Anionische Polymerisationen von 1, 3-Cyclohexadien

The molecular weights obtained in the anionic polymerization of 1.3-cyclohexadiene are exclusively determined by chain transfer with monomer. No dissociation of the ion pairs on the active chain ends seems to occur. Arrhenius plots of the intrinsic viscosities against polymerization temperature yield straight lines going through a common isocinetic point. The activation energy differences of propagation and transfer could be estimated. The extent of chain transfer depends on the solvent and counter-ion present. The disproportionation of cyclohexadiene to benzene and cyclohexene, sometimes observed instead of the polymerization, is shown to occur if the transfer constant approaches the magnitude of unity.     

Quantum well behavior without confining barrier observed via dynamically screened photon field

Angle-resolved photoemission spectra from Na adlayers on Al(111) reveal features which behave like quantum well resonances although the substrate provides no confining barrier. These features are observed in a narrow photon energy range where overlayer collective excitations cause resonant enhancement of the photoemission intensity. The quantum well behavior is shown to be due to surface resonances of the Na/Al system. The resonances are observable using photoemission because of spatial confinement and dynamical enhancement of the local electric field within the Na films.     

Modeling and experimental studies on combustion characteristics of porous coal char: Volume reaction model

A generalized single‐particle model for the prediction of combustion dynamics of a porous coal char in a fluidized bed is analyzed in the present work using a volume reaction model (VRM). A fully transient nonisothermal model involving both heterogeneous and homogeneous chemical reactions, multicomponent mass transfer, heat transfer with intraparticle resistances, as well as char structure evolution is developed. The model takes into account convection and diffusion inside the particle pores, as well as in the boundary layer. By addressing the Stefan flow originated due to nonequimolar mass transfer and chemical reactions, this work enables a more realistic analysis of the combustion process. The model, characterized by a set of partial differential equations coupled with nonlinear boundary conditions, is solved numerically using the implicit finite volume method (FVM) with a FORTRAN code developed in‐house. The use of a FVM for solving such an elaborate char combustion model, based on the VRM, was not reported earlier. Experiments consisting of fluidized‐bed combustion of a single char particle were carried out to determine the internal surface area of a partially burned char particle and to enable model validation. Predicted results are found to compare well with the reported experimental results for porous coal char combustion. The effects of various parameters (i.e., bulk temperature and initial particle radius) are examined on the dynamics of combustion of coal char. The phenomena of ignition and extinction are also investigated. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 299–315, 2010     

A novel synthetic approach towards N-phenylsuccinimides from γ-lactam-2-carboxylic acid derivatives by reaction with CAN-NaBrO3

N-Arylsuccinimides have been synthesized by decarboxylative oxidation of N-aryl-γ-lactam-2-carboxylic acids with the dual oxidant CAN/NaBrO₃ in refluxing acetonitrile-water.     

An Anthracene-Based Metal-Organic Framework for Selective Photo-Reduction of Carbon Dioxide to Formic Acid Coupled with Water Oxidation

A Zr-based metal-organic framework has been synthesized and employed as a catalyst for photochemical carbon dioxide reduction coupled with water oxidation. The catalyst shows significant carbon dioxide reduction property with concomitant water oxidation. The catalyst has broad visible light as well as UV light absorption property, which is further confirmed from electronic absorption spectroscopy. Formic acid was the only reduced product from carbon dioxide with a turn-over frequency (TOF) of 0.69 h⁻¹ in addition to oxygen, which was produced with a TOF of 0.54 h⁻¹. No external photosensitizer is used and the ligand itself acts as the light harvester. The efficient and selective photochemical carbon dioxide reduction to formic acid with concomitant water oxidation using Zr-based MOF as catalyst is thus demonstrated here.     

Ligand-assisted, copper-catalyzed enantioselective benzylic amination

Several classes of ligands, including α-amino acids, diamines, diphosphines, bis-oxazolines, and diimines, support efficient copper-catalyzed amination of benzylic hydrocarbons by anhydrous chloramine-T. Catalysts derived from homochiral ligands, particularly chiral diimines, effect aminosulfonation with low to moderate enantioselectivity.     

