Kinetics of copper(II)‐catalyzed oxidation of S(IV) by atmospheric oxygen in ammonia buffered solutions

To understand the chemistry of Cu(II)–NH₃–S(IV)–O₂ system, the kinetics of the oxidation of sulfur(IV) catalyzed by amminecopper(II) complexes has been studied in the ammonia‐buffered solutions. Sulfur(IV) is oxidized to sulfate. The complexes, Cu(NH₃)²⁺, Cu(NH₃)₂²⁺, and Cu(NH₃)²⁺₃ appear to be equally reactive and Cu(NH₃)₄²⁺ appears to be unreactive. The kinetics obey the rate law: where α₁ and γ₁ are the rate constants for O₂‐dependent and O₂‐independent pathways, respectively, for Cu(NH₃)²⁺, Cu(NH₃)²⁺₂, and Cu(N H₃)₃²⁺ complexes, which appear to be equally reactive. The values of α₁ and γ₁ were found to be (1.32 ± 0.21) × 10⁶ L² mol^?2 s^?1 (1.74 ± 0.40) × 10⁹ L³ mol^?3 s^?1respectively at 30°C. The reaction rate is not influenced by the presence of ethanol—a free radical scavenger, so a nonradical mechanism has been proposed. The results of this study are useful in understanding the atmospheric chemistry of aqueous phase autoxidation of dissolved sulfur dioxide in copper(II)–ammonia–sulfur(IV)–oxygen system at high pH. © 2011 Wiley Peiodicals, Inc. Int J Chem Kinet 43: 379–392, 2011     

Medium-ring aminocyclitols: a concise synthesis of nine-membered aminocarbasugar analogs and the solid-state supramolecular architectures of two key precursors

A stereocontrolled synthesis of nine-membered aminocarbasugar analogs (amino-cyclononanoses) from a rigid bicyclo[4.3.1]deca-2,4-dien-10-one platform, harboring a latent functionalized cyclononane ring, is described.     

Highly sensitive hydrazine chemical sensor based on mono-dispersed rapidly synthesized PEG-coated ZnS nanoparticles

Monodispersed PEG-coated ZnS (P-ZnS) nanoparticles (NPs) were synthesized by facile microwave process and utilized as efficient electron mediators for the fabrication of highly sensitive hydrazine chemical sensor. The detailed morphological and structural properties revealed the monodispersity and good crystallinity for synthesized P-ZnS NPs. A high-sensitivity of ∼89.3 μA cm⁻² μM and low limit of detection of 1.07 μM, based on S/N ratio, were obtained for the fabrication of hydrazine chemical sensor based on P-ZnS NPs. To the best of our knowledge, this is the first report which demonstrates the utilization of P-ZnS NPs for the fabrication of efficient hydrazine chemical sensor. By this work, it could be concluded that simply synthesized ZnS NPs can be used as efficient electron mediators for the fabrication of effective hydrazine chemical sensors.     

N-heterocyclic carbene catalyzed aroylation of 3,5-dichloro-2(1H)-pyrazinones

The N-heterocyclic carbene catalyzed chemoselective C3-aroylation of 3,5-dichloro-2(1H)-pyrazinones with various aldehydes is reported. We herein describe results of this remarkable mild and efficient procedure.     

Mono- and dicarbonyl-bridged tricyclic heterocyclic acceptors: synthesis and electronic properties

A series of trialkylsilyl-substituted 2,2'-dithiophene, 4,4'-di-n-hexyl-2,2'-dithiophene, 5,5'-dithiazole, and 2,2'-diselenophene with carbonyl (2a-d) and α-dicarbonyl bridges (3a-d) were prepared from readily available dihalides, using double lithiation followed by trapping with N,N-dimethylcarbamoyl chloride or diethyl oxalate (or N,N-dimethylpiperazine-2,3-dione), respectively. Cyclic voltammetry reveals that the first half-wave reduction potentials for this series of compounds span a wide range, from -1.87 to -0.97 V vs the ferrocene/ferrocenium couple at 0 V (0.1 M (n)Bu(4)NPF(6) in THF). A significant increase of the first half-wave reduction potential (by 0.50-0.67 V) was observed on substitution of the monocarbonyl bridge with α-dicarbonyl. Adiabatic electron affinity (AEA, gas phase) trends determined via density functional theory (DFT) calculations are in good agreement with the electrochemical reduction potentials. UV-vis absorption spectra across the series show a weak absorption band in the visible range, corresponding to the HOMO→LUMO transition within a one-electron picture, followed by a more intense, high-energy transition(s). Single-crystal X-ray structural analyses reveal molecular packing features that balance the interplay of the presence of the bulky substituents, intermolecular π-stacking interactions, and S···O intermolecular contacts, all of which affect the DFT-evaluated intermolecular electronic couplings and effective charge-carrier masses for the crystals of the tricyclic cores.     

Two-dimensional cell parameters measurement of nematic liquid crystal using optical interferometry and Fourier transform fringe analysis technique

We report a method for the measurement of nematic liquid crystal (NLC) cell parameters i.e., switching voltage, birefringence, retardation, dielectric anisotropy, average tilt angle and change in refractive index with applied DC voltage to LC material. The proposed method is based on optical interferometry and Fourier transform fringe analysis technique, in which we obtain 2-dimensional (2D) phase map of the interferograms as a function of applied voltage. Mach-Zehnder interferometer (MZI) was used for the study of cell parameters and interferograms were recorded at different applied DC voltages to NLC cell using CCD camera. From the phase map, 2D-refractive index distribution of the LC cell with applied voltage was reconstructed. Analytical equations are derived based on optical interferometry and then solved to obtain cell parameters. The present method is fast and can give 2D-cell parameters from only two quick interferograms.     

A fast algorithm to solve viscous two-phase flow in an axisymmetric rocket nozzle

A numerically fast algorithm has been developed to solve the viscous two-phase flow in an axisymmetric rocket nozzle. A Eulerian–Eulerian approach is employed in the computation to couple the gas–particle flow. Turbulence closure is achieved using a Baldwin–Lomax model. The numerical procedure employs a multistage time-stepping Runge–Kutta scheme in conjunction with a finite volume method and is made computationally fast for the axisymmetric nozzle. The present numerical scheme is applied to compute the flow field inside JPL and AGARD nozzles. © 1998 John Wiley & Sons, Ltd.     

Determination of inorganic nitrate impurity from nicorandil and its tablet dosage form by simple reversed phase liquid chromatographic method

A simple, fast, precise, specific and economical reverse phase liquid chromatographic method was developed for determination of nitrate (NIT) impurity from nicorandil (NIC) and its tablet dosage form. NIT is process impurity as well as a degradation product of NIC. This article is based on application of amino propyl silane (APS) column for determination of NIT in presence of NIC and various excipients using potassium nitrate as a standard. The developed method was validated for its intended use by evaluating various important parameters like linearity, accuracy, recovery and specificity. The developed method was applied to evaluate the compatibility study of NIC with various excipients by monitoring the NIT content.     

Short,Convenient Preparative Procedures for 7-Isopropylidenenorbornane, 7-Isopropylidenenorbornene,and 7-Isopropylidenenorbornadiene

Short synthetic routes to the title compounds 1,–3, from readily available Diels-Alder adduct 5 of 6,6-dimethylfulvene and acrylonitrile are described.