Effect of ammonia,ammonia-water,and sulfuric acid on the HO2 + HO2 → H2O2 + 3O2 reaction in troposphere: Competition between stepwise and one-step mechanisms

A detailed theoretical study on the reaction mechanisms for the formations of H₂O₂ + ³O₂ from the self-reaction of HO₂ radicals under the effect of NH₃, H₃N···H₂O, and H₂SO₄ catalysts was performed using the CCSD(T)/CBS//M06-2X/aug-cc-pVTZ method. The rate constant was computed using canonical variational transition state theory (CVT) with small curvature tunneling (SCT). Our results indicate that NH₃-, H₃N···H₂O-, and H₂SO₄-catalyzed reactions could proceed through both one-step and stepwise routes. Calculated rate constants show that the catalyzed routes in the presence of the three catalysts all prefer stepwise pathways. Compared to the catalytic efficiency of H₂O, the efficiencies of NH₃, H₃N···H₂O, and H₂SO₄ are much lower due to their smaller relative concentrations. The present results have provided a definitive example of how basic and acidic catalysts influence the atmospheric reaction of HO₂ + HO₂ → H₂O₂ + ³O₂. These results further encourage one to consider the effects of basic and acidic catalysts on the related atmospheric reactions. Thus, the present investigation should have broad implications in the gas-phase reactions of the atmosphere.     

Thermodynamic analysis of solute-solvent interactions in the solubility-temperature relations of alkaline-earth metal tungstates and sodium tungstate

This paper presents a study of thermodynamic analysis of the solubility-temperature phase diagrams for solutions of calcium, strontium and barium tungstate in sodium tungstate melts in the temperature range 660 to 1200 °C. At temperatures 1000 °C and above, the solutions were ideal but below 1000 °C the solutions became non-ideal and the non-ideality increased with decreasing temperature. At any mole fraction concentration of the solute the excess free energies of mixing and the activity coefficients increased in the order CaWO₄ > SrWO₄ > BaWO₄, whereas the excess chemical potentials decreased in the order CaWO₄ < SrWO₄ < BaWO₄.     

Evaluation of degree of crystallization by optical microscopy and chemical analysis in crystallization of alkaline-earth metal tungstates from solutions in lithium chloride melts

A comparative study of the accuracy of optical microscopy and chemical analysis of residual solutions for evaluation of degree of crystallisation was carried out to ascertain their suitability for kinetics study of CaWO₄ and BaWO₄ crystallisation from LiCl melts (i) by continuous cooling at a constant cooling rate, and (ii) at constant temperature from a supersaturated solution. Chemical analysis of residual solution does not give desirable accuracy for the case (i) for α_t values <0.30, and for the case (ii) for α_t values <0.60. Optical microscopy was more accurate and suitable for both cases.     

Production of Bioactive Compounds with Broad Spectrum Bactericidal Action,Bio-Film Inhibition and Antilarval Potential by the Secondary Metabolites of the Endophytic Fungus Cochliobolus sp. APS1 Isolated from the Indian Medicinal Herb Andrographis paniculata

Endophytes, being the co-evolution partners of green host plants, are factories of pharmaceutically valuable novel natural products. Cochliobolus sp. APS1, an endophyte of Andrographis paniculata (Green Chiretta), produces a plethora of natural bioactive compounds and the multipotent alkaloid Aziridine, 1-(2-aminoethyl)-, is the prime one among them. The isolate exhibited antibacterial, anti-biofilm, and antilarval potency. The MIC and MBC values of the ethyl-acetate culture extract ranged from 15.62 to 250 µg/mL against ten pathogenic microorganisms (including MRSA and VRSA). Killing kinetics data along with the leakage of macromolecules into the extracellular environment supports the cidal activity of the antibacterial principles. The broad spectrum antibacterial activity of Aziridine, 1-(2-aminoethyl)-, was optimized by a one-variable-at-a-time system coupled with response surface methodology, which led to a 45% enhancement of the antibacterial activity. The maximum response (22.81 ± 0.16 mm of zone of inhibition against MRSA) was marked in 250 mL Erlenmeyer flask containing 90 mL potato dextrose broth supplemented with (g%/L) glucose, 9.7; urea concentration, 0.74; with medium pH 6.48; after 8.76 days of incubation at 26 °C. APS1 strongly inhibited biofilm formation in the tested pathogenic microorganisms and acts as a larvicidal agent against the Dengue-vector Aedes aegypti. This is probably the first report of Aziridine, 1-(2-aminoethyl)-, from any endophytic source. Cochliobolus sp. APS1 possesses industrial importance for the production of bioactive alkaloids.     