Mixed-ligand complex formation equilibria of CuII with biguanide in presence of glycine as the auxiliary ligand

Equilibrium study on the mixed ligand complex formation of Cu^II with biguanide(Bg) and glycine (HG), indicated the formation of the complexes: Cu(Bg)²⁺, Cu(Bg) ₂ ²⁺ , Cu(Bg-H)(Bg)+, Cu(Bg-H)₂, Cu(Bg)(OH)⁺, Cu(Bg-H)(OH); Cu(G)⁺, Cu(G)(OH), Cu(G)₂; Cu(G)(Bg)⁺, Cu(G)(Bg-H); (G)Cu(Bg)Cu(G)²⁺, (G)Cu(Bg-H)Cu(G)⁺, and (G)Cu(Bg-2H)Cu(G). From the deprotonation constants of coordinated biguanide (Bg) in the complexes Cu(Bg)(OH)⁺, Cu(Bg-H)(Bg)⁺ and Cu(G)(Bg)⁺, the Lewis basicities of the coordinated ligand species (Bg-H)^-, OH^- and glycinate (G^-) were found to be of the order: (Bg-H)^-≫ OH^- > G^-. Bridging (N¹-N⁴, N²-N⁵) tetradentate mode of coordination by biguanide species Bg, (Bg-H)^- and (Bg2H)^2- was indicated from the occurrence of biguanide-bridged dinuclear mixed ligand complexes (G)Cu(Bg)Cu(G)²⁺, (G)Cu(Bg-H)Cu(G)⁺, (G)Cu(Bg-2H)Cu(G) in the complexation equilibria.     

Formation of ⊥c texture of tungsten disulfide thin films with nickel

The formation of ⊥c texture of WS₂ thin films by solid state reaction between the spray deposited WO₃ and gaseous sulfur vapours with Ni interfacial layer has been reported. X-ray diffraction technique has been used to measure the degree of preferred orientation and texture of WS₂ films. Scanning electron microscopy, transmission electron microscopy and atomic force microscopy have been used to characterize the microstructure and morphology. The electronic structure and chemical composition was studied using X-ray photoelectron spectroscopy. The WS₂ films comprise single crystalline quality hexagonal crystallites of 15 μm × 15 μm size with their basal planes parallel to the substrate. The film consists of turbostratic stacking sequence of 2H and 3R polytypes of WS₂. The tungsten-to-sulfur ratio was estimated to be 1:1.8. The various qualitative models used to explain promotional effects are briefly outlined and the plausible underlying mechanism of formation of ⊥c texture with nickel, in this study, is given.     

Rate coefficients for the reaction of OH with HONO between 298 and 373 K

Rate coefficients, k₁, for the reaction OH + HONO → H₂O + NO₂, have been measured over the temperature range 298 to 373 K. The OH radicals were produced by 266 nm laser photolysis of O₃ in the presence of a large excess of H₂O vapor. The temporal profiles of OH were measured under pseudo-first-order conditions, in an excess of HONO, using time resolved laser induced fluorescence. The measured rate coefficient exhibits a slight negative temperature dependence, with k₁ = (2.8 ± 1.3) × 10^?12 exp((260 ± 140)/T) cm³ molecule^?1 s^?1. The measured values of k₁ are compared with previous determinations and the atmospheric implications of our findings are discussed.     

Simulation of electron solid interactions in NbC and NbN using Monte Carlo method

A computer program has been developed using Rutherford’s Screened Scattering Model and Energy loss model due to Bethe and applied to simulate the electron interaction pattern in the sample of NbC and NbN with a resist layer of PMMA (Polymethyl Methylacrylate). Using the program we have studied the extent of penetration, lateral spread for different electron energies and the degree of electron back scattering. It has been found that backscattering and lateral spread is more in case of NbC than in NbN signifying hard, refractory and ceramic properties of NbC.