Catherine Ringard-Lefebvre

Phase behavior of fully hydrated DMPC-amphiphilic cyclodextrin systems.

With the aim of exploring relationships between the chemical structure and the physico-chemical properties of amphiphilic beta-cyclodextrin, a reappraisal of the obtaining of pure heptakis (2,3-di-O-hexanoyl)-beta-cyclodextrin (beta-CDC(6)) was undertaken. In this paper the chemical characterization of the newly synthesized beta-CDC(6) and its ability to form mixed structures with dimyristoylphosphatidylcholine (DMPC) are reported. Miscibility of the two amphiphiles is examined: (i) in monolayers formed at the air-water interface by analyzing the surface pressure-area isotherms; and (ii) in fully hydrated mixtures by differential scanning calorimetry (DSC) and X-ray diffraction at small and wide angles. Results demonstrate that the beta-cyclodextrin derivative is partially miscible to the phospholipid: intimate mixing occurs at beta-CDC(6) molar ratios smaller than 7-15 mol%, depending on the dimensional scale considered, while beyond these compositions phase separation is observed. At the air-water interface, the miscibility region of the two compounds shows non-ideal behavior characterized by the non-additivity of the molecular areas in the mixed monolayers. At the three-dimension level, the formation of a beta-CDC(6)/DMPC mixed lamellar phase occurs except at beta-CDC(6) molar ratios close to 5 mol% at which a highly ordered structure is depicted below the solid-to-liquid state transition of the DMPC hydrocarbon chains. At beta-CDC(6) contents higher than 7 mol%, the mixed assemblies coexist with excess amphiphilic cyclodextrin which then forms a separated hexagonal structure.

Inclusion Complex of n-Octyl β-d-Glucopyranoside and α-Cyclodextrin in Aqueous Solutions: Thermodynamic and Structural Characterization

Complex formation between octyl beta-D-glucopyranoside (OG) and alpha-cyclodextrin (alphaCD) was investigated on the basis of three highly accurate and appropriate experimental techniques. First, surface tension measurements showed that alphaCD directly acts on the surfactant monomers in the aqueous phase, leading to progressive depletion of the air-water interface with increasing cyclodextrin contents. Significant shift of OG critical micelle concentration (cmc) was consequently observed: the higher alphaCD concentration, the higher the cmc value. Experiments performed at surfactant and cyclodextrin concentrations in the Gibbs regime of surface tension versus OG content were performed on one hand to establish Jobs plot that showed 1:1 stoichiometry of the OG-alphaCD complex and on the other hand to calculate the association constant found equal to (1.85 +/- 0.35) x 10(3) L mol(-1). An inclusion process of the surfactant alkyl residue within the cyclodextrin cavity was confirmed by one-dimensional (1)H NMR, and the structure of the mixed assembly was extensively characterized by two-dimensional NOESY (1)H NMR. OG penetrates alphaCD so that its hydrocarbon chain is embedded inside the cyclodextrin cavity, and its polar head as well as the alpha-methylene group emerges outside the alphaCD secondary face. Solubility behavior of the OG-alphaCD complex in a wide range of host-guest ratios and concentrations was finally examined by turbidity recording and optical microscopy. At very low free cyclodextrin levels in the solution, the complex presented high solubility behavior up to more than 70 mM. By increasing nonassociated alphaCD in the mixture, propensity of the cyclodextrin molecules to crystallize was observed at concentrations far below the 100 mM aqueous solubility of the pure cyclodextrin. The hexagonal shape of the crystals seen in the optical microscopy images suggested they were, partially at least, composed of the solid complex.

Scale-up of nanoemulsion produced by emulsification and solvent diffusion.

