based on second derivative cooling curve. The results showed that $ T_{\text{N}}^{{\alpha {\text{ - Al}}}} $ increased with increasing cooling rate but both the growth temperature ( $ T_{\text{G}}^{{\alpha {\text{ - Al}}}} $ ) and the coherency temperature (T _DCP) decreased. Increase in the temperature difference for dendrite coherency ( $ T_{\text{N}}^{{\alpha {\text{ - Al}}}} - T_{\text{DCP}} $ ) with increasing cooling rate indicate a wider range of temperature before the dendrite can impinge on each other and higher fraction solid ( $ f_{\text{S}}^{\text{DCP}} $ ). Additions of Bi, Sb and Sr to the base alloy produced only a minor effect on $ T_{\text{N}}^{{\alpha {\text{ - Al}}}} $ . Additions of Bi and Sb resulted in an increase in fraction solid and an increase of 30 % in the value of $ T_{\text{N}}^{{\alpha {\text{ - Al}}}} \, - \,T_{\text{G}}^{{\alpha {\text{ - Al}}}} $ to almost 13 °C.     

Synergistic extraction of europium and americium into nitrobenzene by using hydrogen dicarbollylcobaltate and bis(diphenylphosphino)methane dioxide

Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B^?) in the presence of bis(diphenylphosphino)methane dioxide (DPPMDO, L) has been investigated. The equilibrium data have been explained assuming that the species $ {\text{HL}}^{ + } $ , $ {\text{HL}}_{2}^{ + } $ , $ {\text{ML}}_{2}^{3 + } $ , $ {\text{ML}}_{3}^{3 + } $ and $ {\text{ML}}_{4}^{3 + } $ (M³⁺ = Eu³⁺, Am³⁺) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined. It was found that the stability constants of the corresponding complexes $ {\text{EuL}}_{n}^{3 + } $ and $ {\text{AmL}}_{n}^{3 + } $ , where n = 2, 3 and L is DPPMDO, in water–saturated nitrobenzene are comparable, whereas in this medium the stability of the cationic species $ {\text{AmL}}_{4}^{3 + } $ (L = DPPMDO) is somewhat higher than that of $ {\text{EuL}}_{4}^{3 + } $ with the same ligand L.     

Thermal analysis, phase transitions and molecular reorientations in [Sr(OS(CH3)2)6](ClO4)2

Thermal analysis (TG/DTG/QMS), performed for [Sr(OS(CH₃)₂)₆](ClO₄)₂ in a flow of argon and in temperature range of 295–585 K, indicated that the compound is completely stable up to ca. 363 K, and next starts to decompose slowly, and in the temperature at ca. 492 K looses four (CH₃)₂SO molecules per one formula unit. During further heating [Sr(DMSO)₂](ClO₄)₂ melts and simultaneously decomposes with explosion. Differential scanning calorimetry (DSC) measurements performed in the temperature range of 93–370 K for [Sr(DMSO)₆](ClO₄)₂ revealed existence of the following phase transitions: glass ? crystal phase Cr5 at T _g  ≈ 164 K (235 K), phase Cr5 → phase Cr4 at $ T_{\text{c6}}^{\text{h}} $  ≈ 241 K, phase Cr4 → phase Cr3 at $ T_{\text{c5}}^{\text{h}} $  ≈ 255 K, phase Cr3 → phase Cr2 at $ T_{\text{c4}}^{\text{h}} $  ≈ 277 K, phase Cr2 ? phase Cr1 at $ T_{\text{c3}}^{\text{h}} $  ≈ 322 K and $ T_{\text{c3}}^{\text{c}} $  ≈ 314 K, phase Cr1 ? phase Rot2 at $ T_{\text{c2}}^{\text{h}} $  ≈ 327 K and $ T_{\text{c2}}^{\text{c}} $  ≈ 321 K and phase Rot2 ? phase Rot1 at $ T_{\text{c1}}^{\text{h}} $  ≈ 358 K and $ T_{\text{c1}}^{\text{c}} $  ≈ 347 K. Entropy changes values of the phase transitions at $ T_{\text{c1}}^{\text{h}} $ and $ T_{\text{c2}}^{\text{h}} $ (?S ≈ 79 and 24 J mol^?1 K^?1, respectively) indicated that phases Rot1 and Rot2 are substantially orientationally disordered. The solid phases (Cr1–Cr5) are more or less ordered phases (?S ≈ 7, 10, 4 and 3 J mol^?1 K^?1, respectively). Phase transitions in [Sr(DMSO)₆](ClO₄)₂ were also examined by Fourier transform middle infrared spectroscopy (FT-MIR). The characteristic changes in the FT-MIR absorption spectra of the low- and high-temperature phases observed at the phase transition temperatures discovered by DSC allowed us to relate these phase transitions to the changes of the reorientational motions of DMSO ligands and/or to the crystal structure changes.     

