Controlled synthesis of amphiphilic biodegradable polylactide‐grafted dextran copolymers

The whole controlled synthesis of novel amphiphilic polylactide (PLA)‐grafted dextran copolymers was achieved. The control of the architecture of such biodegradable and potentially biocompatible copolymers has required a three‐step synthesis based on the “grafting from” concept. The first step consisted of the partial silylation of the dextran hydroxyl groups. This protection step was followed by the ring‐opening polymerization of D ,L ‐lactide initiated from the remaining OH functions of the partially silylated polysaccharide. The third step involved the silylether group deprotection under very mild conditions. Based on previous studies, in which the control of the first step was achieved, this study is focused on the last two steps. Experimental conditions were investigated to ensure a controlled polymerization of D ,L ‐lactide, in terms of grafting efficiency, graft length, and transesterification limitation. After polymerization, the final step was studied in order to avoid degradation of both polysaccharide backbone and polyester grafts. The chemical stability of dextran backbone was checked throughout each step of the synthesis. PLA‐grafted dextrans and PLA‐grafted (silylated dextrans) were proved to adopt a core‐shell conformation in various solvents. Furthermore, preliminary experiments on the potential use of these amphiphilic grafted copolymers as liquid/liquid interface stabilizers were performed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2577–2588, 2004     

Ostwald ripening of oil-in-water emulsions stabilized by phenoxy-substituted dextrans

The stability of oil-in-water emulsions prepared using dextran, a natural polysaccharide, hydrophobically substituted with phenoxy groups, was studied. The evolution of the emulsion droplet size was investigated as a function of polymer concentration (Cp=0.2 to 1% w/w in a water phase) and the degree of phenoxy substitution (tau=4.2 to 15.7%). For the highest tau values, emulsions, which presented submicrometer droplets, were stable over more than 4 months at room temperature. The most substituted polymers clearly showed a better efficiency to lower the surface tension at the oil/water interface. DexP did not induce real viscosification of the continuous phase. The linearity of the particle volume variation with time, and the invariability of the volume distribution function, proved that Ostwald ripening was the main destabilization mechanism of the phenoxy dextran emulsions. The nature of the oil dispersed phase drastically affected the behavior of emulsions. While the emulsions prepared with n-dodecane presented a particle growth with time, only few size variations occurred when n-hexadecane was used. Furthermore, small ratios of n-hexadecane in n-dodecane phase reduced the particle growth due to the lower solubility and lower diffusion coefficient in water of n-hexadecane, which acted as a ripening inhibitor.     

Amphiphilic derivatives of dextran: adsorption at air/water and oil/water interfaces

Ionic amphiphilic dextran derivatives were synthesized by the attachment of sodium sulfopropyl and phenoxy groups on the native polysaccharide. A family of dextran derivatives was thus obtained with varying hydrophobic content and charge density in the polymer chains. The surface-active properties of polymers were studied at the air-water and dodecane-water interfaces using dynamic surface/interfacial tension measurements. The adsorption was shown to begin in a diffusion-limited regime at low polymer concentrations, that is to say, with the diffusion of macromolecules in the bulk solution. In contrast, at long times the interfacial adsorption is limited by interfacial phenomena: adsorption kinetics or transfer into the adsorbed layer. A semiempirical equation developed by Filippov was shown to correctly fit the experimental curves over the whole time range. The presence of ionic groups in the chains strongly lowers the adsorption kinetics. This effect can be interpreted by electrostatic interactions between the free molecules and the already adsorbed ones. The adsorption kinetics at air-water and oil-water interfaces are compared.     

Synthesis of monomethoxypolyoxyethylene-bound haemoglobins

Monomethoxypolyoxyethylene (M?_w?5000) was chemically modified and activated in order to react with the amino-groups of human haemoglobin. The best active polymeric derivatives were obtained by substituting a carboxymethoxyl group for the hydroxyl function of the polymer and by converting the carboxyl function into a N-hydroxysuccinimide active ester. When such modified polyoxyethylene derivatives were allowed to react with haemoglobin, soluble conjugates were formed with relatively low molecular weights. Some of the polymer-bound haemoglobins exhibit good oxygen-binding properties relative to unbound haemoglobin and could be suitable for use as erythrocyte substitutes.     

