Fully automated high-performance liquid chromatographic assay for the analysis of free catecholamines in urine

A totally automated and reliable high-performance liquid chromatographic method is described for the routine determination of free catecholamines (norepinephrine, epinephrine and dopamine) in urine. The catecholamines were isolated from urine samples using small alumina columns. A standard automated method for pH adjustment of urine before the extraction step has been developed. The extraction was performed on an ASPEC (Automatic Sample Preparation with Extraction Columns, Gilson). The eluate was collected in a separate tube and then automatically injected into the chromatographic column. The catecholamines were separated by reversed-phase ion-pair liquid chromatography and quantified by fluorescence detection. No manual intervention was required during the extraction and separation procedure. One sample may be run every 15 min, ca. 96 samples in 24 h. Analytical recoveries for all three catecholamines are 63-87%, and the detection limits are 0.01, 0.01, and 0.03 microM for norepinephrine, epinephrine and dopamine, respectively, which is highly satisfactory for urine. Day-to-day coefficients of variation were less than 10%.     

Dérivés de la dihydro-2,4 triazole-1,2,4 thione-3 et de l'amino-2 thiadiazole-1,3,4 à partir de nouvelles thiosemicarbazones d'esters

A new general synthesis of 4,5-disubstituted 2,4-dihydro-1,2,4-triazole-3-thiones is proposed. These heterocycles are obtained by the action of primary amines, arylhydrazines or aroylhydrazines on the thiosemicarbazones of eaters. These last compounds are prepared by action of chlorhydrates of iminoethers on thiosemicarbazide in dimethylformamide. These thiosemicarbazones react also with strong acids, acid anhydrides and chlorides; by thermolysis and they give 2-amino-1,3,4-thiadiazole derivatives. Also, two derivatives of 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole have been prepared.     

Direct Isocoumarin Synthesis Through LDA-Promoted Addition of Acetaldehyde on Orsellinate. An Abrupt Synthesis of 6-Hydroxymellein,a Fungal Phytotoxin

The LDA-promoted addition of acetaldehyde on orsellinate gives (±) 6 -hydroxymellein, a fungal phytotoxin, with a 51% yield.     

Synthesis of Anhydronectriachrysone,an Extensively Conjugated γ-Pyrone

The synthesis of anhydronectriachrysone (2) through the DIBAH reduction of toralactone (3), followed by dehydration of the corresponding lactol (4) is reported (38% yield).     

GISAXS study of carbon nanotubes grown by CVD

We report a quantitative Grazing Incidence Small Angle X‐ray Scattering (GISAXS) study of a dense film of mutually oriented carbon nanotubes (CNTs) grown by a catalytically‐activated DC HF CCVD process after dispersion of metallic catalytic (Co) islands on SiO₂/Si(100) substrates. The GISAXS pattern analysis is expanded to non‐correlated surface science systems and is based on CNTs density, characteristic lengths, atomic Co dispersion throughout the CNTs and roughnesses of uncorrelated particles. The results are closely compared to SEM and TEM observations. The GISAXS patterns, even dominated by envelope features of disordered objects, provide significant complementary quantitative data about CNTs films. The results underline that cobalt continuously fills the nanotube in the course of the growth and that the CNTs experience a large tendency toward mutual alignment. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Heat-treated Saccharomyces cerevisiae for antimony speciation and antimony(III) preconcentration in water samples

An analytical method was developed for antimony speciation and antimony(III) preconcentration in water samples. The method is based on the selective retention of Sb(III) by modified Saccharomyces cerevisiae in the presence of Sb(V). Heat, caustic and solvent pretreatments of the biomass were investigated to improve the kinetics and thermodynamics of Sb(III) uptake process at room temperature. Heating for 30 min at 80 degrees C was defined as the optimal treatment. Antimony accumulation by the cells was independent of pH (5-10) and ionic strength (0.01-0.1 mol L(-1)). 140 mg of yeast and 2h of contact were necessary to ensure quantitative sequestration of Sb(III) up to 750 microg L(-1). In these conditions, Sb(V) was not retained. Sb(V) was quantified in sorption supernatant by inductively coupled plasma mass spectrometry (ICP-MS) or inductively coupled plasma optical emission spectrometry (ICP-OES). Sb(III) was determined after elution with 40 mmol L(-1) thioglycolic acid at pH 10. A preconcentration factor close to nine was achieved for Sb(III) when 100mL of sample was processed. After preconcentration, the detection limits for Sb(III) and Sb(V) were 2 and 5 ng L(-1), respectively, using ICP-MS, 7 and 0.9 microg L(-1) using ICP-OES. The proposed method was successfully applied to the determination of Sb(III) and Sb(V) in spiked river and mineral water samples. The relative standard deviations (n=3) were in the 2-5% range at the tenth microg L(-1) level and less than 10% at the lowest Sb(III) and Sb(V) tested concentration (0.1 microg L(-1)). Corrected recoveries were in all cases close to 100%.     

Catalytic wet air oxidation of oleic acid on ceria-supported platinum catalyst.effect of pH

Summary Catalytic wet air oxidation (CWAO) of oleic acid was carried out in a batch reactor on platinum supported ceria catalyst (Pt/CeO₂). Oleic acid is a water insoluble linear unsaturated fatty acid of 18 carbon atoms. To increase the homogeneity of the solution by saponification, the influence of NaOH additions in oleic acid CWAO mechanism and catalyst performances have been investigated. The oxidation of such molecule occurs by two types of mechanisms: successive carboxy-decarboxylation which leads essentially to CO₂and/or C-C bonds splitting in the alkyl chain inducing a high formation of acetic acid. With or without NaOH, the 5%Pt/CeO₂catalyst is active in the conversion of oleic acid and selective to carbon dioxide. In alkaline medium, oleic acid is initially saponified which increases the solubility of the reactant before it to be oxidized. Finally the oxidation is slightly delayed by the presence of NaOH. The catalyst characterizations show no significant difference before and after reaction.</o:p>     

Crystalline structure of oxide-based epitaxial tunnel junctions

Epitaxial metal/oxide based magnetic tunnel-junctions (MTJ) are valuable model systems to investigate the influence of the crystallinity of individual layers on the magnetic properties. We have non-destructively studied the effect of the optical lithography procedure on the crystalline structure of MTJ’s with lateral spatial resolution by performing local x-ray diffraction experiments using a microfocused x-ray spot. We demonstrate that the lithography process produces distortion effects on the crystalline structure of the layers near the edges of the lithographed junction. These distortions are present on all the constituent layers and are most probably driven by the elastic constants of the materials. They translate into tilts of the crystalline planes in the vicinity of the edges and propagate towards the center of the junction; the tilt’s amplitude (up to several degrees) and sign (concave or convex) depend on the junction’s shape, size and the type of materials (interfaces) used. We report results for junctions made with two types of metal-oxide interfaces (Co/CoFe₂O₄ and Co/Fe₃O₄), with sizes from 10 to 150 μm and various shapes (square-, rectangle- and disk-like).