Experimental and DFT study on complexation of Eu3+ with a macrocyclic lactam receptor

From extraction experiments and $ \gamma $ -activity measurements, the extraction constant corresponding to the equilibrium $ {\text{Eu}}^{ 3+ } \left( {\text{aq}} \right) + 3 {\text{A}}^{ - } \left( {\text{aq}} \right) + {\mathbf{1}}\left( {\text{nb}} \right) \Leftrightarrow {\mathbf{1}} \cdot {\text{Eu}}^{ 3+ } \left( {\text{nb}} \right) + 3 {\text{A}}^{ - } \left( {\text{nb}} \right) $ taking place in the two-phase water–nitrobenzene system ( $ {\text{A}}^{ - } = \text {CF}_{3} \text{SO}_{3}^{ - } $ ; 1 = macrocyclic lactam receptor—see Scheme 1; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as $ { \log } K_{{{\text{ex}} }} ({\mathbf{1}} \cdot {\text{Eu}}^{ 3+ } ,{\text{ 3A}}^{ - } )\; = \; - 4. 9 \pm 0. 1 $ . Further, the stability constant of the 1·Eu³⁺ cationic complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: $ { \log } \beta_{{{\text{nb}} }} ({\mathbf{1}} \cdot {\text{Eu}}^{ 3+ } ) \; = \; 8. 2 \pm 0. 1 $ . Finally, using DFT calculations, the most probable structure of the cationic complex species 1·Eu³⁺ was derived. In the resulting 1·Eu³⁺ complex, the “central” cation Eu³⁺ is bound by five bond interactions to two ethereal oxygen atoms and two carbonyl oxygens, as well as to one carbon atom of the corresponding benzene ring of the parent macrocyclic lactam receptor 1 via cation-π interaction.

Thermochemistry of hydroxymethylphenol isomers

The standard (p° = 0.1 MPa) molar enthalpies of formation in the crystalline state of the 2-, 3- and 4-hydroxymethylphenols, $ {{\Updelta}}_{\text{f}} H_{\text{m}}^{\text{o}} ( {\text{cr)}} = \, - ( 3 7 7. 7 \pm 1. 4)\,{\text{kJ}}\,{\text{mol}}^{ - 1} $ , $ {{\Updelta}}_{\text{f}} H_{\text{m}}^{\text{o}} ( {\text{cr) }} = - (383.0 \pm 1.4) \, \,{\text{kJ}}\,{\text{mol}}^{ - 1} $ and $ {{\Updelta}}_{\text{f}} H_{\text{m}}^{\text{o}} ( {\text{cr)}} = - (382.7 \pm 1.4)\,{\text{kJ}}\,{\text{mol}}^{ - 1} $ , respectively, were derived from the standard molar energies of combustion, in oxygen, to yield CO₂(g) and H₂O(l), at T = 298.15 K, measured by static bomb combustion calorimetry. The Knudsen mass-loss effusion technique was used to measure the dependence of the vapour pressure of the solid isomers of hydroxymethylphenol with the temperature, from which the standard molar enthalpies of sublimation were derived using the Clausius–Clapeyron equation. The results were as follows: $ \Updelta_{\rm cr}^{\rm g} H_{\rm m}^{\rm o} = (99.5 \pm 1.5)\,{\text{kJ}}\,{\text{mol}}^{ - 1} $ , $ \Updelta_{\rm cr}^{\rm g} H_{\rm m}^{\rm o} = (116.0 \pm 3.7) \,{\text{kJ}}\,{\text{mol}}^{ - 1} $ and $ \Updelta_{\rm cr}^{\rm g} H_{\rm m}^{\rm o} = (129.3 \pm 4.7)\,{\text{ kJ mol}}^{ - 1} $ , for 2-, 3- and 4-hydroxymethylphenol, respectively. From these values, the standard molar enthalpies of formation of the title compounds in their gaseous phases, at T = 298.15 K, were derived and interpreted in terms of molecular structure. Moreover, using estimated values for the heat capacity differences between the gas and the crystal phases, the standard (p° = 0.1 MPa) molar enthalpies, entropies and Gibbs energies of sublimation, at T = 298.15 K, were derived for the three hydroxymethylphenols.     

