Kinetics of radical telomerization of vinylidene fluoride in the presence of CCl3Z chain transfer agents

The kinetics of radical telomerization of VDF at 141 °C, initiated by ditertbutylperoxide, in the presence of three chain transfer agents (CTAs), HCCl₃, CCl₄ and CCl₃Br, are presented. The values of the chain transfer constants were assessed as 35, 0.25 and 0.06 at 141 °C for CCl₃Br, CCl₄ and HCCl₃, respectively. The values of the degree of polymerization (DP_n) were obtained for each CTA and were compared for the same CTA concentration. Hence, CCl₃Br behaved as an efficient CTA towards VDF and usually afforded the monoadduct selectively, but in certain conditions the VDF diadduct can also be produced. In contrast, HCCl₃ was not so efficient since a polymeric structure was identified as the major product.     

Determination of geosmin and 2-methylisoborneol in water using solid-phase microextraction and gas chromatography-chemical ionisation/electron impact ionisation-ion-trap mass spectrometry

A method for the determination of geosmin and 2-methylisoborneol (MIB) in water by solid-phase microextraction (SPME) is presented. Various SPME fibre chemistries have been compared for their efficiency in extracting MIB from water. Extraction conditions including the extraction time and temperature have been optimised. A 30 ml water sample is extracted for 20 min at 60 degrees C using a divinylbenzene fibre, and the extract analysed by gas chromatography with ion-trap mass spectrometry detection. d5-Geosmin and d3-MIB are added as internal standards to compensate for any variability in the SPME process which is not carried out to equilibrium. Chemical ionisation, using acetonitrile as the reagent gas, was found to give superior sensitivity to electron impact ionisation (EI) for the detection of MIB. EI was used as the ionisation mode for detection of geosmin. The method shows good linearity over the concentration range 5-40 ng l-1 and gives detection limits of 1 ng l-1 for both geosmin and MIB. Recovery (93-110%) and precision (3-12%) over this concentration range, for both raw and treated drinking waters, are comparable to currently employed methods such as closed-loop stripping analysis (CLSA). The method offers the advantage of being simple to use, with much shorter analysis times in comparison to CLSA.     

Separation of peptides and proteins by capillary electrophoresis using acidic buffers containing tetraalkylammonium cations and cyclodextrins

A method for improving separations of peptides and other positively charged species in capillary zone electrophoresis with untreated capillaries using acidic buffers containing tetraalkylammonium cations is described. Tetramethylammonium and tetrabutylammonium cations dynamically modify the capillary surface, leading to a reversal in the direction of the electroosmotic flow. As a result, the adsorption of positively charged peptides and proteins is minimized, and resolution and peak capacity are improved as the migration of cationic analytes is counterbalanced by the electroosmotic flow. The combining effect of reversing electroosmotic flow and cyclodextrin inclusion complexation on separations of closely related peptides and a protein mixture, as well as tryptic digest of hemoglobin is demonstrated.     

On a class of graphs with prescribed mean curvature

We study a class of quasilinear elliptic equations on the unit ball of ℝ ⁿ in the divergence form ∑ _j=1 ⁿ D _j{G(|x|²,|Du|²)D _j u} =H(|x|) and get estimates on the boundary by using a modified barrier-function technique of Bernstein. We establish a maximum principle for the gradients of solutions and get a global gradient estimate. We prove that solutions with constant boundary condition must be radial. Finally, we apply these results to graphs {(x,u(x)):x∈H ⁿ } whereu:H ⁿ →ℝ is a smooth map of then-hyperbolic spaceH ⁿ =B(0,1) with the metric to get the existence of graphs with radial prescribed mean curvature.     

K3 et formules de Riemann-Hurwitzp-adiques

The well-known formula of Riemann-Hurwitz gives the change of genuses in ann-fold covering of compact connected Riemann surfaces. In Iwasawa theory, there existp-adic analogues which give the change of certain ^±-invariants in ap-extension ofCM number fields. Using functorial and arithmetical properties ofK ₃, we extend such Riemann-Hurwitzp-adic formulas to non-CM fields, assuming some restrictive hypotheses on the capitulation ofK ₂.

     

The insertion of the dioxides of carbon and sulphur into the palladium-carbon bond

Bis ( η¹, η²-allyl) palladium phosphine complexes react with carbon dioxide and sulphur dioxide by insertion into the palladium-carbon σ-bond to give η³-allylpalladium-carboxylate and -S-sulphinate complexes.     

Thermodynamics of the decomposition processes of donor-acceptor complexes MX3 x en x MX3 and MX3 x en.

The structural and thermodynamic properties of the donor-acceptor (DA) complexes of Group 13 metal halides (MX3) with ethylenediamine and their decomposition products have been studied theoretically at the B3LYP/LANL2DZ(d,p) level of theory. Gas-phase dissociation into various components and HX elimination reactions are considered. Both processes are endothermic but favored by entropy. Complexes of 2:1 composition are predicted to be stable in the gas phase up to 640-1000 K. It is found that complexation with the second acceptor molecule lowers the HX elimination enthalpy; in turn, HX elimination increases DA bonding with a second MX3 molecule. Exceptionally high values of the dissociation enthalpies (310-390 kJ mol(-1)) and HX elimination reactions (360-420 kJ mol(-1)) of the amido compounds MX2NHC2H4NH2 and MX2NHC2H4NHMX2 make them important intermediates in the decomposition processes. Dissociation reactions of the complexes are more favorable than HX elimination reactions; however, the subsequent oligomerization and cyclization processes of coordinationally unsaturated amido and imido compounds may facilitate HX elimination. Since HI elimination reactions are predicted to be the least endothermic, and aluminum-containing compounds have the strongest M-N dissociation enthalpies, it is expected that compounds based on aluminum iodide are promising objects for experimental studies.     

Polymérisation anionique de l'isoprène: Nature de la paire d'ions et stéréospécificité

With accumulated HR-NMR spectra of anionic polyisoprenes, it has been possible to study the influence of the nature of the propagating species on the microstructure of the obtained polymers If free ions are responsible for the propagation, the microstructure (1,4-: 25%, 1,2-: 33%, 3,4-: 42%) does not depend on the nature of the cations. But with contact ion pairs, the different addition modes are governed by the size of the alkali metal counterions. Mechanisms of anionic propagations via diene–cation coordination are proposed.     

Development of enzyme biosensor based on pH-sensitive field-effect transistors for detection of phenolic compounds.

This article describes a biosensor based on pH-sensitive field-effect transistors (pH-FETs) as transducer, and immobilised enzyme tyrosinase as biorecognition element, which was used for the determination of phenolic compounds in water solutions. The biologically active membrane was formed by cross-linking of tyrosinase with bovine serum albumin (BSA) in saturated glutaraldehyde (GA) vapours on the sensitive transducer surface. The main analytical characteristics were studied under different conditions as well as the possibility to optimise these working parameters. Different factors such as the pH of immobilisation, the enzyme loading, the time of exposition to glutaraldehyde vapours were investigated in regards to the influence on sensitivity, limit of detection, dynamic range, and operational and storage stability.