Influence of anionic and cationic reverse micelles on nucleophilic aromatic substitution reaction between 1-fluoro-2,4-dinitrobenzene and piperidine

The nucleophilic aromatic substitution (S(N)Ar) reaction between 1-fluoro-2,4-dinitrobenzene and piperidine (PIP) were studied in two different reverse micellar interfaces: benzene/sodium 1,4-bis(2-ethylhexyl) sulfosuccinate (AOT)/water and benzene/benzyl-n-hexadecyl dimethylammonium chloride (BHDC)/water reverse micellar media. The kinetic profiles of the reactions were investigated as a function of variables such as surfactant and amine concentration and the amount of water dispersed in the reverse micelles, W0 = [H2O]/[surfactant]. In the AOT system at W0 = 0, no micellar effect was observed and the reaction takes place almost entirely in the benzene pseudophase, at every AOT and PIP concentration. At W0 = 10, a slight increment of the reaction rate was observed at low [PIP] with AOT concentration, probably due to the increase of micropolarity of the medium. However, at [PIP] > or = 0.07 M the reaction rates are always higher in pure benzene than in the micellar medium because the catalytic effect of the amine predominates in the organic solvent. In the BHDC system the reaction is faster in the micellar medium than in the pure solvent. Increasing the BHDC concentration accelerates the overall reaction, and the saturation of the micellar interface is never reached. In addition, the reaction is not base-catalyzed in this micellar medium. Thus, despite the partition of the reactants in both pseudophases the reactions effectively take place at the interface of the aggregates. The kinetic behavior can be quantitatively explained taking into account the distribution of the substrate and the nucleophile between the bulk solvent and the micelle interface. The results were used to evaluate the amine distribution constant between the micellar pseudophase and organic solvent and the second-order rate coefficient of S(N)Ar reaction in the interface. A mechanism to rationalize the kinetic results in both interfaces is proposed.     

Efficient synthesis of B-alkylated oxazaborolidines derived from ephedrine and norephedrine

[reaction: see text] Representative B-butyl- and B-methyl-1,3,2-oxazaborolidines derived from ephedrine and norephedrine were prepared in good yield and excellent purity by one-pot treatment of B-H oxazaborolidines with the corresponding organolithium reagent and subsequent hydrolysis of the cyclic borohydride intermediate with anhydrous ammonium chloride.     

Previous illumination of a water soluble chlorine photosensitizer increases its cytotoxicity

Photodithazine (PDZ) is an N-methyl-D-glucosamine derivative of chlorine e6 that is water soluble and has an intense absorption in the range of 650?C680 nm. PDZ photobleaching and photoproduct formation were induced by illumination with laser at two wavelengths: 514 nm (ion argon laser) as well as in 630 nm (dye laser). The time constants of PDZ photobleaching were: 18 min for 630 nm irradiation and 50 min for 514 nm irradiation, suggesting that degradation after irradiation with red light is faster than with green light. Photoproducts formation was evidenced by the appearance of a new absorption band at 668 nm with slight broaden of the Soret band, suggesting that there was no break of the macrocycle. The cytotoxicity of the photodegradated PDZ was investigated and showed to be lower in the dark and higher than non irradiated PDZ. These results may have important clinical implications for PDT such as the possibility to use the previously irradiated PDZ just before clinical application in order to get increased efficiency.     

Theoretical prediction of the mass transfer coefficients in bubble columns operating in churn-turbulent flow regime. Study in Newtonian and non-Newtonian fluids under different operation conditions

 A comprehensive experimental study of the volumetric transfer coefficient k _L a with Newtonian and non-Newtonian fluids in bubble columns using CO₂ as gas phase is the objective of this work. The evaluation of the hydrodynamic characteristics of the bubble columns and delineated the different hydrodynamic regimes considering column geometry, gas flow, liquid height and type of fluid (Newtonian and non-Newtonian) suggest a general applicability of the proposed model. An explanation about of the k _L a values in non-Newtonian fluid is offered take into account shear rate, column geometry, viscosity and results reported in the literature previously. Received on 31 July 1999     

Selective excitation through tapered silica fibers of fluorescent two-photon polymerized structures

Two-photon polymerization has emerged as a powerful tool to design complex three-dimensional microstructures for applications ranging from biology to nanophotonics. To broaden the application spectrum of such microstructures, different materials have been incorporated to the polymers, aiming at specific applications. In this paper we report the fabrication of microstructures containing rhodamine 610, which display strong fluorescence upon one- and two-photon excitation. The latter increases light-penetration depth and spatial selectivity of luminescence. We also demonstrate that by using silica submicrometric wires we were able to select individual microstructures to be excited, which could be explored for designing microstructure-based optical circuits.     

Sensitivity analysis of markup equilibria in complementary markets

We study the competitive structure of a market in which firms compete to provide various products within a bundle. Firms adopt price functions proportional to their per-unit costs by selecting markups. We consider two measures reflecting, respectively, the intensity of direct competition and the impact of complementarity on each producer’s markup. We characterize the sensitivity of these terms to various changes in the market structure and relate this to changes in producer profits and the social efficiency of the market.     

The viscous mucilage from the weedPortulaca oleracea,L

A polysaccharide complex has been extracted from the invasive and widespread weedPortulaca oleracea (purslane) in yields of up to 25 g% (dry wt). The clear and viscous mucilage displays physicochemical properties appropriate for industrial uses, such as food extenders and viscosifier. Toxic collateral effects can be precluded because of the already known uses in home remedies and animal feed. Anion exchange chromatography fractionated the crude complex into a neutral arabinogalactan and polydisperse pectin-like polysaccharides. This fractionation brings about a reduction in the viscosity observed for the native complex, whereas saponification ofO-acetyl and/or carboxy-methoxyl groups increases it.

     

Eigenvalues of Set-Valued Operators in Banach Spaces

This work deals with the spectral analysis of set-valued operators from a Banach space X into its dual space X^*. The main goal of the paper is to study semicontinuity properties of the spectrum operator.Mathematics Subject Classifications (2000) 47H04, 47H12, 58C40.UMR 2071 Universidad de Chile-CNRS.     

Dynamic Inclusion Complexes of Metal Nanoparticles Inside Nanocups

Host–guest inclusion complexes are abundant in molecular systems and of fundamental importance in living organisms. Realizing a colloidal analogue of a molecular dynamic inclusion complex is challenging because inorganic nanoparticles (NPs) with a well‐defined cavity and portal are difficult to synthesize in high yield and with good structural fidelity. Herein, a generic strategy towards the fabrication of dynamic 1:1 inclusion complexes of metal nanoparticles inside oxide nanocups with high yield (>70 %) and regiospecificity (>90 %) by means of a reactive double Janus nanoparticle intermediate is reported. Experimental evidence confirms that the inclusion complexes are formed by a kinetically controlled mechanism involving a delicate interplay between bipolar galvanic corrosion and alloying–dealloying oxidation. Release of the NP guest from the nanocups can be efficiently triggered by an external stimulus.