Alcaloides steroidiques—CLXVII : Synthese d'azides tertiaires en serie alicyclique—III

Treatment of steroidal tertiary alcohols or olefins with N₃H/BF₃—éthérate/benzene gave 5-azido, 13-azido and 14-azido steroids. Reaction mechanism has been discussed. Chemical degradation and ¹³C NMR study confirmed structural assignments.     

Dipole strengths in the chlorophylls

Measurements of dipole strengths of chlorophylls in solution are reviewed and correlated. The refractive index dependence is found to be expressible in a simple empirical fashion that does not rely on the concept of vacuum dipole strength. The index dependence in some respects contradicts the dependence expected on the basis of effective field theories.     

A comparative potentiostatic study of the electrocrystallization of PbO2 on platinum and glassy carbon electrodes

The deposition of PbO₂ on platinum and glassy carbon electrodes was investigated experimentally. The comparison of the different behaviour on the two types of electrodes is presented. The effects of variation of temperature, potential, nucleation order and induction time-lags on the electrocrystallisation process are discussed.The present investigations have confirmed that electrocrystallisation of PbO₂ occurs through 3-D nucleation and growth on glassy carbon and most probably also on platinum. The data on platinum contains considerable noise from simultaneous chemical processes and is not amenable for analysis in a simple way. The steady state behaviour is unusual because it has generally been assumed that charge transfer is rate determining under most conditions. However, as shown here, if lattice incorporation is slow even at the steady state, it provides a method for separating the activation energies associated with the nucleation and growth rate constants. Finally, the dissolution of PbO₂ into the platinum substrate and its implication on transient rates merits more attention. In this context the Pt-PbO₂ system is probably not a good choice because of the large contribution of substrate oxidation to the measured transient rates.     

Luminescence centers in porous silicon

Photoluminescence studies on porous silicon show that there are luminescence centers present in the surface states. By taking photoluminescence spectra of porous silicon with respect to temperature, a distinct peak can be observed in the temperature range 100–150 K. Both linear and nonlinear relationships were observed between excitation laser power and the photoluminescence intensity within this temperature range. In addition, there was a tendency for the photoluminescence peak to red shift at low temperature as well as at low excitation power. This is interpreted as indicating that the lower energy transition becomes dominant at low temperature and excitation power. The presence of these luminescence centers can be explained in terms of porous silicon as a mixture of silicon clusters and wires in which quantum confinement along with surface passivation would cause a mixing of andX band structure between the surface states and the bulk. This mixing would allow the formation of luminescence centers.     

The limit of detection in transversal photothermal deflection spectroscopy with light scattering samples

The limit of detection for the 4,6 dinitro-orthocresol (DNOC) pesticide, including small latex particles as light scattering samples in water as suspending medium, has been determined for the transversal photothermal deflection technique. The results where compared to conventional spectrophotometry. In the photothermal deflection experiments performed with a continuous Ar⁺-excitation beam (=363.8 nm) a LOD of 0.8 g/l is achieved for the DNOC in water.Awarded poster prize     

The effects of media properties on the horseradish peroxidase-catalyzed fluorogenic reaction

The effects of media properties including buffers, acidity, solvents and surfactant on horseradish peroxidase-catalyzed fluorogenic reaction were investigated. The results showed that the so-called non-fluorescent hydrogen donors were in fact fluorescent. There existed an acid—base equilibrium in the fluorescent dimer product. For p -hydroxyphenylpropionic acid, a pK_a value of 8.0 for the product was obtained from its titration curve. The product fluorescence increased with higher pH, however, a longer time was needed to reach the reaction equilibrium due to the pH mismatch problem. Cationic micelles cetyltrimethylammonium bromide and cetyltrimethylammonium chloride could reduce the pH mismatch and offered a way to further increase the determination sensitivity. Finally, a micelle-enhanced flow-injection analysis of horseradish peroxidase is suggested.     

Study of occupational health impact of atmospheric pollution on exposed workers at an iron and steel complex by using neutron activation analysis of scalp hair

The occupational health impact of atmospheric pollution on exposed workers at one iron and steel complex was studied by instrumental neutron activation analysis of workers' hair samples and medical examination. The experimental results indicate that there is a positive correlation between the high inhalation amounts of iron and other trace elements by the exposed workers and the symptom of their high blood pressure and hypoglycemia, which implies that the atmospheric environment polluted by iron and steel industry has an adverse health impact on the exposed workers. The measures to relieve and abate the occupational diseases caused by air-borne particulate matter should be taken     

Measurement of the Compton profiles of CH4 and C2H4 by high energy electron impact spectroscopy

We present a new experimental determination of the Compton profiles of CH₄ and C₂H₄ molecules using high energy electron impact. The observable q range has been extended up to 10 au (6 au for C₂H₄). Good agreement is found with an earlier X-ray scattering experiment and with new theoretical calculations.     

Flow injection spectrofluorimetric determination of reserpine in tablets by on-line acetone sensitized photochemical reaction

On-line photochemical reaction of reserpine in the presence of acetone was investigated. Acetone was found to speed up the on-line photochemical conversion of reserpine into an intensively fluorescent compound. Not only reaction acidity but also the acetate buffer concentration affected the on-line photochemical induced fluorescence signal. Based on the observation an automated flow injection photochemical fluorimetric approach was developed. An injected sample zone was carried by a water stream to be merged with a acetate buffer (pH 3.4) solution containing 0.02% acetone in a knotted PTFE reactor (KR), which was freely coiled around a 6-W low pressure mercury lamp. While passing the KR, reserpine was transformed into an intensively fluorescent compound. It was on-line detected in a flow-through cell at the emission wavelength of 490 nm and excitation wavelength of 386 nm. At optimized conditions, a detection limit 0.45 mug l(-1) was achieved at a sampling rate of 90 h(-1). Eleven determinations of a 0.5 mg l(-1) reserpine standard solution gave a R.S.D. of 0.3%. The linear dynamic range of reserpine calibration curve was 0.01-0.75 mg l(-1). The proposed method was applied to assay the reserpine content in tablets and to monitor the dissolution profile of reserpine tablets. Satisfactory results were obtained for both the assays and dissolution studies.