Amphiphilic block copolymer nanocontainers as bioreactors

Self-assembly of an amphiphilic triblock copolymer carrying polymerizable end-groups is used to prepare nanometer-sized vesicular structures in aqueous solution. The triblock copolymer shells of the vesicles can be regarded as a mimetic of biological membranes although they are 2 to 3 times thicker than a conventional lipid bilayer. Nevertheless, they can serve as a matrix for membrane-spanning proteins. Surprisingly, the proteins remain functional despite the extreme thickness of the membranes and that even after polymerization of the reactive triblock copolymers. This opens a new field to create mechanically stable protein/polymer hybrid membranes. As a representative example we functionalize (polymerized) triblock copolymer vesicles by reconstituting a channel-forming protein from the outer cell wall of Gram-negative bacteria. The protein used (OmpF) acts as a size-selective filter, which allows only for passage of molecules with a molecular weight below 400 g mol^-1. Therefore substrates may still have access to enzymes encapsulated in such protein/polymer hybrid nanocontainers. We demonstrate this using the enzyme β-lactamase which is able to hydrolyze the antibiotic ampicillin. In addition, a transmembrane voltage above a given threshold causes a reversible gating transition of OmpF. This can be used to reversibly activate or deactivate the resulting nanoreactors. Received 22 August 2000     

Identification of flow mechanisms for a soft crystal

We study the behavior under flow of soft spherical micelles forming a fcc phase at high volume fraction. Due to the size (300 ?) of the elementary objects, the structure can be investigated through X-rays and neutron scattering, at rest and under flow in a Couette cell. Using scattering in two perpendicular directions, different mechanisms of flow are identified. At intermediate shear (around 100 s^-1) the system exhibits the so called layer sliding mechanism where two dimensional hexagonal compact planes of spheres align themselves with the Couette cell walls. At lower shear rate, the fcc structure is locally preserved, and the flow is mediated by defects between crystallites. At high shear rate, we observe the melting of the structure and a liquid-like structure factor. Moreover, we were able to use the existence of the layer sliding regime to generate a fcc monocrystal by annealing the satcking faults between the decorrelated planes created by the layer sliding. Received: 7 July 1997 / Received in final form: 16 January 1998 / Accepted: 5 March 1998     

Bending of charged flexible membranes due to the presence of macroions

We investigate the bending of flexible charged membranes due to the presence of rigid rodlike macroions in the framework of the Debye-Hückel approximation. When the macroions are fixed in space at some distance from the bilayer the membrane bends towards them; we calculate the exact deformation profile. On the other hand a macroion which is adsorbed on the membrane causes a deflection of the bilayer. Finally, we consider swollen lamellar polyanion/charged-lipid complexes where the macroions are intercalated between charged lipid bilayers. We predict the occurrence of a double adsorption (pinching effect) of the macroion for sufficiently flexible membranes. Received: 9 February 1998 / Revised: 9 June 1998 / Accepted: 2 July 1998     

Solubility of highly charged anionic polyelectrolytes in presence of multivalent cations: Specific interaction effect

Studies performed on strong polyelectrolytes and on a weak polyelectrolyte, sodium poly(acrylate), show that their stability in presence of multivalent cations depends on the chemical nature of the charged side groups of the polymer. For sulfonate groups (SO₃ ^-) or sulfate groups (OSO₃ ^-) phase separation generally occurs in presence of inorganic cations of valency 3 (as La³⁺) or larger and a resolubilization takes place at high salt concentration. The interactions of the polyelectrolyte with multivalent cations are of electrostatic origin and the phase diagrams are weakly dependent on the chemical nature of the polymer backbone and on the specificity of the counterions. For acrylate groups, (COO^-), the phase separation was observed with inorganic cations of valency 2 (as Ca²⁺) or larger without resolubilization at high salt concentration. The phase separation is due to a chemical association between cations and acrylate groups of two neighboring monomers of the same chain. This chemical association creates a hydrophobic complex by dehydrating both monomer and cation. With organic trivalent cation, as spermidine ⁺H₃N(CH₂)₄NH₂ ⁺(CH₂)₃NH₃ ⁺, where no chemical association occurs with the charged side groups COO^- or SO₃ ^- of the polyelectrolyte, similar phase diagrams were observed whatever was the polyelectrolyte with a resolubilization at high trivalent cation concentration. Received 3 March 1999 and Received in final form 2 September 1999     

