1H, 13C, NH, HH, CH COSY, HH NOESY NMR and UV-vis studies of Solophenyl red 3BL dye azo-hydrazone tautomerism in various solvents

Azo-hydrazone tautomeric behavior of polyazo Solophenyl red 3BL (C.I. Direct 80) dye in different solvents (water, methanol and DMSO) was investigated using 1H, 13C, NH, HH, CH COSY, HH NOESY NMR techniques and UV-vis spectroscopy. Two-dimensional NMR experiments were used to assign 1H, 13C and 15N NMR lines unambiguously. Results showed that the hydrazone-form proton NMR signal appeared in the weakest field with respect to tetramethylsilane, in comparison with the amide and phenolic proton NMR signals. UV-vis absorption spectroscopic evidences showed that azo-hydrazone mixture exists in water and DMSO solvents, but in methanol, only azo tautomer was dominant, which was in a good agreement with NMR spectroscopic results.     

Extending Time Profile of Morphine‐Induced Analgesia Using a Chitosan‐Based Molecular Imprinted Polymer Nanogel

Chitosan‐based molecular imprinted polymer (CS‐MIP) nanogel is prepared in the presence of morphine template, fully characterized and used as a new vehicle to extend duration of morphine analgesic effect in Naval Medical Research Institute mice. The CS‐MIP nanogel with ≈25 nm size range exhibits 98% loading efficiency, and in vitro release studies show an initial burst followed by an extended slow release of morphine. In order to study the feasibility of CS‐MIP nanogel as morphine carrier, 20 mice are divided into two groups randomly and received subcutaneous injection of morphine‐loaded CS‐MIP and morphine (10 mg kg^?1) dissolved in physiologic saline. Those received injection of morphine‐loaded CS‐MIP show slower and long lasting release of morphine with 193 min effective time of 50% (ET50) analgesia compared to 120 min ET50 in mice received morphine dissolved in physiologic saline. These results suggest that CS‐MIP nanogel can be a possible strategy as morphine carrier for controlled release and extension of its analgesic efficacy.

     

Stability of a fluid in a horizontal saturated porous layer: effect of non-linear concentration profile, initial, and boundary conditions

Carbon dioxide injected into saline aquifers dissolves in the resident brines increasing their density, which might lead to convective mixing. Understanding the factors that drive convection in aquifers is important for assessing geological CO₂ storage sites. A hydrodynamic stability analysis is performed for non-linear, transient concentration fields in a saturated, homogenous, porous medium under various boundary conditions. The onset of convection is predicted using linear stability analysis based on the amplification of the initial perturbations. The difficulty with such stability analysis is the choice of the initial conditions used to define the imposed perturbations. We use different noises to find the fastest growing noise as initial conditions for the stability analysis. The stability equations are solved using a Galerkin technique. The resulting coupled ordinary differential equations are integrated numerically using a fourth-order Runge–Kutta method. The upper and lower bounds of convection instabilities are obtained. We find that at high Rayleigh numbers, based on the fastest growing noise for all boundary conditions, both the instability time and the initial wavelength of the convective instabilities are independent of the porous layer thickness. The current analysis provides approximations that help in screening suitable candidates for homogenous geological CO₂ sequestration sites.     

A converse of Baer’s theorem

Schur’s classical theorem states that for a group $G$ , if $G/Z(G)$ is finite, then $G'$ is finite. Baer extended this theorem for the factor group $G/Z_n(G)$ , in which $Z_n(G)$ is the $n$ -th term of the upper central series of $G$ . Hekster proved a converse of Baer’s theorem as follows: If $G$ is a finitely generated group such that $\gamma _{n+1}(G)$ is finite, then $G/Z_n(G)$ is finite where $\gamma _{n+1}(G)$ denotes the $(n+1)$ st term of the lower central series of $G$ . In this paper, we generalize this result by obtaining the same conclusion under the weaker hypothesis that $G/Z_n(G)$ is finitely generated. Furthermore, we show that the index of the subgroup $Z_n(G)$ is bounded by a precisely determined function of the order of $\gamma _{n+1}(G)$ . Moreover, we prove that the mentioned theorem of Hekster is also valid under a weaker condition that $Z_{2n}(G)/Z_{n}(G)$ is finitely generated. Although in this case the bound for the order of $\gamma _{n+1}(G)$ is not achieved.     

Study Kinetics of Thermal Decomposition and Electrochemical Oxidation by Using Nanocomposite Paste of Novel Poly(amide-ether)s Derived from Asymmetric Diamine

A new asymmetric diamine containing diarylimodazole pendant was synthesized from the nucleophilic substitution reaction of 1-fluoro-4-nitrobenzene and 2,4-dihydroxy benzaldehyde in the presence of K₂CO₃, followed by reaction with benzil and ammonium acetate for the preparation of imidazole ring. This novel diamine was used to prepare poly(amide-ether) (PAE) in reaction with different commercially available dicarboxylic acids via direct polycondensation using triphenyl phosphite and pyridine (Py) as catalyst. The PAEs were fully characterized and their properties such as inherent viscosity, solubility, optical, thermal and kinetics of thermal decomposition, and electrochemical oxidation were investigated. The polymers had inherent viscosity in the range of 0.47–0.65 dL/g and were noncrystalline with excellent solubility in various polar aprotic organic solvents. Their T_g values ranged from 200 to 355°C and 10% weight loss temperature above 450°C in nitrogen and left more than 70% residue at 650°C. The kinetic parameters of thermal degradation such as activation energy, entropy, enthalpy and Gibbs free energy of thermal decomposition have been evaluated using different equations. We also report electrochemical oxidation of the resulting polymers in aqueous solution by using cyclic voltammetry technique on the multi-walled carbon nanotube-modified glassy carbon electrode.     