A thermodynamic study of complexation of 18-crown-6 with Zn2+, Tl+, Hg2+ and {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} cations in acetonitrile-dimethylformamide binary media and study the effect of anion on the stability constant of (18C6-Na+) complex in methanol solutions

The equilibrium constants and thermodynamic parameters for complex formation of 18-crown-6(18C6) with Zn²⁺, Tl⁺, Hg²⁺ and $ {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} $ cations have been determined by conductivity measurements in acetonitrile(AN)-dimethylformamide(DMF) binary solutions. 18-crown-6 forms 1:1 complexes [M:L] with Zn²⁺, Hg²⁺ and $ {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} $ cations, but in the case of Tl⁺ cation, a 1:2 [M:L₂] complex is formed in most binary solutions. The thermodynamic parameters ( $ \Delta {\text{H}}^{ \circ }_{{\text{c}}} $ and $ \Delta {\text{S}}^{ \circ }_{{\text{c}}} $ ) which were obtained from temperature dependence of the equilibrium constants show that in most cases, the complexes are enthalpy destabilized but entropy stabilized and a non-monotonic behaviour is observed for variations of standard enthalpy and entropy changes versus the composition of AN/DMF binary mixed solvents. The obtained results show that the order of selectivity of 18C6 ligand for these cations changes with the composition of the mixed solvent. A non-linear relationship was observed between the stability constants (logK_f) of these complexes with the composition of AN/DMF binary solutions. The influence of the $ {\text{ClO}}^{ - }_{{\text{4}}} $ , $ {\text{NO}}^{ - }_{{\text{3}}} $ and $ {\text{Cl}}^{ - } $ anions on the stability constant of (18C6-Na⁺) complex in methanol (MeOH) solutions was also studied by potentiometry method. The results show that the stability of (18C6-Na⁺) complex in the presence of the anions increases in order: $ {\text{ClO}}^{ - }_{{\text{4}}} $  >  $ {\text{NO}}^{ - }_{{\text{3}}} $  >  $ {\text{Cl}}^{ - } $ .     

Thermodynamic investigations of 1-ethyl-3-methylimidazolium tetrafluoroborate and cycloalkanone mixtures

The densities, ρ, speeds of sound, u, and heat capacities, (C _P)_mix, for binary 1-ethyl-3-methylimidazolium tetrafluoroborate (1) + cyclopentanone or cyclohexanone (2) mixtures within temperature range (293.15–308.15 K) and excess molar enthalpies, H ^E, at 298.15 K have been measured over the entire composition range. The excess molar volumes, V ^E, excess isentropic compressibilities, \( \kappa_{\text{S}}^{\text{E}}, \) and excess heat capacities, \( C_{\text{P}}^{\text{E}}, \) have been computed from the experimental results. The V ^E, \( \kappa_{\text{S}}^{\text{E}} \) , H ^E, and \( C_{\text{P}}^{\text{E}} \) values have been calculated and compared with calculated values from Graph theory. It has been observed that V ^E, \( \kappa_{\text{S}}^{\text{E}} \) , H ^E, and \( C_{\text{P}}^{\text{E}} \) values were predicted by Graph theory compare well with their experimental values. The V ^E, \( \kappa_{\text{S}}^{\text{E}}, \) and H ^E thermodynamic properties have also been analyzed in terms of Prigogine–Flory–Patterson theory.     

