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.     

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.     

Atomistic packing models for experimentally investigated swelling states induced by CO2 in glassy polysulfone and poly(ether sulfone)

Atomistic packing models have been created, which help to better understand the experimentally observed swelling behavior of glassy polysulfone and poly (ether sulfone), under CO₂ gas pressures up to 50 bar at 308 K. The experimental characterization includes the measurement of the time‐dependent volume dilation of the polymer samples after a pressure step and the determination of the corresponding gas concentrations by gravimetric gas‐sorption measurements. The models obtained by force‐field‐based molecular mechanics and molecular dynamics methods allow a detailed atomistic analysis of representative swelling states of polymer/gas systems, with respect to the dilation of the matrix. Also, changes of free volume distribution and backbone mobility are accessible. The behavior of gas molecules in unswollen and swollen polymer matrices is characterized in terms of sorption, diffusion, and plasticization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1874–1897, 2006     

Orientational ordering of liquid crystals containing a difluoro-substituted phenyl ring

The orientational ordering of several liquid crystals containing a difluorosubstituted phenyl ring has been studied through the use of C-13 NMR. The fluorinated phenyl ring of these liquid crystals have C_s symmetry, so three order parameters are required to completely describe the ordering of this ring. All three of these order parameters have been calculated from carbon-fluorine dipolar coupling constants obtained from the carbon-fluorine splittings in the C-13 NMR spectra. Because of the complexity of the fluorine-coupled spectra, variable angle spinning (VAS) was used to resolve the carbon-fluorine splittings. In order to study the orientational ordering over wide ranges of temperature, we have developed an empirical correlation between the order parameter and the value of a carbon-fluorine dipolar coupling constant. This enabled us to study the change in the order parameter with temperature. The results of applying this method to several structurally similar liquid crystals containing the same type of difluorinated phenyl ring are presented. A comparison is made to a similar mono-fluorinated liquid crystal.     

New reals: Can live with them,can live without them

We give a self‐contained proof of the preservation theorem for proper countable support iterations known as “tools‐preservation”, “Case A” or “first preservation theorem” in the literature. We do not assume that the forcings add reals. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)