Ionic physisorption on bubbles induced by pulsed ultra-sound.

Ion flotation processes involve the use of bubbles in order to separate ionic species from a mixed solution. Due to bubble interfaces we may assume null curvature at the molecular scale, where selective ion adsorption might be more easily investigated than with liquid-liquid extraction. In contrast to a classical flotation set-up, where bubbles are introduced via a glass frit, we use here a controlled sono-device generating cavitation bubbles which are initially absolutely clean. Moreover we have a faster process with a smaller device. The liquid phase resulting from the coalescence of the overflowing foam is enriched in some ions versus the initial brine. We show here that this effect follows the Hofmeister series and can be attributed to a weak adsorption of hydrated ions at the surfactant-water interface. The selectivity of alkali metals physisorbed at interfaces is analysed through the concentrations of competing ions remaining in solution by inductively coupled plasma optical emission spectrometry. Cationic selectivity, which is independent of the method for obtaining a foam, is discussed via the Gibbs free energy difference for bulk to hydrated surfactant monolayer. Relative values of effective adsorption energies are determined versus sodium ions taken as reference and correspond to 1-3% of the total hydration free energy.

CO2-switchable oligoamine patches based on amino acids and their use to build polyelectrolyte containers with intelligent gating.

The synthesis of well-defined, homodisperse oligoamine structures based on natural basic amino acids, so-called oligoamine "patches", is presented. They contain an intermediary number of cationic groups (exactly 11 amine groups) to allow sufficiently strong, but reversible, binding to anionic surfaces and polymers and are shown to be non-cytotoxic. Their overall charge can be switched in the ordinary pH range (5.5-7.5) between cationic and anionic by CO2 complexation and carbamate formation. This process turned out to be completely reversible, i.e. it can be used for the chemical "gating" of structures. Polyelectrolyte containers built with these patches as structural interlayers showed overall stability of the architecture, but a reversible gating of the permeation towards large water-soluble polymer species when contacted with CO2, as exemplified with a model dextrane.

Conformational diversity of the fibrillogenic fusion peptide B18 in different environments from molecular dynamics simulations.

The development of specific agents against amyloidoses requires an understanding of the conformational behavior of fibrillogenic peptides in different environments on the microscopic level. We present extensive molecular dynamics simulations of the fibrillogenic Bindin (103-120) B18 fusion peptide for several different environments: a water-trifluorethanol (TFE) mixture, pure water, aqueous buffer containing 100 mM NaCl, and a buffer-vapor interface. The peptide was studied as an isolated molecule in solution or at an interface. In the simulations, the conformational behavior of the peptide was found to strongly depend on the environment in agreement with experimental data. Overall, large portions of the peptide were unstructured. Preformed alpha-helical conformations were least stable in pure water and most stable in the water-TFE mixture and the buffer-vapor interface. In all environments, the alpha-helical conformation was most stable in the region around residues 113-116, which are mainly hydrophilic. Extended configurations in water or buffer folded into structures containing beta-sheets in agreement with data from circular dichroism spectroscopy. In buffer, the beta-sheet content was larger than in water and alpha-beta transitions were observed at elevated temperature. Beta-sheets were formed by hydrophobic residues; turns were formed by hydrophilic residues. A few typical beta-sheets that contain different residues are suggested. A B18 molecule in a strand-loop-strand conformation placed in buffer in contact with vapor was spontaneously adsorbed to the buffer-vapor interface with its hydrophobic side pointing toward the vapor phase. The adsorption induced the formation of turns at positions 108-119 and alpha-helical conformations in the region around residues 114-117. Alpha-helices were parallel to the interface plane in agreement with data from IR reflection absorption spectroscopy.

Counter-ion activity and microstructure in polyelectrolyte complexes as determined by osmotic pressure measurements.

We have investigated the activity of counter-ions at 60 degrees C through the osmotic coefficient K in solutions of anionic and cationic polyelectrolyte complexes of variable compositions. For excess of polyanion in the complexes (molar fraction of polycation f < 0.5), K increases as the polyanion is neutralized by the polycation (f getting closer to 0.5). By contrast, for an excess of polycation (f > 0.5), K stays constant or even slightly decreases as the polycation is getting neutralized by the polyanion. This asymmetric behavior depending on the charge of the complexes indicates that the globally negatively charged complexes are homogeneous and can be treated as a single polyelectrolyte of reduced linear charge density. On the other hand, the positively charged complexes show a micro-phase separation between neutral fully compensated microdomains and domains where the excess polycation is locally segregated. These two different microstructures are reminiscent of the coacervation and segregation regimes observed at higher concentrations and salinities, and also of polyelectrolyte complexes with oppositely charged surfactants. This interpretation is supported by two simple predictive models.

Metallosupramolecular Thin Polyelectrolyte Films.

Molecular recognition and electrostatic interaction of oppositely charged polyelectrolytes are combined in the fabrication of ultrathin metallosupramolecular multilayers [shown schematically in the picture, PEI=polyethyleneimine, PSS=poly(styrene sulfonate)]. The layers between the PSS layers are composed of an iron(II) bis(terpyridine) coordination polymer.