Study on the spatial distribution of 137Cs content in bottom sediment and benthic species of Mumbai off coast

The observed ¹³⁷Cs content in bottom sediment and benthic species of Mumbai off coast varied between 2–370  \( {\text{Bq kg}}_{{ ( {\text{dry)}}}}^{ - 1} \) and <0.08–0.4  \( {\text{Bq kg}}_{{ ( {\text{wet)}}}}^{ - 1} \) respectively. The annual estimated ingestion dose to ‘general public’ due to consumption of benthic species is 0.02 µSv y^?1, which is infinitesimally smaller, in comparison to average annual human exposure of 3.01 mSv and also to the internationally accepted public dose limit of 1,000 µSv y^?1.     

Synthesis of lanthanide(III) complexes appended with a diphenylphosphinamide and their interaction with human serum albumin

Two DOTA-based proligands bearing a pendant diphenylphosphinamide 4a and 4b were synthesised. Their Eu(III) complexes exhibit sensitised emission when excited at 270 nm via the diphenylphosphinamide chromophore. Hydration states of q = 1.5 were determined from excited state lifetime measurements (Eu.4a $ k_{{{\text{H}}_{ 2} {\text{O}}}} = 2. 1 4 \,{\text{ms}}^{ - 1} ,\;k_{{{\text{D}}_{ 2} {\text{O}}}} = 0. 6 4 \,{\text{ms}}^{ - 1} $ ; Eu.4b $ k_{{{\text{H}}_{ 2} {\text{O}}}} = 2. 6 7\, {\text{ms}}^{ - 1} ,\;k_{{{\text{D}}_{ 2} {\text{O}}}} = 1. 1 8 \,{\text{ms}}^{ - 1} $ ). In the presence of human serum albumin (HSA) (0.1 mM Eu.4a/b, 0.67 mM HSA, pH 7.4) q = 0.4 for Eu.4a ( $ k_{{{\text{H}}_{ 2} {\text{O}}}} = 1. 3 4\, {\text{ms}}^{ - 1} ,\;k_{{{\text{D}}_{ 2} {\text{O}}}} = 0. 7 5\, {\text{ms}}^{ - 1} $ ) and q = 0.6 for Eu.4b ( $ k_{{{\text{H}}_{ 2} {\text{O}}}} = 1. 8 3\, {\text{ms}}^{ - 1} ,\;k_{{{\text{D}}_{ 2} {\text{O}}}} = 1.0 5 \,{\text{ms}}^{ - 1} $ ). Relaxivites (pH 7.4, 298 K, 20 MHz) of the Gd(III) complexes in the absence and presence of HSA (0.1 mM Gd.4a/b, 0.67 mM HSA) were: Gd.4a (r ₁ = 7.6 mM^?1s^?1 and r ₁ = 11.7 mM^?1s^?1) and Gd.4b. (r ₁ = 7.3 mM^?1s^?1 and r ₁ = 16.0 mM^?1s^?1). These relatively modest increases in r ₁ are consistent with the change in inner-sphere hydration on binding to HSA shown by luminescence measurements on Eu.4a/b. Binding constants for HSA determined by the quenching of luminescence (Eu) and enhancement of relaxivity (Gd) were Eu.4a (27,000 M^?1 ± 12%), Eu.4b (32,000 M^?1 ± 14%), Gd.4a (21,000 M^?1 ± 15%) and Gd.4b (26,000 M^?1 ± 15%).     

