Systèmes de sortie ℱ Dt prévisibles

Summary Given a random closed setM, adapted to a filtration ( _t ), we construct a local time ofM which is both ( _t ) adapted and ( _Dt ) predictable, whereD _t =inf{s>t: sM}. Similarly an exit system, both ( _t ) optional and ( _Dt ) predictable, is associated withM and with the process representing the future at each timet. The paper is motivated by the markovian case, where the general results are applied to Ray processes.     

Ensembles régénératifs de la droite

Résumé La théorie des ensembles régénératifs stationnaires de la droite a été étudiée récemment par Taksar (Regerative sets on real line — Séminaire de probabilités XIV, Lecture Notes in Mathematics 784, Springer 1980). Dans le présent article, nous développons une théorie des ensembles régénératifs de la droite (non nécessairement stationnaires) à partir d'une définition extrêmement maniable, nouvelle même pour les ensembles régénératifs de ₊, et nous retrouvons de manière simple les résultats de Taksar concernant le cas stationnaire.     

Biocompatible polymers for antibody support on gold surfaces

The elimination or minimization of non-specific protein adsorption from serum is critical for the use of surface plasmon resonance (SPR) sensors for in vitro and in vivo analysis of complex biological solutions. The ultimate goals in this application are to minimize non-specific adsorption of protein and to maximize analyte signal. A reduction of the non-specific protein adsorption from serum of up to 73% compared to carboxymethylated-dextran 500 kDa (CM-dextran) was achieved following a survey of eight biocompatible polymers and 10 molecular weights of CM-dextran. These coatings minimize non-specific adsorption on the sensor while also serving as immobilization matrices for antibody fixation to the probes. Polymers including polysaccharides: CM-dextrans, CM-hyaluronic acid, hyaluronic acid, and alginic acid were investigated. Humic acid, polylactic acid, polyacrylic acid, orthopyridyldisuldfide–polyethyleneglycol–N-hydroxysuccinimide (OPSS–PEG–NHS), and a synthesized polymer; polymethacrylic-acid-co-vinyl-acetate (PMAVA) were also used. The non-specific protein adsorption reduction was measured over a 14 day period at 0 °C for each polymer. Calibration curves using some of these polymers were constructed to show the performance and low detection limit possibilities of these new antibody supports. For many of the polymers, this is the first demonstration of employment as an antibody support for an optical or surface active sensor. CM-dextran is the polymer offering the largest signal for the antigen detection. However, the biocompatible polymers demonstrate a greater stability to non-specific binding in serum. These biocompatible polymers offer different alternatives for CM-dextran.     

Half-sandwich and mixed-ring uranium complexes

The monocyclooctatetraene uranium complex [U(COT)(I)₂(THF)₂] (COT=η-C₈H₈; THF=tetrahydrofuran), isolated from the reaction of bis(cyclooctatetraene)uranium with iodine, is a precursor for the synthesis of the alkyl derivatives [U(COT)(CH₂Ph)₂i (HMPA) ₂], [U(COT)(CH₂SiMe₃)₂(HMPA)] (HMPA=hexamethyl phosphorous triamide) and [U(COT)CH₂SiMe₃)₃] [Li(THF)₃] and of the mixed-ring compounds [U(COT)(η-C₅R₅)(I)] (R=H or Me). The last were used to prepare the amide and alkyl complexes [U(COT)(η-C₅H₅)(N{SiMe₃}₂)] and [U(COT)(η-C₅Me₅)(CH₂SiMe₃)].     

Conservation of [(C2H4NH3)3N]2·(ZrF7)2·H2O layers during the topotactic dehydration of [(C2H4NH3)3N]2·(ZrF7)2·9H2O

Tren amine cations [(C₂H₄NH₃)₃N]³⁺ and zirconate or tantalate anions adopt a ternary symmetry in two hydrates, [H₃tren]₂·(ZrF₇)₂·9H₂O and [H₃tren]₆·(ZrF₇)₂·(TaOF₆)₄·3H₂O, which crystallise in R32 space group with a_H = 8.871 (2) Å, c_H = 38.16 (1) Å and a_H = 8.758 (2) Å, c_H = 30.112 (9) Å, respectively. Similar [H₃tren]₂·(MX₇)₂·H₂O (M = Zr, Ta; X = F, O) sheets are found in both structures; they are separated by a water layer (O_w(2)-O_w(3)) in [H₃tren]₂·(ZrF₇)₂·9H₂O. Dehydration of [H₃tren]₂·(ZrF₇)₂·9H₂O starts at room temperature and ends at 90 °C to give [H₃tren]₂·(ZrF₇)₂·H₂O. [H₃tren]₂·(ZrF₇)₂·H₂O layers remain probably unchanged during this dehydration and the existence of one intermediate [H₃tren]₂·(ZrF₇)₂·3H₂O hydrate is assumed. O_w(1) molecules are tightly hydrogen bonded with -NH₃⁺ groups and decomposition of [H₃tren]₂·(ZrF₇)₂·H₂O occurs from 210 °C to 500 °C to give successively [H₃tren]₂·(ZrF₆)·(Zr₂F₁₂) (285 °C), an intermediate unknown phase (320 °C) and ZrF₄.     

