Evidence for α-elimination from neopentyl chloride in the gas phase

Experimental evidence is presented for a unimolecular gas-phase Wagner-Meerwein shift in neopentyl chloride pyrolysis. In the decomposition of α,α-neopentyl chloride-d₂ at 445°C, maximally inhibited by cyclohexene, the initial products were isotopically pure 2-methyl-1-butene-d₂ and 2-methyl-2-butene-d₁. Rearrangement, accompanied by loss of either α- or γ-hydrogen in the formation of hydrogen chloride, is consistent with an incipient ion-pair type of transition state. The cyclohexene maximally inhibited pyrolysis of neopentyl chloride was also examined over the temperature range 424–478°C and Arrhenius parameters of E, 258.7 kJ/mole and logA/sec^?1, 13.78, were determined.     

Structural modifications of silicon-implanted GaAs induced by the athermal annealing technique

We have used high-resolution X-ray diffraction and Raman spectroscopy to investigate structural modifications inside and outside the focal region of Si-implanted GaAs samples that have been irradiated at high power by a focused short-pulse laser. Si atoms implanted into the GaAs matrix generate exciton-induced local lattice expansion, resulting in a satellite on the lower-angle side of the Bragg peak. After the laser pulse irradiation, surface features inside and outside the focal spot suggest the presence of Bernard convection cells, indicating that a rapid melting and re-crystallization has taken place. Moreover, the laser irradiation induces a compressive strain inside the focal spot, since the satellite appears on the higher-angle side of the Bragg peak. The stress maximizes at the center of the focal spot and extends far outside the irradiated area (approximately 2.5-mm away from the bulls eye), suggesting the propagation of a laser-induced mechanical wave. The maximum compressive stress inside the focal spot corresponds to 2.7 GPa. Raman spectra inside the focal spot resemble that of pristine GaAs, indicating that rapid melting has introduced significant heterogeneity, with zones of high and low Si concentration. X-ray measurements indicate that areas inside the focal spot and annealed areas outside of the focal spot contain overtones of a minor tetragonal distortion of the lattice, consistent with the observed relaxation of Raman selection rules when compared with the parent zinc-blende structure. PACS 61.72.Vv; 62.50.+p; 71.55.Eq; 79.20.Ds; 81.05.Ea     

Synthesis and dynamics studies of barbituric acid derivatives as urease inhibitors

Background

Discovery of potent inhibitors of urease (jack bean) enzyme is the first step in the development of drugs against diseases caused by ureolytic enzyme.

Results

Thirty-two derivatives of barbituric acid as zwitterionic adducts of diethyl ammonium salts were synthesized. All synthesized compounds (4a–z and 5a–s) were screened for their in vitro inhibition potential against urease enzyme (jack bean urease). The compounds 4i (IC₅₀ = 17.6 ± 0.23 µM) and 5l (IC₅₀ = 17.2 ± 0.44 µM) were found to be the most active members of the series, and showed several fold more urease inhibition activity than the standard compound thiourea (IC₅₀ = 21.2 ± 1.3 µM). Whereas, compounds 4a–b, 4d–e, 4g–h, 4j–4r, 4x, 4z, 5b, 5e, 5k, 5n–5q having IC₅₀ values in the range of 22.7 ± 0.20 µM–43.8 ± 0.33 µM, were also found as potent urease inhibitors. Furthermore, Molecular Dynamics simulation and molecular docking studies were carried out to analyze the binding mode of barbituric acid derivatives using MOE. During MD simulation enol form is found to be more stable over its keto form due to their coordination with catalytic Nickel ion of Urease. Additionally, structural–activity relationship using automated docking method was applied where the compounds with high biological activity are deeply buried within the binding pocket of urease. As multiple hydrophilic crucial interactions with Ala169, KCX219, Asp362 and Ala366 stabilize the compound within the binding site, thus contributing greater activity.

Conclusions

This research study is useful for the discovery of economically, efficient viable new drug against infectious diseases.

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Graphical abstract: STD. Thiourea (IC₅₀ = 21.2 ± 1.3 µM)

     

On smoothing of the Crank–Nicolson scheme and higher order schemes for pricing barrier options

Most option pricing problems have nonsmooth payoffs or discontinuous derivatives at the exercise price. Discrete barrier options have not only nonsmooth payoffs but also time dependent discontinuities. In pricing barrier options, certain aspects are triggered if the asset price becomes too high or too low. Standard smoothing schemes used to solve problems with nonsmooth payoff do not work well for discrete barrier options because of discontinuities introduced in the time domain when each barrier is applied. Moreover, these unwanted oscillations become worse when estimating the hedging parameters, e.g., Delta and Gamma. We have an improved smoothing strategy for the Crank–Nicolson method which is unique in achieving optimal order convergence for barrier option problems. Numerical experiments are discussed for one asset and two asset problems. Time evolution graphs are obtained for one asset problems to show how option prices change with respect to time. This smoothing strategy is then extended to higher order methods using diagonal (m,m)$(m,m)$—Padé main schemes under a smoothing strategy of using as damping schemes the (0,2m-1)$(0,2m-1)$ subdiagonal Padé schemes.     

