Substituent effects in eight-electron electrocyclic reactions

The main features of transition structures associated with eight-electron electrocyclic reactions have been studied with Density Functional Theory. It is found that conrotatory electrocyclization reaction of (3Z,5Z)-octa-1,3,5,7-tetraenes takes place via M?bius aromatic transition structures of helical conformation. The reaction is completely periselective. In general, transition structures having outward substituents are preferred with respect to the inward transition structures, irrespective of the pi-donor or pi-acceptor character of the substituent. In contrast with four-electron thermal conrotatory electrocyclic reactions, there is no satisfactory correlation between the difference in energy of activation between inward and outward substituents and the Taft resonance sigma(R) parameter.     

Conformational mobility of thianthrene-5-oxide

[reaction: see text] Data on the apparent dipole moment of thianthrene-5-oxide (1) and (1)H NMR spectra in different solvents support the conformational mobility of 1, which flaps between two limit boat conformations with the sulfinyl group in pseudoequatorial and pseudoaxial positions, respectively. The conformational equilibrium of 1 occurs too fast for the (1)H NMR (500 MHz) time-scale even at -130 degrees C, and the equilibrium constant has not been determined. The apparent dipole moments of 1 in n-hexane and 1,4-dioxane and the (1)H NMR spectra of 1 and the model compounds cis- and trans-thianthrene-5,10-dioxides (2) and thianthrene (5) in different solvents and at various temperatures confirm that the relative position of the conformational equilibrium of 1 is solvent-dependent, and more polar solvents favor the conformation with the sulfoxide group in the pseudoaxial position (1(')(ax)). Variable-temperature (1)H NMR spectra have established the interconversion barrier of trans-2 and confirmed that the conformational equilibrium of cis-2 is strongly displaced toward the conformation with both sulfinyl groups in the pseudoequatorial position. The (1)H NMR data support the transannular interaction of the functional groups in 1 and trans-2.     

Determination of imazalil by on-line coupled capillary isotachophoresis with capillary zone electrophoresis

A simple, rapid and reproducible capillary isotachophoretic on-line coupled with capillary zone electrophoresis (CITP-CZE) method for the determination of IMz in food packaging extracts and its residues in apples is described. A good separation of the IMZ from other sample constituents was achieved within 15 minutes without any sample clean up. Method characteristics (linearity, accuracy, intra-assay and detection limit) were determined. Less amount of time involved, sufficient sensitivity and low running cost are the important attributes of CITP-CZE method.     

Kinetic Determination of Microquantities of Rutin by Perturbation of the Bray-Liebhafsky Oscillatory Reaction in an Open System

A kinetic method is described for the microquantitative (microconcentration/microvolume) determination of rutin based on potentiometric monitoring of the concentration perturbations of the Bray-Liebhafsky (BL) oscillatory reaction being in a non-equilibrium stationary state close to a bifurcation point. The experiments are carried out in an open reactor. The response of the matrix system to perturbations by different concentrations of rutin ethanolic solutions is followed by a Pt-electrode. In the concentration range between 7.8×10^–8moldm^–3 and 9.1×10^–6mol dm^–3, we found a linear dependence of the maximal potential shift, E_m, on the logarithm of the rutin concentrations. The unknown concentrations can be determined from the calibration curve up to an accuracy of ±5%. The detection limit is 3.6×10^–8mol dm^–3. The amount of required sample can be as small as 10µL.     

Lanthanide nitrate complexes with 2-azacyclononanone

Thermal behavior of rare earth nitrate complexes with 2-azacyclononanone (AZA) with Ln(NO₃)₃·3(AZA) composition (where Ln=Gd, Er and Ho) was analyzed in kinetic point of view. Kinetic parameters were calculated from thermogravimetric data. All obtained results were similar. The first decomposition step was representative to the loss of ligand and the residue was essentially Ln₂O₃. Furthermore, a reaction path was proposed for the thermal decomposition of the Ln(NO₃)₃·3(AZA).     

Elastic scattering cross sections for 160<Superscript>°</Superscript> and 170<Superscript>°</Superscript>backscattering of 1.40-2.64 MeV protons from natural vanadium

Summary The elastic scattering cross sections of natural vanadium for protons have been measured for beam energies below 2.64 MeV in steps of 10 keV and in the angular 160° and 170°. The overall standard error (Δσ_Exp/σ_Exp) in the measured cross sections is estimated to be better than ±3% at all the beam energies and angles. The results are presented in graphical and tabular forms that should be useful for those who wish to use the cross sections for material analysis.     

Energy Recovery from Municipal Solid Waste in Small Communities

The heating values of municipal solid waste generated in three towns with a population of less than 50 000, situated in Galicia (Spain), were measured with a static bomb calorimeter. Samples of raw refuse were burnt either as received or after sorting of the different combustible components. A study was made of samples from controlled and uncontrolled landfills. The calorific values were compared with those corresponding to a commercial residual derived fuel in order to study the possibility of using municipal solid waste as a source of recovered energy. This revised version was published online in July 2006 with corrections to the Cover Date.     

Inexpensive device for measurements with ion-selective and pH electrodes

The design and construction of a simple device for measuring ionic concentrations (or pH) with ion-selective electrodes are described. The automated system includes a special electronic circuit with an operational amplifier, a signal conditioner and a personalcomputer. A digital multimeter can be used if automation is not required. The results obtained in tests with iodide-, chloride- and nitrate-selective electrodes and glass electrodes show very good agreement with those obtained with sophisticated commercial apparatus.     

Extraction and spectrophotometric determination of titanium(IV) with alizarin and fluoride

The characteristics of the mixed-ligand titanium(IV)-fluoride-alizarin complex, including the optimum conditions of formation and extraction into methyl isobutyl ketone, are described. A simple and sensitive procedure for spectrophotometric determination of titanium has been developed. At pH 9.5-10.3 titanium reacts with alizarin in the presence of fluoride to form a red-violet complex that is completely extractable into methyl isobutyl ketone, and has its absorption maximum at 513 nm. The molar absorptivity at 513 nm is 7.0 x 10(4)l.mole(-1).cm(-1). Beer's law is obeyed up to 22 mug of titanium in 30 ml of solution. The method has been used for the determination of titanium in an oxide mixture and aluminium alloy samples.     

Labelling of organotin compounds for fluorimetric detection

A systematic study of the fluorescence of complexes of some flavone derivatives with organotin compounds in hexane and in an aqueous micellar medium on Triton X-100 is reported. Some relationships between fluorescence intensity and the structure of the fluorogenic reagent or that of the organotin compound can be deduced, and the most suitable reagent for each organotin species can be chosen on the basis of sensitivity and selectivity. Results point out that flavone derivatives are appropriate post-column derivatization reagents for organotin compounds in liquid chromatography.