Experimental study on the energetics of two indole derivatives

The standard (p ^o = 0.1 MPa) molar energies of combustion, $ \Updelta_{\text{c}} H_{\text{m}}^{\text{o}} $ , for indole-2-carboxylic acid and indole-3-carboxaldehyde, in the crystalline state, were determined, at T = 298.15 K, using a static bomb combustion calorimeter. For both compounds, the vapour pressures as function of temperature were measured, by the Knudsen effusion technique, and the standard molar enthalpies of sublimation, $ \Updelta_{\text{cr}}^{\text{g}} H_{\text{m}}^{\text{o}} $ , at T = 298.15 K, were derived by the Clausius–Clapeyron equation. From the experimental results, the standard (p ^o = 0.1 MPa) molar enthalpies of formation in the condensed and gaseous phases, at T = 298.15 K, of indole-2-carboxylic acid and indole-3-carboxaldehyde were derived. The results are analysed in terms of structural enthalpic increments.     

Crystal structure and standard molar enthalpy of formation of ethylenediamine dilauroleate (C12H24O2)2C2N2H8(s)

The crystal structure of ethylenediamine dilauroleate was determined by X-ray crystallography. A thermochemical cycle was designed in accordance with Hess law. The enthalpy change of the synthesis reaction of ethylenediamine dilauroleate was determined to be $ \Updelta_{{\text{r}}} H_{{\text{m}}}^{\Uptheta } $ Δ r H m Θ  = ?(49.07 ± 0.11) kJ mol^?1 by an isoperibol solution–reaction calorimeter. The standard molar enthalpy of formation of the title compound was calculated to be $ \Updelta_{\text{f}} H_{\text{m}}^{\Uptheta } $ Δ f H m Θ  = ?(38.78 ± 0.43) kJ mol^?1 by the designed thermochemical cycle, the enthalpies of dissolution and other auxiliary thermodynamic quantities.     

Densities and Volumetric Properties of Butyl Acrylate + 1-Butanol, or +2-Butanol, or +2-Methyl-1-propanol, or +2-Methyl-2-propanol Binary Mixtures at Temperatures from 288.15 to 318.15 K

The densities, ρ, of binary mixtures of butyl acrylate with 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol, including those of the pure liquids, were measured over the entire composition range at temperatures of (288.15, 293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K and atmospheric pressure. From the experimental data, the excess molar volume $ V_{\text{m}}^{\text{E}} $ V m E , partial molar volumes $ \overline{V}_{\text{m,1}} $ V ¯ m,1 and $ \overline{V}_{\text{m,2}} $ V ¯ m,2 , and excess partial molar volumes $ \overline{V}_{\text{m,1}}^{\text{E}} $ V ¯ m,1 E and $ \overline{V}_{\text{m,2}}^{\text{E}} $ V ¯ m,2 E , were calculated over the whole composition range as were the partial molar volumes $ \overline{V}_{\text{m,1}}^{^\circ } $ V ¯ m,1 ° and $ \overline{V}_{\text{m,2}}^{^\circ } $ V ¯ m,2 ° , and excess partial molar volumes $ \overline{V}_{\text{m,1}}^{{^\circ {\text{E}}}} $ V ¯ m,1 ° E and $ \overline{V}_{\text{m,2}}^{{^\circ {\text{E}}}} $ V ¯ m,2 ° E , at infinite dilution,. The $ V_{\text{m}}^{\text{E}} $ V m E values were found to be positive over the whole composition range for all the mixtures and at each temperature studied, indicating the presence of weak (non-specific) interactions between butyl acrylate and alkanol molecules. The deviations in $ V_{\text{m}}^{\text{E}} $ V m E values follow the order: 1-butanol < 2-butanol < 2-methyl-1-propanol < 2-methyl-2-propanol. It is observed that the $ V_{\text{m}}^{\text{E}} $ V m E values depend upon the position of alkyl groups in alkanol molecules and the interactions between butyl acrylate and isomeric butanols decrease with increase in the number of alkyl groups at α-carbon atom in the alkanol molecules.     

