Radial electric fields and confinement in the TJ-II stellarator

Radial plasma potential profiles have been obtained in the TJ-II by the Heavy Ion Beam Probing (HIBP) diagnostics. Results show that the potential increases up to 1 kV near the magnetic axis in ECRH low-density plasmas. The secondary ion current profiles, which directly reflect the plasma density, are hollow. In low-density ECRH operation, radial electric fields are found to be positive in the plasma core, however, a reduction in these fields is observed with increasing density. Radial plasma potential profiles show evidence of structures in configurations with low-order rational surfaces. In particular, HIBP measurements have permitted characterization of the plasma potential profile during e-ITB formation. Experiments in TJ-II have shown that it is possible to modify the global confinement and edge plasma parameters with limiter biasing, illustrating the direct impact of radial electric fields on confinement properties. Plasma potential measurements by the HIBP diagnostic show a strong impact of heating method (ECRH versus NBI) on radial electric fields.Presented at the Workshop Electric Fields Structures and Relaxation in Edge Plasmas, Nice, France, October 26–27, 2004.     

Liquid-liquid extraction followed by solid-phase extraction for the determination of lipophilic pesticides in beeswax by gas chromatography-electron-capture detection and matrix-matched calibration

Analytical methods for the simultaneous analysis of lindane, chlorpyriphos, z-chlorfenvinphos, endosulfan A and B, 4,4'-DDE, 4,4'-TDE, acrinathrine, bromopropylate, tetradifon, coumaphos and fluvalinate in pure beeswax samples are studied. For the analysis of bleached beeswaxes, a liquid-liquid extraction with acetonitrile followed by a clean-up on polymeric cartridges is the best option in terms of recovery and precision. However, some interferences that hinder the identification and quantification of important varroacides are found when non-bleached beeswaxes are analyzed. The analysis of all compounds in the latter samples require a clean-up by coupling an ODS cartridge before the polymeric cartridge. Considerations about the influence of the matrix in the quantitative analysis by a classical external standard calibration are also made and the use of a matrix-matched calibration is advised. Recoveries resulted to be about 100% with coefficients of variation between 10% and 20% (n = 5) for concentrations of 0.5 and 5 mg/kg.     

Efficient synthesis of enantiomerically pure alpha-alkyl cyclopropanecarbonitrile derivatives from pyrazolines

[reaction: see text] Thermolysis of enantiopure sulfonyl pyrazolines 4 and 5, easily obtained from (Z)-3-p-tolylsulfinylacrylonitriles (1), afforded sulfonyl cyclopropanes (6, 7) in a completely stereoselective manner in almost quantitative yields. Both cyclopropanes and alkylidenecyclopropanes, containing one or two chiral carbon atoms, one of them being quaternary, were obtained by hydrogenolysis of the C-S bonding and under the conditions reported by Julia, respectively. The highly stereoselective extrusion of nitrogen suggests a concerted mechanism.     

Generation of strong, homochiral bases by electrochemical reduction of phenazine derivatives

Electrochemical reduction of enantiomerically pure amino- and alkoxy-phenazine derivatives forms strongly basic radical anions which give asymmetric induction in the conversion of 3,4-epoxytetrahydrothiophene-1,1-dioxide into the allylic ester with facile regeneration of the phenazine.     

Optical trapping microfabrication with electrophoretically delivered particles inside glass capillaries

We have developed a new technique for rapid microfabrication that uses electrophoretically delivered particles and an optical trap. The material particles, micrometer- and nanometer-sized polystyrene beads in aqueous solution, are continuously delivered to an optical trap by means of the electrophoretic effect inside glass capillaries or similar microstructures. The optical trap is used to manipulate and deposit the polystyrene beads onto a substrate. The continuous, on-demand delivery of particles allows for microfabrication in two and three dimensions with high speed and high efficiency and without material waste. This new technique has many potential applications in microelectronics and biotechnology.     

Conformational preferences driven by the C-methyl substituent in chelated o-diphenylphosphino-alpha-methyl-N,N-dimethylbenzylamine rhodium complexes

The stereochemistry of the chelate rings of a number of rhodium aminophosphine complexes is studied by NMR spectroscopy. The similarity in the variable-temperature behavior for the different compounds is consistent with them having in common highly preferred chelate ring conformations. The six-membered metallacycle of coordinated (R)-PN (PN = o-diphenylphosphino-alpha-methyl-N,N-dimethylbenzylamine) adopts a delta conformation in the solid state. NMR experiments indicate that this conformation is strongly favored in solution as well. The preferred sense of helicity is imposed by the absolute configuration of the stereogenic carbon atom on the ligand, which exerts an important steric control. The complex [Rh(TFB)((C(6)H(4)CHMeNMe(2))(2)P(C(6)H(4)CHMeNHMe(2)))](BF(4))(2).H(2)O.Me(2)CO crystallizes in the monoclinic space group P2(1) with a = 12.0548(11) A, b = 16.139(2) A, c = 12.1804(10) A, beta = 100.742(9) degrees, Z = 4.     

Collision of a Solid with an Incompressible Fluid

We give a predictive theory of the collisions of a viscous incompressible fluid with solids. The theory is based on interior percussions which account for the very large stresses and contact forces resulting from the kinematic incompatibilities responsible for the collision. New equation of motion and constitutive laws result from the theory. Examples dealing with a fluid colliding with its container and with a diver impacting the water of a swimming pool are studied.     

Experimental design methodologies to optimise the spectrofluorimetric determination of Losartan and Valsartan in human urine

A spectrofluorimetric method has been developed for the determination of two angiotensin II receptor antagonists (ARA II): Losartan and Valsartan. A fractional factorial design and a central composite design were used. The key factors considered in the optimization process were pH, temperature and emission slit width. Maximum fluorescent intensity was established as response for each experiment. The response surfaces confirmed the robustness of the method. A clean-up procedure was used for urine samples that consisted of a solid-phase extraction using C8 cartridges. The total analysis time was lower than 30 min. This method proved to be accurate (RE, 8%), precise (intra- and inter-day coefficients of variation were lower than 8% and sensitive enough (LOQ c.a. 0.5 μg ml⁻¹) to be applied to the determination of Losartan and Valsartan in urine samples.