Relevance of Reflection in Static and Dynamic Light Scattering Experiments

Using a monodisperse PMMA dispersion, it was shown that light reflection at the sample cuvette walls may greatly influence the results of both static (SLS) and dynamic (DLS) light scattering experiments. Considering SLS, this reflection phenomenon mostly causes an overestimation of the scattered intensity at high scattering angles, which may give rise to the emergence of an additional, artificial peak in the lower region of the particle size distribution. On the other hand, the influcence of reflection on DLS measurements was shown to be particularly important in the upper region of the particle size distribution. The experimentally observed phenomena were explained from the basic principles of both particle sizing methods. Finally, it was shown that the disturbing effect of reflection could be avoided by modifying either the hardware or the software of the static and dynamic light scattering technique.     

Hybrid organosilazane/organosilylamine telechelic oligomers—I. Two-dimensional NMR spectroscopy characterization of dimethylsilylethylenediamine oligomers

The detailed characterization of multifunctional hybrid organosilazane/organosilylamine telechelic oligomers by IR and ¹H, ¹³C and ²⁹Si NMR spectroscopy in one and two dimenions has been undertaken. The specific multifunctional oligomers, comprising NH/NH₂ or SiCl functionalities depending on the monomer feed-ratio, were prepared from mono- and di-functionally reacted dichlorodimethylsilane (DDS) and mono-, di-, tri- and tetra-functionally reacted ethylenediamine (EDA). Varying the feed-ratio afforded control of the microstructures of the oligomers and the preparation of oligomers with, in some cases, conterminously located silicon–chlorine (SiCl) groups. The combination of the NMR methods with the IR technique has enabled the detailed microstructural characterization of the oligomers and the identification of the functionalities therein. This approach and the knowledge gained from the DDS/EDA system has been applied to the microstructural characterization of other hybrid organosilazane/silylamine preceramic telechelic oligomers.     

Liquid crystal properties of some substituted pyrazines

A number of biphenyl, terphenyl analogues and ethynes which contain a pyrazine ring have been made and their liquid crystal transition temperatures, together with examples of birefringence measurements, are reported. All the 2,5-disubstituted pyrazine systems are liquid crystalline showing high birefringence values for the biphenyl and terphenyl analogues, whereas the 1,5-disubstituted systems are not liquid crystalline. The pyrazine ethyne systems exhibit very high birefringence values. X-ray diffraction has been used to identify the liquid crystal phases of 2-n-nonyloxy-5-(4'-propylbiphenyl-4-yl)pyrazine.     

Molecular addressing? Studies on light-induced reorientation in liquid-crystalline side chain polymers

Polarized light leads to an effective reorientation of the optic axis in the glassy state of liquid-crystalline side chain polymers containing azobenzene mesogenic groups, via a trans-cis and cis-trans isomerization. Using a combination of U V and IR dichroitic studies it is shown for copolymers consisting of chromophores (azobenzene) and non-chromophores (phenylbenzoate) that only the chromophores are reoriented by light as far as the glassy state is concerned. Individual chromophores are thus addressed by photoselection. Photoselection in the fluid nematic state, on the other hand, leads also to a reorientation of the non-chromophores.     

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.