Birefringence induite dans les directions remarquables d'une suspension de particules rigides en ecoulement

A theoretical formula is derived for the flow birefringence exhibited along the streamlines and in the direction of the shear rate (G) by dilute suspensions of rigid spheroid-like macromolecules; numerical values are computed up to σ = G/D = 900 (D = rotary diffusion coefficient). These results provide two tests for identifying prolate and oblate particles; when combined with the data for observation perpendicular to the plane of flow, they confirm the connection between non-Newtonian viscosity and the Maxwell effect for monodisperse samples; for vanishing rate of shear, they allow a mixture of particles to be characterized by means of a mean rotary diffusion constant ($\text{D}$) and a mean shape coefficient ($\text{R}$).     

Wang resin-type linker containing a nitro group for polymer support oligosaccharide synthesis: polymer-supported glycosyl donor

A nitro-introduced Wang resin-type linker for soluble and insoluble polymer support oligosaccharide synthesis is described. The linker was used for connecting glycosyl donors and polymer supports, and was completely stable under the glycosylation conditions tested. The cleavage of the linker was performed under reductive conditions without affecting the protecting groups to release disaccharides.     

Segregation of two amphiphilic molecules within nonspherical micelles: A neutron scattering study

The internal structure of the disk-like aggregate of a lyotropic nematic phase formed by two amphiphiles, potassium laurate and decanol, in the presence of water was studied by neutron scattering with contrast variation method. These experiments show that the two amphiphiles are not distributed uniformly in the aggregate. The potassium laurate concentration is higher in the rim of the disk, where the interface exhibits a semitoroidal curvature, than in its central core, where the curvature is lower. This segregation of the two amphiphiles within the aggregate may be invoked to explain the existence of finite bilayered aggregates which had been suggested to be unstable relative to infinite bilayers by previous models.     

Assay for monoamine oxidases A and B by high-performance liquid chromatography with fluorescence detection

A sensitive method for the assay of monoamine oxidases A and B is described which employs high-performance liquid chromatography with fluorescence detection. Rat brain mitochondria were used as a preparation of the enzymes. p-Sulfamoylbenzaldehyde and benzaldehyde formed enzymatically from p-sulfamoylbenzylamine (the substrate of monoamine oxidase A) and benzylamine (the substrate of monoamine oxidase B), respectively, are converted simultaneously into fluorescent compounds with 2,2'-dithiobis(1-aminonaphthalene). These compounds are separated by reversed-phase chromatography on mu Bondapak CN. The limits of detection for p-sulfamoylbenzaldehyde and benzaldehyde formed enzymatically are 30 and 10 pmol per assay tube, respectively.     

Influence of extended π-conjugation units on carrier mobilities in conducting polymers

Carrier mobilities in thin films of copolymers with repeat units consisting of oligothiophenes bridged by Si atoms are measured over a range of doping levels, where the numbers of thienylenes in the repeat unit are 7, 8, 10, 12, and 14. The mobilities for these polymer films increased with the increase in doping level and the mobility enhancement followed an increasing order of the π-conjugation length. The magnitude of the mobility increase for the Si polymer comprising 14 thiophene units reached ca. 10⁴, implying that this π-conjugation length is almost sufficient to reproduce transport properties of polythiophenes.     

Simultaneous determination of cefazolin in rat blood and brain by microdialysis and microbore liquid chromatography

