Diffusion in ethylene–propylene rubber

A study of sorption in a copolymer of ethylene and propylene is presented. Long-time sorption and desorption measurements provided the actual diffusion coefficient in the limit of zero concentration gradient. An analysis of the diffusion–sorption data reinforced the Frisch hypothesis about diffusion in a polymer matrix. The better solvent deforms the microstructure, allowing a more marked dependence of the diffusivity upon concentration.     

Solvent‐free microwave synthesis of bis‐pyrazolo[3,4‐b:4′,3′‐e]‐pyridines and study of their antifungal properties

The synthesis of a series of bis‐pyrazolo[3,4‐b:4′,3′‐e]pyridines ( 3 ) in the reaction of 5‐amino‐3‐methyl‐1‐phenylpyrazole ( 1 ) with aldehydes ( 2 ) under microwave irradiation and solvent‐free conditions is described. The structure elucidation of the products is based on detailed nmr analysis of experiments such as ¹H‐COSY, NOESY, DEPT, HSQC and HMBC. These compounds showed moderate antifungal in vitro activity against dermatophytes.     

Oxidation of propene over various doped tungsten oxides

The oxidation of propene was studied on several tungsten oxides which contained small amounts of Ti, Ta, Nb and Sn. Only the Sn-containing specimen was found to be selective in the conversion of propene to acrolein. The catalytic results are correlated with crystal structures determined by electron microscopy.

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, Ti, Ta, Nb Sn. , , Sn, . , .

     

Excess Gibbs free energies of mixtures of tetrakis(2-ethylbutoxy)silane + cyclohexane, + benzene,and + carbon tetrachloride at 308.15 K

The excess Gibbs free energies G^E for tetra(2-ethylbutoxy)silane (tkebs) + cyclohexane, + benzene, and + carbon tetrachloride have been measured at 308.15 K with a new vapour-pressure apparatus. For tkebs + cyclohexane, G^E is negative with a minimum value of ?538 J mol^?1 near x₂(tkebs) = 0.39. For tkebs + benzene, the minimum value of G^E is ?453 J mol^?1 near x₂ = 0.41, and for tkebs + carbon tetrachloride, G^E has a minimum value of ?715 J mol^?1 near x₂ = 0.39.     

Absorption of amines on cation exchange resins

All the amines studied are absorbed in excess of the exchange capacity bysulfonated polystyrene resins from aqueous solutions; the absorption is greatest with benzylamine, whose molecular structure is the closest to that of the monomer of the resin. The absorption is greater, then less the crosslinking of the resin, and it is influenced by the electrostatic field of the resin cations. There is no excess absorption from solvents such as alcohols, acetic acid or dioxane. The absorption characteristics of amines are sufficiently different that separations by elution chromatography on cation exchange resins are possible. Two such separations have been demonstrated. For quantitative analytical use, however, it would be wise to use very fine mesh resins on account of the slowness of diffusion of large amine molecules within the resins.     

Photophysical aspects of single-molecule detection by two-photon excitation with consideration of sequential pulsed illumination.

An important goal in single molecule fluorescence correlation spectroscopy is the theoretical simulation of the fluorescence signal stemming from individual molecules and its autocorrelation function. The simulation approaches developed up to now are based exclusively on continuous-wave (cw) illumination and consequently on cw-excitation. However, this approximation is no longer valid in the case of two-photon excitation, for which pulsed illumination is usually employed. We present a novel theoretical model for the simulation of the fluorescence signal of single molecules and its autocorrelation function with consideration of the time dependence of the excitation flux and thus of all illumination-dependent photoprocesses: two-photon excitation, induced emission and photobleaching. Further important characteristics of our approach are the consideration of the dependence of the photobleaching rate on illumination and the low intersystem-crossing rates of the studied coumarins. Moreover, using our approach, we can predict quantitatively the effect of the laser pulse width on the fluorescence signal of a molecule, that is, the contributions of the photobleaching and saturation effects, and thus we can calculate the optimal laser pulse width. The theoretical autocorrelation functions were fitted to the experimental data, and we could ascertain a good agreement between the resulting and the expected parameters. The most important parameter is the photobleaching constant sigma, the cross section of the transition Sn<--S1, which characterises the photostability of the molecules independent of the experimental conditions. Its value is 1.7 x 10(-23) cm2 for coumarin 153 and 5 x 10(-23) cm2 for coumarin 314.     

Reagentless system for sulphite determination based on polyaniline

A new reagentless system for sulphite (or sulphur dioxide) determination is reported based on the use of an organic conducting polymer, polyaniline, and its absorbance variation at 550 nm, depending on the sulphite concentration. After chemical polymerisation of aniline a very thin film of polyaniline is obtained. Although the response is not fully reversible, each film can be used for at least 10 measurements for low analyte concentrations (up to 0.5 mg l⁻¹) and five measurements for higher sulphite concentrations. Moreover, the reproducibility, ease of preparation and low cost of the films, permit the use of a new disposable system for each measurement. When the change in absorbance at 550 nm was measured for 210 s (stabilisation time), the system showed a linear response, which ranged from 0.025 to 1.50 mg l⁻¹ of sulphite. A theory with regard to the reaction mechanism between the polyaniline films and sulphite is also proposed. The system was applied to sulphite determination in wine samples and the results were in agreement with those obtained by the Official Method of Analysis (iodometric titration).     

Synthesis and derivatization of ethynyl alpha,alpha-dibromomethyl ketones: formation of highly functionalized vinyl triflates

[reaction: see text] We describe the synthesis of alpha,alpha-dibromomethyl ynones (8) and their subsequent derivatization to vinyl acetates (10). These vinyl acetates feature a 1,1-dibromo-olefin moiety, which is readily exploited in palladium-catalyzed Sonogashira, Stille, and Suzuki cross-coupling reactions with alkynes, stannanes, and boronic acids, respectively. A novel one-pot process then directly converts the resulting vinyl acetates 11-13 to the vinyl triflate derivatives 14a-j.     

Cloud-point preconcentration of fulvic and humic acids

The cloud-point extraction technique was used for preconcentration of fulvic and humic acids. The effect of the acidity of solution, the equilibration temperature and time, the amount of added surfactant (Triton X-100) and the time of centrifugation on the recovery were examined. The recoveries of fulvic and humic acids achieved under optimised conditions were 82% and 96%, respectively.     

The use of sample additives in flame emission spectrometry

New kinds of sample additives were investigated to increase the efficiencies of desolvation and atomization in flame spectrometry. Hydrazine and nigrosin were chosen as chemical and dye additives, respectively; an enhancement in the flame-emission signal was obtained in both cases. With nigrosin, it was possible to eliminate completely the interference of phosphate on a calcium emission signal. The increase in the signal for both additives was believed initially to be due to the more rapid evaporation of droplets in the sample aerosol. Further evidence, however, suggested that enhanced vaporization is responsible for the observed signal increase. It is suggested that similar sample additives might be useful also in inductively-coupled plasma emission spectrometry.