Competitive Photoisomerization and Energy Transfer Processes in Fluorescent Multichromophoric Systems

Multichromophoric systems showing both fluorescence and photoisomerization are fascinating, with complex interchromophoric interactions. The experimental and theoretical study of a series of compounds, bearing a variable number of 4-dicyanomethylene-2-tert-butyl-6-(p-(N-(2-azidoethyl)-N-methyl)aminostyryl)-4H-pyran (DCM) units are reported. The photophysical properties of multi-DCM derivatives, namely 2DCM and 3DCM , were compared to the single model azido-functionalized DCM , in the E and Z isomers. The (EE)- 2DCM and (EEE)- 3DCM were synthesized via the click reaction. Steady-state spectroscopy and photokinetics experiments under UV or visible irradiation indicated the presence of intramolecular energy transfer processes among the DCM units. Homo- and hetero-energy transfer processes between adjacent chromophores were confirmed by fluorescence anisotropy and decays. Molecular dynamics simulations for 2DCM were carried out and analyzed using a Markov state model, providing geometrical parameters (orientation and distance between chromophores) and energy transfer efficiency. This work contributes to a better understanding and rationalization of multiple energy transfer processes occuring within multichromophoric systems.     

Gas-Phase Lithium Cation Basicity: Revisiting the High Basicity Range by Experiment and Theory

According to high level calculations, the upper part of the previously published FT-ICR lithium cation basicity (LiCB at 373 K) scale appeared to be biased by a systematic downward shift. The purpose of this work was to determine the source of this systematic difference. New experimental LiCB values at 373 K have been measured for 31 ligands by proton-transfer equilibrium techniques, ranging from tetrahydrofuran (137.2 kJ mol^?1) to 1,2-dimethoxyethane (202.7 kJ mol^?1). The relative basicities (ΔLiCB) were included in a single self-consistent ladder anchored to the absolute LiCB value of pyridine (146.7 kJ mol^?1). This new LiCB scale exhibits a good agreement with theoretical values obtained at G2(MP2) level. By means of kinetic modeling, it was also shown that equilibrium measurements can be performed in spite of the formation of Li⁺ bound dimers. The key feature for achieving accurate equilibrium measurements is the ion trapping time. The potential causes of discrepancies between the new data and previous experimental measurements were analyzed. It was concluded that the disagreement essentially finds its origin in the estimation of temperature and the calibration of Cook’s kinetic method. Graphical Abstract

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2-Groupe des classes positives d'un corps de nombres et noyau sauvage de la K-théorie

We compute the 2-rank of the wild kernel WK₂(F) of a number field by constructing a 2-class group ad hoc. The main result generalizes in the more intricate case the canonical isomorphism established for odd primes under the assumption in a previous article (cf. (Acta. Arith. 67 (1994) 335; Math. Z. 238 (2001) 335)). It involves a criterium of triviality for the 2-part of the wild kernel of Galois number fields and, in the particular case of quadratic fields, it leads to a logarithmic interpretation of the diophantine conditions obtained by other authors.     

Concentration of sodium ion as the determining factor for the association of dansyl amino acids with the teicoplanin molecule in reversed-phase liquid chromatography

The mechanism of the binding of D,L dansyl amino acids to teicoplanin was investigated. Na+ was used as an indicator of the interactions between the solutes and teicoplanin. The number (n) of sodium ions, Na+, excluded from the solute-teicoplanin interface when analyte transfer occurred was determined. A thermodynamic study and enthalpy-entropy compensation were performed to further explore the interaction mechanism. From these results, it was shown that teicoplanin was balanced between 2 conformational states characterized by distinct enantioselective properties. This approach indicates that liquid chromatography (LC) is a useful tool to extract physicochemical and molecular information from retention data. Thus, LC can be used as a complementary technique with the conventional techniques of molecular interaction analysis.