Formation of a tetranuclear copper (II) cluster assembled by metal-assisted hydrolysis and desulfurization of bis(3,5-dimethylpyrazolyl)methylphosphine sulfide, MeP(S)(3,5-Me2Pz)2

The reaction of methylphosphine sulfide, MeP(S)(3,5-Me2Pz)2, 1, with anhydrous CuCl2 affords a tetranuclear copper cluster[Cu2Cl2(3,5-Me2Pz)3(MePO3)]2, 2, and a dinuclear compound Cu2Cl4(3,5-Me2Pz)4, 3. This reaction involves a metal-assisted desulfurization along with concomitant hydrolysis of P-N bonds. The X-ray structures of 1-3 have been determined, and the crystal parameters for these are the following. 1: space group = C2/c, a = 15.2552(1) A, b = 8.7364(2) A, c = 21.4490(3) A, beta = 93.349(1) degrees, V = 2853.74(8) A3, and Z = 8. 2: space group = P2(1)/n, a = 12.5964(4) A, b = 15.7773(4) A, c = 13.9781(4) A, beta = 116.6280(10) degrees, V = 2483.32(12) A3, and Z = 2. 3: space group = P2(1)/c, a = 8.7137(8) A, b = 13.5493(14) A, c = 11.8847(12) A, beta = 106.179(2) degrees, V = 1347.6(2) A3, and Z = 2. The structure of 2 shows that it comprises two dinuclear copper cores bridged together by two tripodal methylphosphinate, MePO3, ligands. 2 is weakly antiferromagnetically coupled, as revealed by variable temperature magnetic susceptibility measurements.     

Silicon‐containing trifunctional and tetrafunctional cyanate esters: Synthesis,cure kinetics,and network properties

The synthesis and physical properties of new silicon‐containing polyfunctional cyanate ester monomers methyl[tris(4‐cyanatophenyl)]silane and tetrakis(4‐cyanatophenyl)silane, as well as polycyanurate networks formed from these monomers are reported. The higher crosslinking functionality compared to di(cyanate ester) monomers enables much higher ultimate glass transition temperatures to be obtained as a result of thermal cyclotrimerization. The ability to reach complete conversion is greatly enhanced by cocure of the new monomers with di(cyanate ester) monomers such as 1,1‐bis(4‐cyanatophenyl)ethane. The presence of silicon in these polycyanurate networks imparts improved resistance to rapid oxidation at elevated temperatures, resulting in char yields as high as 70% under nitrogen and 56% in air in the best‐performing networks. The water uptake in the silicon‐containing networks examined is 4–6 wt % after 96 h of immersion at 85 °C, considerably higher than both carbon‐containing and/or di(cyanate ester) analogs. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 767–779     

Debye process and dielectric state of an alcohol in a nonpolar solvent

To investigate the origin of the first order molecular kinetics of the most prominent, Debye-type polarization, a detailed dielectric relaxation study of 66.5, 40, and 20 mole% solutions of 5-methyl-2-hexanol in 2-methylpentane (2:1, 0.67:1, and 0.25:1 molar ratios) was performed. The Debye-type polarization remains prominent in the solutions, despite the extensive loss of intermolecular hydrogen bonds. At high temperatures, its contribution to permittivity extrapolates close to the statistically scaled values for the 2:1 solution. For others, the measured values of its contribution crossover the scaled values in a temperature plane. The faster relaxation process of about 4% magnitude has an asymmetric distribution of times in the solutions and, relative to those of the pure alcohol, their values decrease on heating more at high temperatures and less at low. This is attributed to an increase in the alcohol cluster size by consumption of monomers as well as the growth of smaller clusters as the solution is cooled. It is argued that structural fluctuation in solutions, as in the pure alcohol, is determined by the rates of both the Debye-type and the faster polarizations in the ultraviscous state.     

The high frequency dielectric response of a ferroelectric liquid crystal

Abstract

The temperature and frequency dependences of the complex dielectric susceptibility of a ferroelectric liquid crystal near the smectic C*-smectic A phase transition have been calculated using the classical and generalized Landau models. It is shown that although the dielectric response of the S*_C phase consists generally of four modes (soft, Goldstone, and two high frequency polarization modes) only three bands appear in the dielectric loss spectrum of ferroelectric liquid crystals at the S_A–S*_C phase transition. These results are in agreement with recent experimental data.     

Sequence of four orthogonal smectic phases in an achiral bent-core liquid crystal: evidence for the SmAP(α) phase

The mesomorphic properties of an achiral bent-core liquid crystal derived from 4-cyanoresorcinol are studied by polarizing optical microscopy, x-ray diffraction, and second harmonic electro-optic response. It shows a novel sequence of four nontilted or orthogonal smectic phases on cooling: SmA-SmAP(R)-SmAP(X)-SmAP(A). Here SmAP(X) is the new orthogonal polar uniaxial smectic phase. The electric-field-induced transformations in the SmAP(X) phase give rise to two biaxial states separated by a uniaxial one. The second harmonic electro-optic response in this phase is interpreted in terms of the polar interaction with the electric field. A comparison of the experimental results with the next-nearest-neighbor model for the structure of the SmAP(X) phase shows it to be an SmAP(α) phase.     

Nonlinear budó model for dielectric relaxation: Comparison with new experimental data

Zeitschrift für Physik B Condensed Matter -     

Orientation polarization from faster motions in the ultraviscous and glassy diethyl phthalate and its entropy

Dielectric spectra of the beta relaxation in glassy and ultraviscous liquid diethyl phthalate show that its relaxation strength Delta epsilon(beta), the distribution of times, and the relaxation rate are more sensitive to temperature T in the ultraviscous liquid than in the glassy state. The Delta epsilon(beta) against temperature plot has an elbow-shaped break near T(g) of approximately 181 K, which is remarkably similar to that observed in the entropy, enthalpy, and volume against temperature plots, and in the plot of Delta epsilon(beta) against the liquid's entropy minus its 0 K value. The ratio of Delta epsilon(beta) to diethyl phthalate's entropy, after subtracting the 0 K value, is 1.08 x 10(-3) mol K/J in the glassy state at 120.4 K, which decreases slowly to 0.81 x 10(-3) mol K/J at 176 K near T(g) and thereafter rapidly increases to 1.57 x 10(-3) mol K/J at 190 K. Variation in Delta epsilon(beta) parallels the variation of the entropy. A change in the activation energy of the beta process at T>T(g) indicates that its rate is also determined by the structure of the ultraviscous liquid. Features of beta relaxation are consistent with localized motions of molecules and may not involve small-angle motions of all molecules.     

Toward the identification of a reliable 3D QSAR pharmacophore model for the CCK2 receptor antagonism

The present study describes application of computational approaches to identify a validated and reliable 3D QSAR pharmacophore model for the CCK-2R antagonism through integrated ligand and structure based studies using anthranilic sulfonamide and 1,3,4-benzotriazepine based CCK-2R antagonists. The best hypothesis consisted five features viz. two aliphatic hydrophobic, one aromatic hydrophobic, one H-bond acceptor, and one ring aromatic feature with an excellent correlation for 34 training set (r2(training) = 0.83) and 58 test set compounds (r2(test) = 0.74). This model was validated through F-test and docking studies at the active site of the plausible CCK-2R where the 99% significance and well corroboration with the pharmacophore model respectively describes the model's reliability. The model also predicts well to other known clinically effective CCK-2R antagonists. Therefore, the developed model may useful in finding new scaffolds that may aid in design and develop new chemical entities (NCEs) as potent CCK-2R antagonists before their synthesis.