Matrix effects in the determination of butyltin compounds in environmental samples by GC AA after hydride generation

Experiments for the determination of mono-, di and tri-butyltin (MBT, DBT and TBT) by hydride generation/gas chromatography/atomic absorption spectrometry in various matrices (sediment, suspended matter, mussel, algae and water) have revealed that poor butyltin recoveries are obtained in sediments displaying high sulphur and hydrocarbon contents; very poor recoveries were also observed for TBT in sediments with high chlorophyll pigment contents as well as in algal samples. It was however not clear whether the hydride generatin was inhibited by these infering compounds, as was previously assumed in the case of hydrocarbons, or whether interferences affected the atomization rate. Further studies were performed to solve this problem in order to validate this method in the case of analyses of, for example, oil-contaminated sediment and algae. This paper presents the results obtained. It is concluded here that the poor recoveries were due to an inhibition of hydride generation rather than to interference at the atomization stage.     

TLC-screening of important pharmaceutical substances using fluorescence detection

Summary Observation of fluorescence reactions on TLC plates is a valuable additional tool within the scope of screening procedures for many toxicologically relevant substances commonly encountered in clinical- and forensic-toxicological analysis. The reactions are based on native fluorescence without any treatment and on reactions obtained with an approved derivatization procedure. Due to the enormous sensitivity of the fluorescence detection, the method is also applicable to very low concentrations and small amounts of biological materials. The procedures described in this article have proven their high pragmatic usefulness in many practical cases.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Structure of thin block copolymer films studied by X-ray reflectivity

Summary X-ray reflectivity may be used to determine the internal structure of thin polymer films. An electron density difference of 10% for polystyrene and polyisoprene is sufficient to distinguish between a random distribution of lamellae, complete orientation parallel to the substrate surface and a surface induced formation of lamellae. The disappearance of the lamellar Bragg-peaks, with heating of the film, shows the transition into the disordered state.     

X-ray diffraction study of 'side-on fixed' homopolysiloxanes from nematic to smectic C phases

The X-ray patterns for the nematic phase in a series of side-on fixed polysiloxanes show different kinds of diffuse elements which imply complex short range ordering. A systematic structural study of the evolution of the patterns versus two molecular parameters, namely the spacer length and the length of the terminal aliphatic tails, suggests the possible occurrence of a smectic C phase for certain values of these parameters. Taking into account these tendencies, new synthesis led to a nematic-smectic C polymorphism observed for the first time in side-on fixed polysiloxanes.     

Molecular electric field mapping of some anions and cations of 2- aminopurine and 6- thioguanine

Electric fields of the anions, cations and neutral forms of 2-aminopurine and 6-thioguanine have been mapped. Certain important features of the maps are similar to those found earlier in the neutral and ionic forms of adenine and guanine. The computed electric field patterns satisfactorily explain reactive sites and biological activity of the molecules.     

Branched chain discotics Phase structure and orientation behaviour

Studies show that branching the side chains of hexakis(acoyloxy)-benzenes (HAB) and -cyclohexanes (HAChx) does not modify the structure of the discotic mesophase formed. Shear fields appear to act on entire columns, not on individual discs, thereby causing alignment of columns in the shear direction. X-ray diffraction patterns of samples at temperatures between 30°C and 40°C above the clearing temperature provide evidence for the presence of mesophase order.     

On the Causes and Effects of Contaminations during rf Diode Deposition of Cr-Si Alloys

Investigations to the causes and effects of contaminants at the rf diode deposition of CrSi films in a non-heated high vacuum apparatus were carried out comparing an oxygen-free fusion target with an oxygen-containing cermet target. The films of the fusion target contained considerable amounts of oxygen; analogously the oxygen concentration in the films was increased in the case of the cermet target. Moreover, hydrogen was found. The concentration of the contaminants decreased with the sputtering power, however the rate of incorporation increased. For high sputtering rates the contamination process was reproducible and independent of the plant conditioning; the deposited films were depth-homogeneous. The reasons for this behaviour lie in water sources which are activated first of all by the discharge itself. The electrical properties found are explained by the contaminants and the deposition conditions.     

A shock tube study of the reaction of methyl radicals with hydroxyl radicals

The reaction of CH₃ with OH has been studied near 1200 K and 1 atmosphere pressure in shock tube experiments in which UV absorption was used to monitor [OH]. A rate coefficient of (1.1 ± 0.3) × 10¹³ cm³/mol-s was measured for removal of OH by CH₃. This measured value is compared with previous experimental data and calculations. Several possible reaction channels are discussed, and although products were not monitored, it seems probable, on the basis of other work and theoretical estimates, that the primary mechanism (?75%) for the removal of OH by CH₃ at these conditions is their combination to form CH₃OH. Rate coefficients of (5.3 ± 0.8) × 10¹² and (9.0 ± 1.4) × 10¹² cm³/mol-s were measured for the reactions of OH with acetone and ethane, respectively, at the same temperature and pressure.     

The liquid-crystalline behaviour of amphiphilic ethane-1,2-diol derivatives incorporating a six membered ring in their principal structure

Novel 3-phenyloxy substituted propane-1,2-diol derivatives, 4-(4-n-hexyloxyphenyl)-butane-1,2-diol and 4-(trans-4-n-pyropylcyclohexyl)-butane-1,2-diol have been synthesized and their thermal behaviour has been studied. These compounds exhibit thermotropic and, after addition of water, also lyotropic liquid-crystalline behaviour. The clearing temperatures of the smectic mesophases were found to be strongly dependent on the alkyl chain length and on the structural units that link the aromatic ring to the alkyl chain and to the diol unit. The behaviour of the aromatic compounds is compared with that of the cyclohexane derivative. Thereby it has been realized that the mesophase stability of the amphiphilic diols incorporating a rigid unit is largely determined by both, the molecular geometry (molecular shape and intramolecular flexibility) and the amphiphilic structural pattern.