The scale-up of nanoemulsions (NEs) produced by emulsification and solvent diffusion process was successfully achieved in the present work. Up to 1500 mL of NEs were produced with olive oil, castor oil, almond oil, or Arlamol™ E by using a Y-shaped mixer device. NE droplet sizes were significantly modulated from 290 to 185 nm by changing the process parameters without modification of the formulation composition. Smaller NE droplet sizes were obtained by (1) decreasing the internal diameter of the Y-mixer from 5 to 0.8 mm, (2) increasing the flow rates of the organic and the aqueous phases upon mixing, and (3) increasing the temperature of the experiment from 5°C to 40°C. All the results of NE diameters (d(sc) ) expressed as a function of the Reynolds number (Re) and the shear rate inside the Y-mixer (\documentclass{article}\usepackage{amssymb}\begin{document}\pagestyle{empty}

Study of Surface Charge Instabilities by EOF Measurements on a Chip: A Real-Time Hysteresis and Peptide Adsorption Based Methodology

\dot \gamma

Adhesion of polymer monolayers to the water subphase. Effect of solvents and polymer functionality

\end{document}) showed the existence of typical power-law relationships: d(sc) = 10(2.82) Re(- 0.14) and \documentclass{article}\usepackage{amssymb}\begin{document}\pagestyle{empty}

Drug-Cyclodextrin Association Constants Determined by Surface Tension and Surface Pressure Measurements.

d_{{\rm sc}} = 10^{2.60} \dot \gamma ^{- 0.06}

Effect of spread amphiphilic β-cyclodextrins on interfacial properties of the oil/water system

\end{document}, respectively. The existence of these power-laws for NE formation by emulsification and solvent diffusion process has never been reported in the literature yet and constitutes a new finding in this work. We definitely proved that the high turbulences created upon NE formation are the most important parameter allowing to decrease droplet size.

Drug-cyclodextrin association constants determined by surface tension and surface pressure measurements. II. Sequestration of water insoluble drugs from the air-water interface : Retinol-β cyclodextrin system

This paper describes the measurement of the electroosmotic mobility (EOF) in a Wheatstone fluidic bridge (μFWB) as a direct probe of the surface instability. The variation of EOF known as one major contribution of the electrokinetic migration has been determined with a real-time measurement platform after different conditionings on chips. We also scan the pH of the background electrolytes with three different ionic strengths to evaluate the dependencies of the EOF as a function of the pH. A hysteresis methodology has been developed for probing the surface charge instabilities. EOF mobility has been recorded during on-a-chip electrophoresis to estimate the effect of such instability on the analytical performance. As expected, our experimental curves show that a decrease in the ionic strength increases the surface charge stability of the hybrid microchip. This result demonstrates that ionic exchanges between the surface and the fluid are clearly involved in the stability of the surface charge. With this original method based on real-time EOF measurement, the surface state can be characterized after hydrodynamic and electrophoresis sequences to mimic any liquid conditioning and separation steps. Finally, as a demonstrative application, isotherms of the adsorption of insulin have been recorded showing the change in surface charge by unspecific adsorption of this biomolecule onto the microfluidic channels wall. These methodologies and findings could be particularly relevant to investigating various analytical pathways and to understanding the molecular mechanisms at solid/liquid interfaces.

Behavior of poly(D,L-lactic acid) monolayers at the air-water interface. Effect of spreading solvents

Abstract The properties and the organization of poly (D, L-lactic acid) monolayers spread at the air/water interface were shown to be dramatically dependent on whether these monolayers have been spread from a good or a bad solvent. Whereas a good solvent, such as chloroform, favored the deployment of polymer chains from their coiled structure in solution to the unfolded structure, a bad solvent, as exemplified by acetone, enhanced strong intersegment interactions resulting in the formation of microdomains capable of respreading and favored adhesion of the polymer monolayer to water. Independently carried out experiments with monolayers of ester derivatives of hyaluronic acid demonstrated that the nature of a chemical group substituted on the glucuronic acid moieties of the polymer can considerably influence surface properties of these monolayers. Thus, if monolayers of the ethyl ester derivative were shown to be rather compressible, those of the benzyl ester derivative were more rigid and, relative to the...