Synthetic Membrane Technology Sessions,Instrumentation Symposium

When a protein is exposed to a ligand linked to a water soluble polymer, a macrocomplex can be formed that can be isolated from the contaminant medium by different methods such as affinity partitioning or gel filtration. Ultrafiltration technique has also been tested in the separation of trypsin and chymotrypsin using a high molecular weight dextran—p-aminobenzamidine as a macroligand. Some theoretical considerations are given in order to evaluate the performance that can be expected from this biospecific complexation—ultrafiltration technique in the separation of biological species.     

The influence of cell geometry on the Godunov scheme applied to the linear wave equation

By studying the structure of the discrete kernel of the linear acoustic operator discretized with a Godunov scheme, we clearly explain why the behaviour of the Godunov scheme applied to the linear wave equation deeply depends on the space dimension and, especially, on the type of mesh. This approach allows us to explain why, in the periodic case, the Godunov scheme applied to the resolution of the compressible Euler or Navier–Stokes system is accurate at low Mach number when the mesh is triangular or tetrahedral and is not accurate when the mesh is a 2D (or 3D) cartesian mesh. This approach confirms also the fact that a Godunov scheme remains accurate when it is modified by simply centering the discretization of the pressure gradient.     

Noyaux potentiels associés à une filtration

We study from the point of view of potential theory some operators V which are “integrals of martingales” and noteworthy the formula (I + V)⁻¹ = I − N where N is a submarkovian kernel. We give an explicit expression of N when the filtration is finite and get the general case with an usual approximation procedure. Some links are made with the matrix theory (ultrametric and Stieltjes matrices) and the graph theory (flows and capacities) when the space is finite.

Résumé

On étudie, du point de vue de la théorie du potentiel, des opérateurs V du type “intégrales de martingale”, et notamment la formule (I + V)⁻¹ = I − N où N est un noyau sous-markovien. On donne une expression explicite de N dans le cas d'une filtration finie, et on traite le cas général par un procédé d'approximation usuel. On fait le lien avec la théorie des matrices (matrices ultramétriques et de Stieltjes) et la théorie des graphes (flots et capacités) quand l'espace est fini.     

Compared stability of Sepharose-based immunoadsorbents prepared by various activation methods.

During the use of chromatographic supports for the purification of proteins or the selective removal of substances by immunoaffinity, leakage of the antibodies immobilized on the matrix is systematically observed. When the cleansing of blood plasma by extracorporeal circulation is concerned, it is of prime importance that the immunoadsorbents exhibit an extensive chemical stability over the whole range of experimental conditions. To study and minimize this leakage, a matrix, Sepharose CL-4B, was activated by various chemical reagents and coupled to goat anti-apolipoprotein B polyclonal antibodies. Immunoadsorbents thus prepared were compared with those obtained earlier by cyanogen bromide activation. It turns out that divinyl sulphone- and tresyl chloride-activated supports lead to similar results in terms of coupling yield and adsorption capacity, but to a significant reduction in released antibodies.     

Hydrophobically Associating Alginate Derivatives: Surface Tension Properties of Their Mixed Aqueous Solutions with Oppositely Charged Surfactants

The comparative study of the interfacial properties of an anionic polysaccharide, sodium alginate (Alg), and its hydrophobically modified derivative (Alg-C(12)), covalently substituted by dodecyl chains (12% mol/mol saccharide unit), was carried out in the absence or in the presence of an oppositely charged surfactant, dodecyltrimethylammonium bromide (DTAB). The drastically different behaviors which were observed are interpreted in terms of the arrangement and mobility of the hydrophobic long alkyl chains, depending on the nature of their fixation, covalent or ionic, on the polysaccharide backbone. Copyright 2000 Academic Press.