The electronic gas-phase spectrum of B3 radical revisited

The gas-phase electronic spectrum of cyclic-B₃ (D_3h) radical has been remeasured in a supersonic molecular beam using a mass-selective resonant 2-color 2-photon technique, leading to a revision of previously reported spectroscopic constants. The species was prepared by ablation of a boron nitride rod in the presence of helium. Ab intio calculations on the geometries and vertical electronic excitation energies, as well as mass identification, indicate that the detected band, centered at 21848.77(2) cm⁻¹, is the origin of the cyclic-¹¹B₃ system. A spectral fit yields the rotational constants as B″ = 1.2246(45) and C″ = 0.62131(72) cm⁻¹ in the ground state, and B′ = 1.1914(44) and C′ = 0.61173(69) cm⁻¹ in the excited 2 ²E′ state.     

Varying the metal/metal ratio in related Cu–Ca complexes

We demonstrate with the help of structural determinations and spectroscopic data that the nuclearity of Cu–Ca complexes derived from compartmental Schiff base ligands does not depend on the ionic radius of calcium. The main factors governing these reactions are the different affinities of the calcium ions for the anionic species present in solution: the tetradentate O₂O₂ coordination site of the ligand and the nitrato ions. Because these affinities do vary upon going from calcium to lanthanide ions, it is not possible to use the template effect of the trinuclear Cu–Ca–Cu complexes in order to prepare the corresponding Cu–Ln–Cu complexes.     

Effect of surfactant and mineral additive on the efficiency of lead-acid battery positive active material

The effect of Sodium tripolyphosphate (STPP) and mineral additive on the performance of the lead-acid battery positive plate has been investigated. The addition of alumina-silicate to the positive paste and STPP to the electrolyte modifies the shape and size of PbO₂ crystals and improves the utilization of the positive active material (PAM). The electrochemical performance of the positive active material was determined using galvanostatic discharge and electrochemical impedance spectroscopy (EIS). The crystal structure and morphology of the PAM (PbO₂) were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The water content of the PAM was calculated using Thermogravimetric analysis (TGA) technique. The results showed that the addition of surfactant and mineral additive changes the morphology and the crystallite size of the PAM. We observe a remarkable improvement of the discharge capacity of the PAM when the surfactant (STPP) is added in the electrolyte. The discharge capacity increases with the decrease of the crystallite size and the charge transfer resistance R_ct of the PAM. This shows that the addition of mineral additive and the surfactant together improves the electrical performance of lead-acid battery.     

Production of l-menthyl acetate through kinetic resolution by Candida cylindracea lipase: effects of alkaloids as additives

Research on Chemical Intermediates - Enzymatic transesterification of dl-menthol with vinyl acetate in tert-Butyl methyl ether (TBME) catalyzed by Candida cylindracea lipase (CCL) was carried out...     

Kinetics and Equilibrium Swelling Properties of Hydrophilic Polymethacrylate Networks

Summary: Hydrogels were synthesized by polymerization of 2-Hydroxy ethylmethacrylate (HEMA) in the presence of ethyleneglycoldimethacrylate (EGDMA) as a crosslinking agent. Structural information and thermophysical properties of the hydrogels were analyzed using Fourier-Transform Infrared spectroscopy, thermogravimetrical analysis, and differential scanning calorimetry. The swelling behaviour of the obtained chemically crosslinked P(HEMA-EGDMA) networks in aqueous solution was investigated as a function of the pH value and concentration of crosslinking agent. Plateau values were found at equilibrium swelling for a low pH value after one day swelling, whereas increasing water uptake was obtained for pH = 6.32 even at swelling times of more than five days. For short swelling times, a linear relationship between swelling ratio and time was found. Experimental data were rationalized using Fick's second law of diffusion. For early and moderate times of diffusion, threshold values were found in all cases considered here, indicating a Fickian behaviour below and a non-Fickian diffusion mechanism above the threshold.     

Distances between elements of a semigroup and estimates for derivatives

This paper is concerned first with the behaviour of differences T（t） - T（s） near the origin, where （T（t）） is a semigroup of operators on a Banach space, defined either on the positive real line or a sector in the right half-plane （in which case it is assumed analytic）. For the non-quasinilpotent case extensions of results in the published literature are provided, with best possible constants; in the case of quasinilpotent semigroups on the half-plane, it is shown that, in general, differences such as T（t） -T（2t） have norm approaching 2 near the origin. The techniques given enable one to derive estimates of other functions of the generator of the semigroup; in particular, conditions are given on the derivatives near the origin to guarantee that the semigroup generates a unital algebra and has bounded generator.     

Fabrication and characterization of nanocrystalline Al,Co:ZnO thin films by a sol–gel dip coating

The consequence of annealing on the micro-structural and electrochemical characteristics of Al doped CoZnO thin films deposited by sol–gel dip coating technique are studied. X-ray diffraction indicates that films have a hexagonal wurtzite structure oriented towards the (100). Optical properties of films are recorded by transmission curves utilising a UV–VIS spectrophotometer. The investigation of the optical transmission spectra indicates that the band gap of the films decrease from 3.99 eV to minimum 3.83 eV upon annealing. All films show room temperature ferromagnetism whose magnetization increases with annealing. Dip coated films possess polycrystalline nanosized grains with porous morphology.     

Synthesis,characterization and self-assembly of amphiphilic block copolymer poly(4-vinyl benzene chloride)-b-poly(N-vinylpyrrolidone) in aqueous solution

The synthesis, characterization and self-assembly of a novel amphiphilic block copolymer containing a poly(N-vinylpyrrolidone) as a segment of hydrophilic and poly(4-vinyl benzene chloride) (PVBC) arms are reported. The copolymer was characterized by FT-IR spectroscopy ¹H NMR. The composition and the molecular weights of the block copolymers were established using gel permeation chromatography and ¹H NMR. The water-soluble fraction of poly(N-vinyl-2-pyrrolidone) (PVP)/PVBC block copolymers formed micelles which were investigated at 25 °C in water at 5 mg/ml concentration using a tensiometer. The morphology of micelles in aqueous solution was determined by the AFM, SANS, and SAXS methods.     

A new technique to characterize mono-molecular micelles in random ethylene–propylene copolymers

A new technique to investigate the nano-structure of ethylene–propylene (EP) random copolymers has been developed. It consists in the measurement of the turbidity which develops at a lower critical solution temperature (LCST) in pentane solutions. The information on the solution comes from different types of turbidity obtained during a step-by-step temperature increase. The transient turbidity (h_i) is associated with random coils (I) and structured coils (II) while the stable turbidity comes from aggregates (III). The proportion of (I), (II) and (III) depends on the solution history and on the solvent. The M_w distribution can be obtained from the set h_i (T_i) of (I). Turbidity (II) has an unexpected gap in the h_i (T_i) trace. The gap (10–20 K) is explained by the presence of two entities in solution. Their temperatures of phase separation permit their identification as monomolecular micelles, whose outer core is either E-rich or P-rich. This nano-structure is thought to exist in the solid and also in solution as a metastable state. The technique can differentiate between mobile chains in solutions (I, II) and attached chains in a network (III) through the sedimentation behaviour of the concentrated phase. Three samples with a similar (EP) content (0.75) made with different catalysts have been analysed by LCST and slow calorimetry.