Elise Rotureau

Emulsifying properties of neutral and ionic polymer surfactants based on dextran

The emulsifying properties of neutral and anionic polymer surfactants derived from dextran (a neutral polysaccharide) are described. The kinetics of interfacial tension lowering by the amphiphilic polymers is first characterized by the use of semi-empirical equations. These equations allow the determination of the equilibrium value of surface tension by extrapolation to infinite time. Oil-in-water emulsions are prepared by sonication in the presence of the polymers previously dissolved in the aqueous phase. The average droplet size of the emulsions is determined immediately after preparation and followed during several weeks. Ageing of the emulsions is shown to result from molecular diffusion in accordance with previous work. The increase of droplet size with time is correctly depicted by the theoretical equation derived by Lifshitz, Slyozov and Wagner (LSW). It seems that creaming has no real effect on emulsion ageing up to 1 μm. The influence of oil nature is clearly related to the physical properties of the oil (solubility in water, diffusion coefficient, interfacial tension), a typical consequence of molecular diffusion. An increase in the amount of hydrophobic groups fixed on the polymer leads to slower ageing. An increase in the anionic group content of the polymer has the reverse effect. Ionic strength has a significant effect on ageing of emulsions stabilized by dextran derivatives bearing ionic groups. Increasing ionic strength in the continuous phase gives rise to slower emulsion ageing. An attempt is made to rationalise all these facts by relating emulsion ageing to the data of interfacial tension measurements. The results follow approximately the tendency predicted by the LSW equation.

Kinetics of metal ion binding by polysaccharide colloids.

The dynamics of metal sorption by a gel-like polysaccharide is investigated by means of the electrochemical technique of stripping chronopotentiometry (SCP). The measured response reflects the diffusive flux properties of the metallic species in the dispersion. The colloidal ligand studied here is a functionalized carboxymethyldextran. Its complexation with Pb(II) reveals a time dependence that identifies strong differences in the dynamic nature of the successive metal complexes formed. Apparently, the formation of intramolecular bidentate complexes requires a slow conformational reorganization of the macromolecule that becomes the rate-limiting step in the complexation reaction. The relevant parameters for metal binding and release kinetics are computed and thus provide knowledge of the time-dependent stability and lability of metal polysaccharide complexes.

Kinetic and thermodynamic determinants of trace metal partitioning at biointerphases: the role of intracellular speciation dynamics

There is a large body of work evidencing the necessity to evaluate chemical speciation dynamics of trace metals in solution for an accurate definition of their bioavailability to microorganisms. In contrast, the integration of intracellular metal speciation dynamics in biouptake formalisms is still in its early stages. Accordingly, we elaborate here a rationale for the interplay between chemodynamics of intracellular metal complexes and dynamics of processes governing metal biouptake under non-complexing outer medium conditions. These processes include the conductive diffusion of metal ions to the charged soft biointerphase, metal internalisation, excretion of intracellular free metal species and metal depletion from bulk solution. The theory is formulated from Nernst-Planck equations corrected for electrostatic and reaction kinetic terms applied at the biosurface and in the intracellular volume. Computational illustrations demonstrate how biointerfacial metal distribution dynamics inherently reflects the chemodynamic properties of intracellular complexes. In the practical limits of high and weak metal affinity to biosurface internalisation sites, the metal concentration profile is explicitly solved under conditions of strong intracellular complexing agents. Exact analytical expression is further developed for metal partitioning at equilibrium. This provides a way to evaluate the metal biopartition coefficient from refined analysis of bulk metal depletion measured at various cell concentrations. Depending on here-defined dimensionless parameters involving rates of metal internalisation-excretion and complex formation, the formalism defines the nature of the different kinetic regimes governing bulk metal depletion and biouptake. In particular, the conditions leading to an internalisation flux limited by diffusion as a result of demanding intracellular metal complexation are identified.

Structure of Multiresponsive Brush-Decorated Nanoparticles: A Combined Electrokinetic, DLS, and SANS Study

Particles consisting of a glassy poly(methyl methacrylate) core (ca. 40 nm in radius) decorated with a poly(N-isopropylacrylamide) anionic corona are synthesized using either methacrylic acid (MA) or acrylic acid (AA) as reactive comonomers in the shell. The different reactivity ratios of MA and AA toward N-isopropylacrylamide originates p(MA-N) and p(N-AA) particles with carboxylate charges supposedly located, preferentially, in the close vicinity of the core and at the shell periphery, respectively. The corresponding swelling features of these nanoparticles are addressed over a broad range of pH values (4 to 7.5), NaNO3 concentrations (3 to 200 mM), and temperatures (15 to 45 °C) by dynamic light scattering (DLS) and small angle neutron scattering (SANS). DLS shows that the swelling of the particle shells increases their thickness from ∼10 to 90 nm with decreasing temperature, ionic strength, or increasing pH, with the effect being more pronounced for p(N-AA) whose lower critical solution temperature is shifted to higher values compared to that of p(MA-N). Potentiometric titration and electrokinetic results further reflect the easier dissociation of carboxyl groups in p(N-AA) and a marked heterogeneous interfacial swelling of the latter with decreasing solution salt content. The DLS response of both particles is attributed to the multiresponsive nature of a peripheral dilute shell, while SANS only probes the presence of a quasi-solvent-free dense polymer layer, condensed on the core surface. The thickness of that layer slightly increases from ∼6 to 9.5 nm with increasing temperature from 15 to 45 °C (at 15 mM NaNO3 and pH 5) due to the collapse of the outer dilute shell layer. Overall, results evidence a nonideal brush behavior of p(MA-N) and p(N-AA) and their microphase segregated shell structure, which supports some of the conclusions recently formulated from approximate self-consistent mean-field computations.