A sensitive microbore liquid chromatographic method combined with the minimally invasive technique of microdialysis was devised for simultaneously and continuously monitoring the levels of unbound blood and brain cefazolin in rats. Microdialysis probes were inserted into the jugular vein and brain striatum for blood and brain sampling, respectively. Chromatographic conditions consisted of a mobile phase of methanol-acetonitrile-100 mM monosodium phosphoric acid (20:10:70, v/v, pH 4.5) pumped through a microbore reversed-phase column at a flow rate of 0.05 mL/min. The ultraviolet detection wavelength was set at 270 nm. An on-line design allowed direct and continuous analysis of protein-free samples in the dialysate. Microdialysis probes, being home-made, were screened for acceptable in vivo recovery. Chromatographic resolution and detection were validated for response linearity as well as intra-day and inter-day variabilities. This method was then applied to pharmacokinetic profiling of protein unbound cefazolin in both the blood and brain following intravenous administration (10 mg/kg, i.v., n = 6). Rapid appearance of cefazolin in the rat brain striatal dialysate following drug injection suggested good blood-brain barrier penetration. According to a non-compartmental pharmacokinetics model, the area under the concentration (AUC) vs time ratio of cefazolin in rat brain and blood was 6%.     

New results on photoion pair formation from application of the velocity imaging photoionisation coincidence technique

The velocity imaging photoionisation coincidence (VIPCO) technique is shown to be a powerful tool for studies of ion pair formation. Sequential mechanisms are demonstrated for some three-body ion pair formation reactions. Observation of a new type of reaction producing one negatively and two positively charged ions plus an electron is reported.     

The effect of gamma-irradiation of anthracite coal and oil bitumen

Anthracite coal and oil bitumen were submitted to γ-radiation at a total dose of 1 MGy and the radiation-processed samples were studied by FT-IR spectroscopy, thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The coal samples were studied also by TGA coupled with FT-IR spectroscopy of the evolved gases. Thermal analysis has revealed a completely different behavior of the radiolyzed samples in comparison to the unirradiated samples. Both for coal and bitumen significantly less volatile fraction was released during the TGA and in both cases a significant increase in the amount of carbon coke produced at 800-900 °C was observed. The radiation processed bitumen increased significantly its ethyl acetate insolubles content. These results were interpreted in terms of extensive crosslinking and coalification of the samples under the action of γ-radiation. The results of this study have been applied to the carbonization process of terrestrial sedimentary organic matter which is commonly attributed to the action of heat flux from the depth of the Earth but which may be also due to the action of natural radiation. Other application of the results of the present study is to the complex organic matter present on the surfaces of comets and meteorites. This complex matter was formed by exposure of simple precursors to a field of high energy radiation for millions or billions of years and is consequently transformed into coal-like and bitumen-like matter. The same arguments apply to the carbon grains present in the interstellar and circumstellar medium. This revised version was published online in July 2006 with corrections to the Cover Date.     

New integrated measurement protocol using capillary electrophoresis instrumentation for the determination of viscosity, conductivity and absorbance of ionic liquid-molecular solvent mixtures

The low vapor pressure and the versatility of the physico-chemical properties of ionic liquids make them really attractive as an alternative for conventional molecular solvents. The knowledge of their physico-chemical properties (viscosity, conductivity, miscibility with organic solvents and anion-cation interactions) has appeared mandatory for better targeting their applications, although it is generally still lacking or incomplete.This work promotes capillary electrophoresis instrumentation as an integrated apparatus for measurement of viscosity, conductivity and absorbance of pure ionic liquids and ionic liquid-molecular solvent mixtures. Compared to current conventional techniques, the assets of this instrumentation for this purpose are the combined availability of a pressure delivery system, power supply, diode array absorbance detector and thermoregulation device, allowing unattended, automatic and easy operation, involving minimum sample handling. Most importantly, the required sample volume can be reduced to about 50 μL, making this protocol very cost-effective. A protocol was optimized with respect to time, sample consumption and data reliability for the determination of these physico-chemical parameters. Ionic liquids selected for method development and validation differed in the nature of their cation (butyl- and ethyl-methylimidazolium) and anion (trifluoromethanesulfonate and bis(trifluoromethanesulfonyl)imide). Various molecular solvents were mixed with these ionic liquids (acetonitrile, methanol, dimethylformamide and trifluoroethanol) and the same physico-chemical properties were determined by optimized methods. The knowledge of these data should be of great support in various application areas, including the development of new separation media for capillary electrophoresis and chromatographic techniques.