Pharmacophore interactions analysis and prediction of inhibitory activity of 1,7-diazacarbazoles as checkpoint kinase 1 inhibitors: application of molecular docking, 3D-QSAR and RBF neural network

In the present study, we mainly focused on new synthesized 1,7-diazacarbazole derivatives (44 active molecules) as Chk1 inhibitors to build 3D-QSAR model. Comparative molecular field analysis (CoMFA) model with three principal components was developed. The relative contributions in building of CoMFA model were 64.41 % for steric field and 35.59 % for electrostatic field. R ² values for training and test sets of CoMFA model were 0.8724 and 0.7818, respectively, and squared correlation coefficient for leave-one-out cross-validation test (q ²) was 0.6753. To improve the predictive power, a new 3D-QSAR model was developed by using radial basis function network (RBFN) and score of CoMFA interactions energy values as input variables. Scores 1, 2 and 3 were used as input variables, and a RBFN model with seven centers and spread value equal to 95 was developed to create a nonlinear 3D-QSAR model. R ² values for training and test sets were 0.9613 and 0.8564, and q ² for leave-one-out cross-validation test was 0.9258. Docking of all molecules to 3DX ligand binding site of Chk1 receptor indicated six interactions as pharmacological interactions between compounds and binding site of receptors. These pharmacological interactions were hydrogen bonding with LEU-15 and GLU-85 in main chain and four van der Waals interactions with LEU-15, VAL-23, TYR-86 and LEU-137 in side chain. CoMFA contour plots were used to design new inhibitors, and inhibitory activity of each compound was predicted by using CoMFA and RBFN models.     

Effect of nano‐modified SiO2/Al2O3 mixed‐matrix micro‐composite fillers on thermal,mechanical, and tribological properties of epoxy polymers

Thermo‐mechanically durable industrial polymer nanocomposites have great demand as structural components. In this work, highly competent filler design is processed via nano‐modified of micronic SiO₂/Al₂O₃ particulate ceramics and studied its influence on the rheology, glass transition temperature, composite microstructure, thermal conductivity, mechanical strength, micro hardness, and tribology properties. Composites were fabricated with different proportions of nano‐modified micro‐composite fillers in epoxy matrix at as much possible filler loadings. Results revealed that nano‐modified SiO₂/Al₂O₃ micro‐composite fillers enhanced inter‐particle network and offer benefits like homogeneous microstructures and increased thermal conductivity. Epoxy composites attained thermal conductivity of 0.8 W/mK at 46% filler loading. Mechanical strength and bulk hardness were reached to higher values on the incorporation of nano‐modified fillers. Tribology study revealed an increased specific wear rate and decreased friction coefficient in such fillers. The study is significant in a way that the design of nano‐modified mixed‐matrix micro‐composite fillers are effective where a high loading is much easier, which is critical for achieving desired thermal and mechanical properties for any engineering applications. Copyright © 2016 John Wiley & Sons, Ltd.     

Mechanism for the degradation of erythromycin A and erythromycin A 2'-ethyl succinate in acidic aqueous solution

A major drawback of the antibiotic erythromycin A is its extreme acid sensitivity, leading to rapid inactivation in the stomach. The accepted model for degradation in aqueous acidic solution has erythromycin A in equilibrium with erythromycin A enol ether and degrading to anhydroerythromycin A. We report a detailed kinetic study of the acidic degradation of erythromycin A and of erythromycin A 2'-ethyl succinate (the market-leading pediatric prodrug), investigating the reaction rates and degradation products via NMR. This reveals that the accepted mechanism is incorrect and that both the enol ether and the anhydride are in equilibrium with the parent erythromycin. By implication, both the anhydride and enol ether are antibacterially inactive reservoirs for the parent erythromycin. The actual degradation pathway is the slow loss of cladinose from erythromycin A (or erythromycin A 2'-ethyl succinate), which is reported here for the first time in a kinetic study. The kinetic analysis is based on global, nonlinear, simultaneous least-squares fitting of time course concentrations for all species across multiple datasets to integrated rate expressions, to provide robust estimates of the rate constants.     

A new insight to the role of bubble properties on inertial effect in particle–bubble interaction

In this study the impact of bubble surface characterization (mobility or immobility), its diameter and velocity is investigated on inertial forces in particle–bubble collision efficiency (E_C). Three models including Sutherland (E_C-SU), Schulze (E_C-SC), and generalized Sutherland Equation (E_C-GSE) were taken into account with regard to their differences from the inertial point of view in the particle size range of 1–100?µm. Bubble diameters of 0.08, 0.12, and 0.15?cm and bubble velocities of 10, 20 and 30?cm/s were selected to study the flotation of chalcopyrite. Weber and Paddock collision model (E_C-W&P) was taken for evaluation of the effect of bubble surface mobility on E_C. It was found that when the bubble diameter is 0.12?cm, reducing bubble velocity from 30 to 20?cm/s, the inertia force can be ignored for wider range of particle size. Corresponding particle size in cross-sectional point between GSE and Schulze collision models was introduced for better evaluation of the positive and negative particle inertial effects. The best agreement between them was taken for bubble diameter of 0.12?cm and velocity of 20?cm/s. It was concluded that the influence of bubble velocity is more effective than bubble diameter regarding its role on particle inertial forces in particle–bubble interaction.