Kinetic features of metal complexes with polysaccharide colloids: Impact of ionic strength

The dynamic features of metal binding by a gel-like polysaccharide, carboxymethyldextran (CMD), are investigated by stripping chronopotentiometry (SCP). This technique measures the diffusive flux properties of the metallic species in the ligand dispersion as defined by their concentration, mobility, and lability. Cadmium(II) forms only 1:1 complexes with CMD, the lability of which is well described by Eigen mechanism principles, that is, the removal of a water molecule from the inner hydration sphere of the metal ion is limiting the complex formation rate. Lead(II) and copper(II), however, also form intramolecular bidentate complexes with CMD, which requires a conformational reorganization of the polymeric chain. The reorganization process appears to be the rate-limiting step of the overall complexation reaction, which takes place on a time scale of hours. The influence of ionic strength on the rate of bidentate complex formation is insignificant. In contrast, its impact on the stability of the monodentate complex follows the corresponding Donnan potential of the soft CMD particle.

Structural effects of soft nanoparticulate ligands on trace metal complexation thermodynamics

Metal binding to natural soft colloids is difficult to address due to the inherent heterogeneity of their reactive polyelectrolytic volume and the modifications of their shell structure following changes in e.g. solution pH, salinity or temperature. In this work, we investigate the impacts of temperature- and salinity-mediated modifications of the shell structure of polymeric ligand nanoparticles on the thermodynamics of divalent metal ions Cd(ii)-complexation. The adopted particles consist of a glassy core decorated by a fine-tunable poly(N-isopropylacrylamide) anionic corona. According to synthesis, the charges originating from the metal binding carboxylic moieties supported by the corona chains are located preferentially either in the vicinity of the core or at the outer shell periphery (p(MA-N) and p(N-AA) particles, respectively). Stability constants (KML) of cadmium-nanoparticle complexes are measured under different temperature and salinity conditions using electroanalytical techniques. The obtained KML is clearly impacted by the location of the carboxylic functional groups within the shell as p(MA-N) leads to stronger nanoparticulate Cd complexes than p(N-AA). The dependence of KML on solution salinity for p(N-AA) is shown to be consistent with a binding of Cd to peripheral carboxylic groups driven by Coulombic interactions (Eigen-Fuoss mechanism for ions-pairing) or with particle electrostatic features operating at the edge of the shell Donnan volume. For p(MA-N) particulate ligands, a scenario where metal binding occurs within the intraparticulate Donnan phase correctly reproduces the experimental findings. Careful analysis of electroanalytical data further evidences that complexation of metal ions by core-shell particles significantly differ according to the location and distribution of the metal-binding sites throughout the reactive shell. This complexation heterogeneity is basically enhanced with increasing temperature i.e. upon significant increase of particle shell shrinking, which suggests that the contraction of the reactive phase volume of the particulate ligands promotes cooperative metal binding effects.

Light-Responsiveness of C12E6/Polymer Complexes Swollen with Dodecane

The association behavior of light-responsive azobenzene modified poly(sodium acrylate)s (AMPs) with C(12)E(6) (hexa-oxyethyleneglycol n-dodecyl ether) surfactant micelles swollen with dodecane was investigated using dynamic light scattering, UV spectrophotometry, and capillary electrophoresis techniques. AMPs complexes with oligoethyleneglycol n-alkyl ether show promising properties as emulsifiers for the light-triggered control of inversion of emulsions and the present work aims at giving new insights with respect to the nature of their photoresponse. Depending on the dodecane amount, the size of the spherical surfactant micelles was varied with radii ranging from 4 to 8 nm. AMPs can be viewed as long PAANa chains bearing several randomly distributed azobenzene groups. First, the binding behavior of the AMPs chains to the micelles swollen with various amounts of oil was thoroughly studied under dark-adapted conditions, which means that most azobenzene groups are in their trans conformation (less polar than the cis conformation obtained under UV irradiation). The binding of azobenzene to surfactant micelles, which leads to the formation of AMPs/surfactant complexes, is controlled by the energy of transfer of the azobenzene moiety from water to the micelle core and by the energy of loops formation since multiple attachments of azobenzene to a single micelle are expected with long AMPs chains. We show that the change in the energy of transfer of the azobenzene group between water and micelles upon increasing the amount of dodecane within the core of micelles was quite weak (not exceeding 0.7 kT). Within the investigated range of curvature, we observed that the energy of loops formation, which decreases with increasing micelle size (decrease of curvature or increase of oil amount) was similarly weak. The effect of the presence of dodecane on the photoresponse of the complex formation was investigated. It is shown that exposure to UV light markedly weakens the association of the AMPs with surfactant within a domain of surfactant concentrations much larger for swollen micelles than for pure surfactant micelles. Consequently, we suggest that emulsion inversion triggered by light could be due to the photomodulation of the binding of AMPs to colloidal objects with various and/or specific curvatures including surfactant mesophases or small size emulsion droplets.