Synergistic extraction of europium and americium into nitrobenzene by using hydrogen dicarbollylcobaltate and 1,3-bis(diphenylphosphino)propane dioxide

Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B^?) in the presence of 1,3-bis(diphenylphosphino)propane dioxide (DPPPrDO, L) has been investigated. The equilibrium data have been explained assuming that the species $ {\text{HL}}^{ + } ,\,{\text{HL}}_{2}^{ + } ,\,{\text{ML}}^{3 + } \,{\text{and}}\,{\text{ML}}_{3}^{3 + } $ HL + , HL 2 + , ML 3 + and ML 3 3 + (M³⁺ = Eu³⁺, Am³⁺) are extracted into the organic phase. The values of extraction and stability constants of the complex species in nitrobenzene saturated with water have been determined. It was found that the stability constants of the corresponding complexes $ {\text{EuL}}_{n}^{ 3+ } \,{\text{and}}\,{\text{AmL}}_{n}^{ 3+ } , $ EuL n 3 + and AmL n 3 + , where n = 1, 3 and L is DPPPrDO, in water-saturated nitrobenzene are comparable.     

Excess Molar Volumes and Excess Isentropic Compressibilities of o-Toluidine + Tetrahydropyran with Pyridine or Benzene or Toluene Ternary Mixtures at 298.15, 303.15 and 308.15 K

The densities, ρ ₁₂₃, and speeds of sound, u ₁₂₃, of ternary o-toluidine (OT, 1) + tetrahydropyran (THP, 2) + pyridine (Py) or benzene or toluene (3) mixtures have been measured as a function of composition at 298.15, 303.15 and 308.15 K. Values of the excess molar volumes, $ V_{123}^{\text{E}} , $ and excess isentropic compressibilities, $ (\kappa_{\text{S}}^{\text{E}} )_{123} , $ of the studied mixtures have been determined by employing the measured experimental data. The observed thermodynamic properties were fitted with the Redlich–Kister equation to determine adjustable ternary parameters and standard deviations. The $ V_{123}^{\text{E}} $ and $ (\kappa_{\text{S}}^{\text{E}} )_{123} $ values were also analyzed in terms of Graph theory. It was observed that Graph theory correctly predicts the sign as well as magnitude of $ V_{123}^{\text{E}} $ and $ (\kappa_{\text{S}}^{\text{E}} )_{123} $ values of the investigated mixtures. Analysis of the data suggests strong interactions and a more close packed arrangement in OT (1) + THP (2) + Py (3) mixtures as compared to those of the OT (1) + THP (2) + benzene (3) or toluene (3) mixtures. This may be due to the presence of a nitrogen atom in Py which results in stronger interactions for the OT:THP molecular entity as compared to those with benzene or toluene.     

Volumetric Properties of the Nucleoside Thymidine in Aqueous Solution at T = 298.15 K and p = (10 to 100) MPa

Sound speeds have been measured for aqueous solutions of the nucleoside thymidine at T = 298.15 K and at the pressures p = (10, 20, 40, 60, 80, and 100) MPa. The partial molar volumes at infinite dilution, $ V_{2}^{\text{o}} $ , the partial molar isentropic compressions at infinite dilution, $ K_{S,2}^{\text{o}} $ , and the partial molar isothermal compressions at infinite dilution, $ K_{T,2}^{\text{o}} $ $ \{ K_{T,2}^{\text{o}} = - (\partial V_{2}^{\text{o}} /\partial p)_{T} \} $ , have been derived from the sound speeds at elevated pressures using methods described in our previous work. The $ V_{2}^{\text{o}} $ and $ K_{T,2}^{\text{o}} $ results were rationalized in terms of the likely interactions between thymidine and the aqueous solvent. The $ V_{2}^{\text{o}} $ results were also compared with those calculated using the revised Helgeson–Kirkham–Flowers (HKF) equation of state.     

