Intertwined Analytical,Experimental and Theoretical Studies on the Formation and Structure of a Copper Dienolate

The reaction of a silyl dienolate, a Cu(II) salt and TBAT yielding the corresponding copper dienolate is addressed. A combined NMR and cyclic voltammetry analysis first highlight the role of TBAT in the Cu(II) to Cu(I) reduction and the structure of the precatalytic species. From these first results a second set of NMR and theoretical studies enable the determination of the structure and the mechanism of formation of the copper dienolate catalytic species. Finally, we showed that that the copper catalyst promote the E/Z s-cis/s-trans equilibration of the silyl dienolate precursor through a copper dienolate intermediate. All of these results unveil some peculiarities of the catalytic and asymmetric vinylogous Mukaiyama reaction.     

Simultaneous determination of a drug candidate and its metabolite in rat plasma samples using ultrafast monolithic column high-performance liquid chromatography/tandem mass spectrometry

An ultrafast bioanalytical method using monolithic column high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) was evaluated for the simultaneous determination of a drug discovery compound and its metabolite in plasma. Baseline separation of the two compounds was achieved with run times of 24 or 30 s under isocratic or gradient conditions, respectively. The monolithic column HPLC/MS/MS system offers shorter chromatographic run times by increasing flow rate without sacrificing separation power for the drug candidate and its biotransformation product (metabolite). In this work, the necessity for adequate chromatographic resolution was demonstrated because the quantitative determination of the drug-related metabolism product was otherwise hampered by interference from the dosed drug compound. The chromatographic performance of a monolithic silica rod column as a function of HPLC flow rates was investigated with a mixture of the drug component and its synthetic metabolite. The assay reliability of the monolithic column HPLC/MS/MS system was checked for matrix ionization suppression using the post-column infusion technique. The proposed methods were successfully applied to the analysis of study rat plasma samples for the simultaneous quantitation of both the dosed drug and its metabolite. The analytical results obtained by the proposed monolithic column methods and the 'standard' silica particle-packed HPLC column method were in good agreement, within 10% error.     

Total serum IgE quantification by microfluidic ELISA using magnetic beads

The present work reports on the quantification of total IgE in human serum using a microanalytical device whose fluidics is driven by gravity and capillary forces only. Thanks to the eight parallel microchannels in each microchip, calibration and sample analysis are performed simultaneously. A mixture of magnetic bead/analyte/second antibody is incubated off-line and then percolated through the channels where magnetic beads are trapped, enabling the separation of the solid phase from the excess reagents. The entire assay is performed in less than 1 h, and thanks to the miniaturized format, only a small volume of serum is required. Non-specific adsorption was first investigated and a blocking agent compatible with this allergy-based test was chosen. Then, the assay was optimized by determining the best magnetic bead and labelled antibody concentrations. After achievement of a calibration curve with a reference material, the protocol was applied to total IgE quantification of a patient serum sample that showed results in good accordance with those obtained by ImmunoCap® and Immunoaffinity capillary electrophoresis measurements. A detection limit of 17.5 ng ml^?1 was achieved and good reproducibility (RSD?

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Figure Off-line incubation of the patient sample with anti-IgE grafted magnetic beads and ALP-labelled anti-IgE is carried out in an Eppendorff. Detection is then performed with the GRAVI®-Cell device from DiagnoSwiss, where fluidics is driven by gravity and capillary forces only.

Determination of mineral filler orientation in reinforced thermoplastics by x-ray diffraction

Orientation of mica and talc platelets in injection-molded polyamide 6.6 was investigated by X-ray diffraction (diffractometry, pole figures). The platelets are nearly perpendicular to the plane of the molded plaque in the core, and parallel to it in the skin. These orientations are related to the shear and elongation rate distribution in the thickness of the molding.     

Investigations of Miscibility in Interpenetrated Systems of Polyurethane and Polystyrene Obtained at Room Temperature

Interpenetrating polymer systems based on crosslinked polyurethane (PU) and polystyrene (PS) were prepared at room temperature by a one-shot (in situ) method, starting from an initial homogeneous mixture of reagents via non interfering mechanisms. Both polymerizations were performed either simultaneously or one after the other. Crosslinks and/or covalent bonds between components were deliberately introduced by the addition of appropriate monomers, in order to tailor the degree of microphase separation. Depending on the formation process, transluscent or transparent films were obtained, despite the difference in refractive index of the components. The maximum of miscibility, taken as from the glass transition criterion, was obtained for sequential tightly graft interpenetrating networks.     

1, 1-dichloroalkylphosphonates: Convenient starting materials for low-coordinated trivalent phosphorus compounds

Diisopropyl 1,1-dichloroalkylphosphonates bearing various groups (alkyl, aryl, allyl, benzyl, phenylthiolate, trimethylsilyl) in the α-position were reduced to the corresponding primary 1,1-dichlorophosphines by the LiAlH₄-AlCl₃ system in diethyl ether. Subsequent dehydrochlorination with tertiary amines in the presence of trapping dipolar compounds (ethyl diazoacetate or n-hexylazide) led to the expected 1,2,4-diazaphospholes or 3H-1,2,3,4-triazaphospholes.     

Synthesis and properties of polyampholytes prepared in microemulsions

A series of polyampholytes of sodium 2-acrylamido-2-methylpropanesulfonate (NaAMPS) and 2-(methacryloyloxy)ethyltrimethylammonium chloride (MADQUAT) has been synthesized by polymerization in microemulsions. The reaction products are stable inverse latexes consisting of high molecular weight copolymers entrapped in water droplets of small size (d % 80 nm) and dispersed in an isoparaffinic oil. The optimization of the formulation was by a selection procedure based on the hydrophile-lipophile balance of the emulsifiers and solubility parameters of the different components. Both ionomers play an important role in the formulation owing to their amphiphilic and electrolyte characters. Reactivity parameter studies yield r_A and r_M values of 0.81 and 1.97 for NaAMPS and MADQUAT, respectively. The properties of polyampholytes in pure water and in salt solutions were investigated by turbidimetry and viscometry experiments. The results are compared with the recently developed theory of Higgs and Joanny (J. Chem. Phys. 94, 1543 (1991)).