Countercurrent chromatographic isolation of lolitrem B from endophyte-infected ryegrass (Lolium perenne L.) seed

This paper describes a new method of purification of the Lolitrem B, a tremorgenic mycotoxin produced in planta by the endophytic fungus Neotyphodium lolii. The method is based on the large-scale isolation of the toxin by countercurrent chromatography (CCC). The lolitrem B content in endophyted ryegrass seed, 11 microg/g or 11 ppm, is extracted by stirring finely ground seeds with ethanol for 3 h at room temperature. The concentrated crude extract contains about 0.6 mg/g or 600 ppm of lolitrem B. It is then submitted to CCC purification with a biphasic four-solvent liquid system. A 160-fold enrichment was obtained in one step producing a raffinate containing 10% or 100 mg/g of the toxin. Further purifications were then performed by thin layer and low pressure liquid chromatography. Twenty-eight micrograms of lolitrem B with a 96% purity grade were obtained from 8 kg of seeds (yield 32%).     

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.     

A self-consistent reaction field model of solvation using distributed multipoles. I. Energy and energy derivatives

The self-consistent reaction field model developed previously by the authors in the case of single center multipole expansion of the electronic structure of the solute has been extended to the case of a distributed multipole expansion. Three different expansions have been tested and two of them have proved to be rapidly convergent. The performances of the code are illustrated by the density functional theory treatment of few test systems: guanine, cytosine, and cytosine hydrated with one and three water molecules. A robust fast computer code has been tested to get the electronic structure, the electrostatic contribution to the solute-solvent free energy of interaction, and the optimized molecular geometry in solution.     

Experimental analysis of floc size distributions in a 1-L jar under different hydrodynamics and physicochemical conditions

This study focuses on the relation among hydrodynamics, physicochemical conditions, and floc size. During ortho-kinetic flocculation, the floc size is controlled by a balance between hydrodynamic stress and aggregate strength. Special attention was paid to the influence of a hydrodynamic sequencing on both the aggregate strength and the flocculation processes. Experimental research was conducted in a 1-L jar for two different pH values. The hydrodynamic sequencing was made up of successive slow and rapid mixing periods, and different slow mixing intensities were studied. First, the large floc size was shown to decrease with increasing velocity gradient (G), with an expected trend (d proportional variant epsilon(-1/4)). Then, the aggregate strength was shown to depend on two main factors: the flocculation history and the physicochemical conditions, which control the cohesion forces between primary particles. Finally, flocculation processes are discussed in terms of aggregation and breakup phenomena, with relation to local hydrodynamics and physicochemical conditions.     

Theoretical study of the adsorption of silver atoms on the (111) face of silicon

The adsorption of one or many silver atoms on a (111) silicon face (reduced to 61 dangling atomic orbitals) is investigated by means of a self-consistent Hartree–Fock method parametrized from atomic and thermodynamical data. The valley sites (above three Si atoms) are favored over the top sites (above one Si atom). The extrapolation of the results obtained for several structures corresponding to the adsorption of n = 1, 2, 3, 4, 6, and 7 Ag atoms allows us to conclude that the most stable structures correspond: for \documentclass{article}\pagestyle{empty}\begin{document}$ \theta = \frac{1}{3} $\end{document} to linear Ag chains (3 × 1 phase), for \documentclass{article}\pagestyle{empty}\begin{document}$ \theta = \frac{2}{3} $\end{document} to an honeycomb lattice (\documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt 3 \times \sqrt 3 $\end{document} phase), and for θ = 1 to a centred hexagonal lattice (\documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt 3 \times \sqrt 3 $\end{document} phase), the Ag atoms located at the centers of the hexagons being beneath the plan of the hexagons. The adsorption energies corresponding to the various θ are practically equal (ca. 3 eV/Ag). The net charges of Ag atoms are equal to 0.35.     

Ester interchange reactions catalyzed by tin compounds in reactive processing: NMR contribution via reactions with model compounds

Interchange reactions involving esters were used in reactive processing with a view to obtaining polymer blends with stabilized morphology. Dibutyltinoxide (DBTO) appeared to be an excellent catalyst for these reactions. In fact, it was shown that the true catalytic entity is a dimeric alkoxy, acyloxy distannoxane entity formed in situ, during processing, by the reaction of the DBTO with the polymer ester groups. This compound was first obtained with model esters and characterized by multinuclear NMR analysis (¹H, ¹³C, ¹¹⁹Sn). The catalytic efficiency of the in situ polymeric distannoxane was compared with other added parent distannoxanes. Later on – still with model compounds – ligand exchanges at the tin sites were investigated and it was shown that these exchanges are not essential to the catalyst activity, but when they take place it increases the catalytic efficiency. Then, this type of catalysis was successfully used for interchange reactions in reactive extrusion of different polymer blends, some applications are briefly presented. To cite this article: M.-F. Llauro and A. Michel, C. R. Chimie 9 (2006).     

Localization of tetra(m-hydroxyphenyl)chlorin (Foscan) in human healthy tissues and squamous cell carcinomas of the upper aero-digestive tract, the esophagus and the bronchi: a fluorescence microscopy study

To date, little is known about precise time-dependent distribution and histological localization of tetra(m-hydroxyphenyl)chlorin (mTHPC) in human healthy tissues and squamous cell malignancies in the upper aero-digestive tract. A fluorescence microscopy study was performed on 50 healthy tissue biopsies and on 13 tumors (graded from Tis to T1 SCC) from 30 patients. Tissue samples were taken between 4 h and 11 days following injection of 0.15 mg/kg mTHPC. A fairly comparable distribution pattern in various tissues was observed over time in different patients. Vascular localization of mTHPC fluorescence predominates at a short delay, whereas the dye is essentially located in the tumoral and healthy mucosa after longer delays. A much lower uptake and retention of mTHPC fluorescence was noted in striated muscle and cartilage as compared to neoplastic lesions. No significant selectivity was found between healthy and tumoral mucosa. The obtained data are important to confirm drug-light interval that have been selected for effective PDT for early SCC malignancies while minimizing the risks of over- or under-treatment. The low fluorescence level in striated muscle provides the opportunity to develop interstitial PDT as a treatment modality for invasive SCC of unfavorable locations in the oral cavity or pharynx, such as the base of the tongue.     

Heterocyclisation de diols βγ′-alleniques.

The silver nitrate assisted cyclization of the entitled diols $\text{3}$ leads, depending on the substitution of the allenic linkage, specifically to dihydropyranes $\text{4}$, when R is alkyl or to an equimolecular mixture of $\text{4}$ and its tetrahydrofuranyl isomer $\text{5}$ when R is hydrogen.     

Équations de type de Boltzmann,spatialement homogènes

Summary We study the construction of a nonhomogeneous ⁿ -valued Markov process, whose laws at fixed times evolve according to a Boltzmann type equation (spatially homogeneous). We then consider the problem of the asymptotic propagation of chaos for a system of a large number of interacting particles.