Characteristics of electrochemically grown dendritic metallic zinc

A simple electrochemical process has been implemented to fabricated fractal structured leaf-like metallic zinc. The fabricated material was structurally characterized using X-ray diffraction that reveals the hexagonal unit cell structure. Also the growth of the structure is anisotropic. Field emission scanning electron microscopic images revealed clearly the leaf-like morphology of the fabricated material is fern like and ∼500 μm in length, ∼50-60 μm wide and the platelets thickness is ∼5 μm. The growth of this structure is diffusion controlled and locally accomplished with the oriented attachment. Raman shift measurement revealed the existence of surface optical phonon modes which is very significant for surface defects.     

Weak Galerkin finite element methods combined with Crank-Nicolson scheme for parabolic interface problems

This article is devoted to the a priori error estimates of the fully discrete Crank-Nicolson approximation for the linear parabolic interface problem via weak Galerkin finite element methods (WG-FEM). All the finite element functions are discontinuous for which the usual gradient operator is implemented as distributions in properly defined spaces. Optimal order error estimates in both $L^{\infty}(H^1)$ and $L^{\infty}(L^2)$ norms are established for lowest order WG finite element space $({\cal P}_{k}(K),\;{\cal P}_{k-1}(\partial K),\;\big[{\cal P}_{k-1}(K)\big]^2)$. Finally, we give numerical examples to verify the theoretical results.     

A theoretical study of antioxidant activity of some Schiff bases derived from biologically important phenolic aldehydes and phenylenediamines

Because of their numerous biological as well as industrial importance, the study of Schiff bases is an emerging field for the researchers, in recent time. In this study, we have designed some Schiff bases derived from biologically important precursors. The antioxidant activities of the designed compounds are thoroughly studied theoretically using density functional theory taking various parameters like bond dissociation enthalpy, ionization enthalpy, proton dissociation enthalpy, and electron transfer enthalpy followed by the study of effects of solvent, spin density, and molecular orbital on antioxidant activity of the compounds. The comparison of antioxidant activity of the compounds with that of phenol and their parent aldehydes reveals the superior antioxidant activity of the designed compounds. This study contributes towards the information of an important bridge between bioorganic and computational chemistry.     

Nonparaxial effects on the propagation and scattering of a polarized optical pulse

Propagation characteristics of a polarized optical solitary pulse are analyzed by taking into account the effect of nonparaxiality and mutual interaction. To start with, a pair of generalized nonlinear Schrodinger equations is deduced through an operator approach. Stationary solutions of such a system are then analyzed numerically through a boundary value problem in two stages, with and without the nonparaxial effect. In the second stage, the propagating form of the corresponding spatial soliton is studied by an extended split step algorithm ETDRK. The initial profile is considered to be both a one- and two-soliton solution, to visualize the event of scattering and fusion. From this data, we have computed the intensity, root mean square spectral width, and chirp of a single soliton as it propagates. In the case of the two-soliton solution, we observe that for source parameter values, the fusion is more favored than scattering. It is observed that nonparaxiality and the interaction between A(x) and A(y) tends to destroy the periodic behaviors of these parameters. Lastly, we have investigated the modulational instability of the system as function of frequency detuning and nonparaxiality. The form of the gain is discussed as a function of nonparaxiality.