Solvent extraction of strontium and barium into nitrobenzene by using hydrogen dicarbollylcobaltate in the presence of dicyclohexano-24-crown-8

Extraction of microamounts of strontium and barium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B^?) in the presence of dicyclohexano-24-crown-8 (DCH24C8, L) has been investigated. The equilibrium data have been explained assuming that the complexes HL⁺, $ {\text{HL}}_{2}^{ + }, $ ML²⁺ and $ {\text{ML}}_{ 2}^{2 + } $ (M²⁺ = Sr²⁺, Ba²⁺) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined. It was found that in water–saturated nitrobenzene, the stability constants of the complexes BaL²⁺ and $ {\text{BaL}}_{ 2}{^{2 + }}, $ where L = DCH24C8, are somewhat higher than those of the corresponding species SrL²⁺ and $ {\text{SrL}}_{ 2}{^{2 + }} $ with the same ligand L.     

Solvent extraction of microamounts of strontium and barium into nitrobenzene by using synergistic mixture of hydrogen dicarbollylcobaltate and dicyclohexano-18-crown-6

Extraction of microamounts of strontium and barium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B^?) in the presence of dicyclohexano-18-crown-6 (DCH18C6, L) has been investigated. The equilibrium data have been explained assuming that the complexes HL⁺, $ {\text{HL}}_{ 2}^{ + } $ , ML²⁺ and $ {\text{ML}}_{ 2}^{ 2+ } $ (M²⁺ = Sr²⁺, Ba²⁺) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined. It was found that in the mentioned medium the stability constants of the complexes BaL²⁺ and $ {\text{BaL}}_{2}^{2 + }, $ where L = DCH18C6, are somewhat higher than those of the species SrL²⁺ and $ {\text{SrL}}_{2}^{2 + } $ with the same ligand L.     

Density functional study on structures, stabilities, and electronic properties of size-selected Pd n Si q (n = 1–7 and q = 0, +1, −1) clusters

The density functional theory (DFT) calculations within the framework of generalized gradient approximation have been employed to systematically investigate the geometrical structures, stabilities, and electronic properties of Pd _n Si ^q (n = 1–7 and q = 0, +1, ?1) clusters and compared them with the pure ${\text{Pd}}_{n + 1}^{q}$ (n = 1–7 and q = 0, +1, ?1) clusters for illustrating the effect of doping Si atom into palladium nanoclusters. The most stable configurations adopt a three-dimensional structure for both pure and Si-doped palladium clusters at n = 3–7. As a result of doping, the Pd _n Si clusters adopt different geometries as compared to that of Pd _n+1. A careful analysis of the binding energies per atom, fragmentation energies, second-order difference of energies, and HOMO–LUMO energy gaps as a function of cluster size shows that the clusters ${\text{Pd}}_{4}^{ + }$ , ${\text{Pd}}_{4}$ , ${\text{Pd}}_{8}^{ - }$ , ${\text{Pd}}_{5} {\text{Si}}^{0, + , - }$ , and ${\text{Pd}}_{7} {\text{Si}}^{0, + , - }$ possess relatively higher stability. There is enhancement in the stabilities of palladium frameworks due to doping with an impurity atom. In addition, the charge transfer has been analyzed to understand the effect of doped atom and compared further.     

Solvent extraction of calcium into nitrobenzene by using hydrogen dicarbollylcobaltate in the presence of dicyclohexano-18-crown-6 and dicyclohexano-24-crown-8

Extraction of microamounts of calcium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B^?) in the presence of dicyclohexano-18-crown-6 (DCH18C6, L) and dicyclohexano-24-crown-8 (DCH24C8, L) has been investigated. The equilibrium data have been explained assuming that the species HL⁺, $ {\text{HL}}_{2}^{ + },$ CaL²⁺ and $ {\text{CaL}}_{2}^{2 + } $ (L = DCH18C6, DCH24C8) are present in the organic phase. The values of extraction and stability constants of the complex species in nitrobenzene saturated with water have been determined. It was found that the stability constants of CaL²⁺ (L = DCH18C6, DCH24C8) for both ligands under study are practically the same in nitrobenzene saturated with water, whereas in this medium the stability of the complex $ {\text{CaL}}_{2}^{2 + } $ involving the DCH24C8 ligand is somewhat higher than that of $ {\text{CaL}}_{2}^{2 + } $ with the ligand DCH18C6.