Inclusion complexes of cyclodextrins with hydrophobic ionic liquids

Two imidazolium-based hexafluorophosphate ionic liquids (ILs), 1-butyl-3-methylimidazolium hexafluorophosphate and 1-dodecyl-3-methylimidazolium hexafluorophosphate, were used to form inclusion complexes (ICs) with α- and β-cyclodextrins (CDs). Formation of the ICs of each CD with each IL was confirmed by the appearance of a characteristic peak in the UV region. Characterisation of the ICs by NMR and FT-IR spectroscopy provided information about the interactions between the host and guest molecules and the structure of the ICs. Temperature-dependent particle size analysis by dynamic light scattering suggested that the size of the host and the guest governs their stability.     

Calcination temperature-dependent morphology of photocatalytic ZnO nanoparticles prepared by an electrochemical–thermal method

ZnO nanoparticles (NPs) with tunable morphologies were synthesized by a hybrid electrochemical–thermal method at different calcination temperatures without the use of any surfactant or template. The NPs were characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction, dynamic light scattering, thermogravimetry–differential thermal analysis, scanning electron microscope and N₂ gas adsorption–desorption studies. The FT-IR spectra of ZnO NPs showed a band at 450 cm^?1, a characteristic of ZnO, which remained fairly unchanged at calcination temperatures even above 300 °C, indicating complete conversion of the precursor to ZnO. The products were thermally stable above 300 °C. The ZnO NPs were present in a hexagonal wurtzite phase and the crystallinity of ZnO increased with an increasing calcination temperature. The ZnO NPs calcined at lower temperature were mesoporous in nature. The surface areas of ZnO NPs calcined at 300 and 400 °C were 51.10 and 40.60 m² g^?1, respectively, which are significantly larger than commercial ZnO nanopowder. Surface diffusion has been found to be the key mechanism of sintering during heating from 300 to 700 °C with the activation energy of sintering as 8.33 kJ mol^?1. The photocatalytic activity of ZnO NPs calcined at different temperatures evaluated by photocatalytic degradation of methylene blue under sunlight showed strong dependence on the surface area of ZnO NPs. The ZnO NPs with high surface area showed enhanced photocatalytic activity.     

Efficient smoothing of Crank-Nicolson method for pricing barrier options under stochastic volatility

Most of the option pricing problems have nonsmooth payoff. In barrier options certain aspects of the option are triggered if the asset price becomes too high or too low. Standard smoothing schemes used to solve problems with nonsmooth payoff do not work well for the barrier option because a discontinuity is introduced in the time domain each time a barrier is applied. An improved smoothing strategy is introduced for smoothing the A -stable Cranck-Nicolson scheme at each time when a barrier is applied. A partial differential equation (PDE) approach is utilized for the evaluation of complex option pricing models under stochastic volatility which brings major mathematical and computational challenges for estimation and stability of the estimates. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

High pressure X-ray diffraction studies on UAI2, UAI2, and UAI4 systems

Abstract

The UAI₂, UAI₂, AND UAI₄ compounds have been studied by high pressure X-ray diffraction up to a maximum pressure of ～ 35 GPa. The compressibility behaviour of UAI₂ has been found to be consistent with the itinerant 5f states, whereas that of UAI₂ and UAI₄, indicate a more localized nature. Further, UAI₂ has been found to undergo a structural transition at ～ 11 GPa and the structure of the high pressure phase has been identified to be of MgNi₂ type with space group P6₃/mmc. The structure of UAI₂ at ambient pressure is of MgCu₂ type with space group Fd3m. From the electronic considerations, for instance, free electrons per atom ratio e/a, it is anticipated that it may transform back to MgCu₂ type structure at still higher pressures. On similar considerations, it is expected that most of the AB₂ type Laves phase compounds of the ‘f’ electron systems may undergo the structural sequence: MgCu₂ – MgZn₂ (or MgNi₂) – MgCu₂ due to increased delocalization of their ‘f’ electron states.     

Potentiodynamic studies on corrosion of copper by chloride ions and its inhibition by inorganic and organic ions in aqueous buffer solution

Electrochemical oxidation of copper in aqueous phosphate buffer solution leads to the formation of passive films, which breakdown in the presence of aggressive chloride (Cl^?) ions. The addition of Cl^? ions in the medium causes shift in current and potential for both cathodic and anodic peaks. At low Cl^? ion concentrations, the corrosion current is greatly enhanced and continues to increase up to a certain concentration, after which it decreases. The effect of inorganic ions, chromate (CrO ₄ ^2? ) and tungstate (WO ₄ ^2? ), and organic ions, acetate (CH₃COO^?) and oxalate (C₂O ₄ ^2? ), on the formation and breakdown of passive films in aqueous buffer solution containing 0.10 M Cl^? ions have also been investigated. All of the ions inhibit corrosion of copper in the presence of aggressive Cl^? ions following the order of overall inhibition efficiency of CrO ₄ ^2? > C₂O ₄ ^2? > WO ₄ ^2? > CH₃COO^? under the experimental conditions.