Lithium diorganocuprate reactions with l-serine derivatives

The lithium diorganocuprate reactions with L-serine derivatives are studied. Retention of configuration, or at least a high enantiomeric excess (>80%) of the formed α-amino esters is observed in all cases. Attempts are made to restrict side-reactions.     

Optimization,validation and comparison of various extraction techniques for the trace determination of polycyclic aromatic hydrocarbons in sewage sludges by liquid chromatography coupled to diode-array and fluorescence detection

There is a need for a better characterization of sludges from wastewater treatment plants which are destined to be spread on agricultural lands. Inorganic pollutants are regularly controlled but organic pollutants have received few attention up to now. On this paper, we have been interested on the analysis of the 16 polycyclic aromatic hydrocarbons (PAHs) listed in the US Environmental Protection Agency (US EPA) priority list and more particularly of the six PAHs listed in the European community list (fluoranthene, benzo[b and k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene). The analysis step consists on liquid chromatography with both fluorescence and UV detections as described in the EPA Method 8310. As for the extraction step, several techniques such as supercritical fluid extraction, pressurized liquid extraction, focused microwave extraction in open vessels, Soxhlet and ultrasonic extractions are compared after optimization of the experimental conditions (solvent nature and quantity, temperature, pressure, duration, ... ) and validation with certified sludges. When optimized, these five extraction techniques are as much efficient with similar relative standard deviation. Whatever the extraction techniques used, the whole analysis protocol permits to quantify PAHs in the range of 0.09 to 0.9 mg/kg of dried sludges.     

An Absence of Non-specific Immune Response towards para-Sulphonato-calix[n]arenes

The effects of para-Sulphonato-calix[4]arene, para-Sulphonato-calix[6]arene and para-Sulphonato-calix[8]arene on the activation of NADPH oxidase in neutrophils has been studied. All three molecules do not induce NADPH oxidase activation, and hence do not stimulate neutrophils. Measurement of cell viability demonstrates that these three water-soluble calix[n]arene derivatives are not cytotoxic.     

Synthesis of novel poly(ethylene glycol) supported benzazepines: the crucial role of PEG on the selectivity of an intramolecular Heck reaction

Poly(ethylene glycol) (PEG 3400) was used as a soluble polymeric support for the synthesis of a series of novel benzazepines. The key step for the preparation of these heterocycles was a phosphine-free palladium-catalyzed Heck reaction. Palladium nanoparticles formed during the course of the reaction were characterized. The presence of PEG 3400 influenced the outcome of the reaction in terms of selectivity.     

Plasma surface modification of organic materials: comparison between polyethylene films and octadecyltrichlorosilane self-assembled monolayers

Low-pressure low-frequency NH3 plasmas have been used for the surface modification of bulk polyethylene films and of octadecyltrichlorosilane (OTS) self-assembled monolayers deposited on oxidized silicon wafers. The incorporation of nitrogen-containing groups by the plasma treatment has been followed by contact angle measurements and by X-ray photoelectron spectroscopy. The surface degradation of the OTS monolayers due to plasma etching has been measured separately by optical ellipsometry with subnanometric accuracy. Our data show clear evidence for the existence of an optimum treatment time, yielding a high density of NH2 functional groups without significant variation of the structural features of the organic material. Self-assembled monolayers appear as excellent model systems to characterize the effects of plasma discharges on polyolefins. In particular, they allow testing the influence of molecular orientation, packing density, and crystallinity on the final results.     

An ab-initio study of the molecular structure and properties of HPO

An ab-initio gaussian lobe function study of the structure and some molecular properties of the HPO molecule is reported. By a partial optimization of the geometrical structure the following equilibrium structure parameters are found: r_PO = 1.536 Å; r_PH = 1.475 Å; the bond angle is found to be close to 102° with a bending force constant of 0.58 mdyne/Å. The dipole moment, effective charges and quadrupole term components at various bond angles are reported. The wavefunction of the equilibrium geometry is available from the authors upon request.     

Effects of structural factors on the pi-dimerization and/or disproportionation of the cation radical of extended TTF containing thiophene-based pi-conjugated spacers

The electrochemical and chemical oxidation of extended TTF 4 and 5 are analysed by cyclic voltammetry, Visible/NIR and ESR spectroscopies, and the X-ray structures of the new salts 5 x BF(4)(CH(2)Cl(2)) and 4 x ClO(4)(THF)(1/2) are presented. The effects of structural factors on the pi-dimerization or the disproportionation reaction of the cation radical are shown. The oxidation of compound 4 presents the successive formation of stable cation radical and dication species both in dichloromethane (DCM) and in a CH(3)CN/THF mixture. In contrast, for compound 5, the stability of the oxidation states strongly depends on the nature of the solvent. In DCM, the oxidation of 5 proceeds by two close one-electron transfers while in CH(3)CN/THF the dication is directly formed via a two-electron process. The X-ray structures of the two salts reveal the formation of pi-dimers of cation radical. While the dimer (5(2))(2+) is due mainly to pi-pi interactions between the conjugating spacer, the multiplication of the sulfur atoms in compound 4 contributes to stabilize the dimer by the combined effects of S-S and pi-pi interactions. Visible/NIR and ESR experiments confirm the higher tendency of 4(+)(.) to dimerize with the occurrence of dimer and monomer in solution, while for 5(+)(.) only the monomer is detected in DCM. On the other hand, by dissolution of 5 x BF(4)(CH(2)Cl(2)) in CH(3)CN, only the neutral and the dicationic states of compounds 5 are observed owing to the disproportionation reaction.     

Chromatographie par complexe de transfert de charge. Application à l'analyse d'hydroliquéfiats du charbon par HPLC

Résumé L'analyse de coupes lourdes (huile de distillation sous vide et huile issue du séparateur à chaud) provenant de l'hydroliquéfaction catalytique du charbon a été réalisée par mise en ouvre de différentes techniques chromatographiques. L'identification des principales structures résulte de l'application de la chromatographie par couplage de transfert de charge en mode HPLC et des spectroscopies UV et de masse.

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Donotor-acceptor complex chromatography —Application to analysis of coal liquefaction products by HPLC

Summary A Vacuum gas oil and the corresponding residue of a coal liquefaction product were investigated by means of HPLC and MS. Nearly a complete identification was performed by chromatographic, UV-spectroscopic methods and MS.

     

New polycyclic diamine scaffolds from dimerization of 3-alkyl-1,4-dihydropyridines in acidic medium

[reaction: see text] 3-Alkyl-1,4-dihydropyridines dimerize in acidic medium, at low temperature, to give polycyclic imminium salts derivatives that were reduced to afford new polycyclic diamine scaffolds. The reaction can be extended to enantiopure series starting from R-(+)- or S-(-)-1-phenylethylamine. Long exposure of the polycyclic imminium salt intermediates to air moisture at 20 degrees C resulted in formation of new amide derivatives. This is probably due to the addition of water followed by an intramolecular oxido-reduction process.