InBr3‐ and AgOTf‐catalyzed beckmann rearrangement of (E)‐benzoheterocyclic oximes

Beckmann rearrangement of (E)‐4‐chromanone oxime, (E)‐5‐oximino‐3,4‐dihydro‐1(2H)‐benzoxepines, and (E)‐5‐oximino‐3,4‐dihydro‐1(2H)‐benzothiepine are catalyzed by InBr₃ and AgOTf in refluxing acetonitrile resulting in the formation of pharmaceutically active heterocycles benzoxazepin‐4‐one, 5‐oxo‐benzoxazocines, and 5‐oxo‐benzothiazocine derivative, respectively, in excellent yield. J. Heterocyclic Chem., (2012).     

On-line laser desorption/ionization mass spectrometry of matrix-coated aerosols

Matrix-assisted laser desorption/ionization (MALDI) was used for the on-line analysis of single particles. An aerosol was generated at atmospheric pressure and particles were introduced into a time-of-flight (TOF) mass spectrometer through a single-stage differentially pumped capillary inlet. Prior to entering the mass spectrometer, a matrix was added to the particles using a heated saturator and condenser. A liquid matrix, 3-nitrobenzyl alcohol (NBA), and a solid matrix, picolinic acid (PA), were used. Particles were ablated with a 351 nm excimer laser and the resulting ions were mass-separated in a two-stage reflectron TOF mass spectrometer. Aerosol particles containing the biomolecules erythromycin and gramicidin S were analyzed with and without the matrix addition step. The addition of NBA to the particles resulted in mass spectra that contained an intact molecular ion mass peak. In contrast, PA-coated particles did not yield molecular ion peaks from matrix-coated particles.     

Curcumin,A Novel Natural Photoinitiator for the Copolymerization of Styrene and Methylmethacrylate

Curcumin (Cur), a natural colorant found in the roots of the Turmeric plant, has been reported for the first time as photoinitiator for the copolymerization of styrene (Sty) and methylmethacrylate (MMA). The kinetic data, inhibiting effect of benzoquinone and ESR studies indicate that the polymerization proceeds via a free radical mechanism. The system follows ideal kinetics (R_p α[Cur]^0.5[Sty]^0.97[MMA]¹). The reactivity ratios calculated by using the Finemann–Ross and Kelen‐Tudos models were r₁(MMA)=0.46 and r₂(Sty)=0.52. IR and NMR analysis confirmed the structure of the copolymer. NMR spectrum showing methoxy protons as three distinct groups of resonance between 2.2–3.75 δ and phenyl protons of styrene at 6.8–7.1 δ confirmed the random nature of the copolymer. The mechanism for formation of radicals and random copolymer of styrene and MMA [Sty‐co‐MMA] is also discussed.     

Nanofibrous polyaniline thin film prepared by plasma‐induced polymerization technique for detection of NO2 gas

A nanofibrous polyaniline (PANI) thin film was fabricated using plasma‐induced polymerization method and explored its application in the fabrication of NO₂ gas sensor. The effects of substrate position, pressure, and the number of plasma pulses on the PANI film growth rate were monitored and an optimum condition for the PANI thin film preparation was established. The resulting PANI film was characterized with UV–visible spectrophotometer, FTIR, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The PANI thin film possessed nanofibers with a diameter ranging from 15 to 20 nm. The NO₂ gas sensing behavior was studied by measuring the change in electrical conductivity of PANI film with respect to NO₂ gas concentration and exposure time. The optimized sensor exhibited a sensitivity factor of 206 with a response time of 23 sec. The NO₂ gas sensor using nanofibrous PANI thin film as sensing probe showed a linear current response to the NO₂ gas concentration in the range of 10–100 ppm. Copyright © 2009 John Wiley & Sons, Ltd.     

Reduction of Copper Oxide by Low-Temperature Hydrogen Plasma

The paper presents experimental results of reduction of cupric oxide (CuO) by low-temperature hydrogen plasma in a microwave-assisted plasma set-up. The experiments were carried out at low microwave powers in the range of 600–750 W and low hydrogen flow rates in the range of 0.833 × 10^?6 to 2.5 × 10^?6 m³ s^?1. In all the experiments for reduction of CuO with hydrogen plasma, an initial induction period was observed in the kinetic plots. The induction period decreases with increase in pressure or temperature. The induction period leads to the formation of active sites for adsorption of H₂. After the induction period, fast autocatalytic reduction takes place followed by a sluggish period towards the end. The reduction process proceeds in sequential steps through the formation of sub-oxides. The kinetic data fits the Avrami-Erofeev equation with ‘n’ value close to 3. The resultant activation energy measured during hydrogen plasma processing is around 75.64 kJ mol^?1. This is lower compared to activation energies measured by other methods of reduction indicating a clear advantage.     

Theoretical investigation on the kinetics and thermochemisty of H-atom abstraction reactions of 2-chloroethyl methyl ether (CH<Subscript>3</Subscript>OCH<Subscript>2</Subscript>CH<Subscript>2</Subscript>Cl) with OH radical at 298 K

Kinetics and thermochemistry of the H-atom abstraction reaction of CH₃OCH₂CH₂Cl with OH radical have been carried out using dual level of methods. Initially, geometry optimization and frequency calculations are performed at M06-2X/6-31+G(d, p) level of theory, and energetic calculations are further refined using CCSD(T)/6-311++G(d, p) level of theory in order to characterized all stationary points on potential energy surface (PES). The result shows that H-atom abstraction from –OCH₂ site of CH₃OCH₂CH₂Cl is dominant path. The rate constants are calculated using canonical transition state theory at 298 K, which are found to be in good agreement with the experimental data. We have presented the standard enthalpies of formation for CH₃OCH₂CH₂Cl and the radicals generated during the H-atom abstraction using group-balanced isodesmic reactions scheme. The atmospheric lifetime of title molecule is also calculated.     

Heteronuclear Mn-Ca/Sr complexes, and Ca/Sr EXAFS spectral comparisons with the oxygen-evolving complex of photosystem II

Heterometallic Mn-Ca and Mn-Sr complexes have been prepared and employed as model complexes for Ca and Sr EXAFS spectral comparisons with the Oxygen-Evolving Complex (OEC) of Photosystem II (PS II); these have revealed similarities that support the presence of at least one O atom bridge between the Mn and Ca/Sr in the OEC.     

Diversity-oriented synthetic approach to naturally abundant S-amino acid based benzannulated enantiomerically pure medium ring heterocyclic scaffolds employing inter- and intramolecular mitsunobu reactions

The diversity-oriented organic synthesis of enantiomerically pure benzannulated oxazepine, diazepine, thiazepine, oxazocine, and diazocine scaffolds is described from easily accessible naturally occurring S-amino acids as chiral synthons. Inter- and intramolecular Mitsunobu reactions for the formation of carbon-nitrogen, carbon-oxygen, and carbon-sulfur bonds have been used as key transformations to construct these biologically important privileged heterocycles. This is the first example where the Mitsunobu approach has been utilized for the construction of S-amino acid based seven- and eight-membered ring systems.