Electric field light scattering by flexible linear polyelectrolytes in aqueous solution

Electric field light scattering results on aqueous solutions of linear, flexible NaPSS at minimal ionic strength are reported. Samples of molecular weights between 356 kg/mol and 2870 kg/mol were investigated. With increasing field strength the intensity as a function of wavenumber develops a pronounced oscillating behaviour. Besides the well-known first peak a second maximum is observed at the position at which a weak maximum for some samples already occurs at zero field. The overall intensity strongly depends on the frequency of the electric field. The electro-optical effect shows a maximum at 300 kHz. Increasing the particle concentration gives a large increase of the peak maximum, normalized to concentration. If plotted versus scattering angle the relative intensity increase is maximum for samples of medium molecular weight. The results strongly indicate a stretching and alignment of the chains, thus leading to or enlarging the short range order of the chains. Received 9 April 1999 and Received in final form 18 August 1999     

Lattice-Boltzmann study of spontaneous emulsification

We study the dynamics of spontaneous emulsification of an initially planar oil-water interface when surfactants are added. The thermodynamic properties of the ternary oil-water-surfactant system are modeled by a Ginzburg-Landau-type free energy. The lattice Boltzmann method is used to solve the dynamic equations. The dynamics is found to be governed by a complicated interplay of convection and diffusion as the two relevant transport mechanisms. As long as the interface is almost flat, we find the interfacial area to grow first exponentially and then linearly in time. Later finger-like structures form which grow with a constant velocity. The tip velocity is found to increase roughly linearly with the mobility of the amphiphile, and to decrease as with the solvent viscosity . Received 5 January 1999     

Rapid hydrogen peroxide release in cell suspensions ofCapsicum spp. elicited by fungal preparations

The release of H₂O₂ by plant cell suspensions elicited with crude hyphal wall preparations has been studied in a complex of plant genotypes (two cvs ofCapsicum annuum and one of C.frutescens) and fungus species(Phytophthora capsici, Ph. parasitica andVerticillium dahliae), representing several combinations of compatibility and both host and nonhost resistance. Production of H₂O₂ was revealed as peroxidasedependent and catalase-inhibited fluorescence quenching of an extracellular probe (Pyranine). All the plant genotypes responded to at least one elicitor, but the cell sensitivity showed a great age-dependent variability. Riboflavine and Mn²⁺ added in the incubation medium acted to some extent as primers for activated cell response, as well as a high Na⁺ concentration. Cell rest condition, however, was not removed. Some quantitative features of responsive plant/elicitor combinations (dose-response relation and lasting time) have been recorded. The complex PO/H₂O₂ of elicited cells could perform detectable lignin-like polymerization of an exogenous natural substrate (coniferyl alcohol). The time-course of pyranine oxidation and lignin-like polymer formation could be recorded by adopting a fluorimetric procedure that allowed sequential observations on the same cell sample. In one instance, the cell reaction seemed associated with thein planta host/parasite incompatibility.     

Effects of the degree of surface modification on the rheological responses of precipitated silica suspensions in benzyl alcohol

Two types of precipitated silica powders modified by poly (dimethylsiloxane) (PDMS) were suspended in benzyl alcohol and their rheological properties were investigated as a function of silica volume fraction, φ. The suspensions were classified into sol, pre-gel, and gel states based on the increase in φ. An increase in the degree of surface modification by PDMS caused gelation at higher φ. Plots of apparent shear viscosity against shear rate in the sol and pre-gel states of highly modified silica suspensions showed weak shear thickening behavior, while the same plots for silica suspensions with a low modification level exhibited shear thinning behavior. The dynamic moduli of hydrophobic suspensions in the pre-gel and gel states were dependent on the surface modification: the storage modulus G′ was larger than the loss modulus G″ in the linear region and these moduli increased with increasing φ, irrespective of the silica powder. The linear region of the φ range for the precipitated silica suspensions was wider than that for the fumed silica powders modified by PDMS suspended in benzyl alcohol, while the G′ value in the linear region for the precipitated silica suspensions was less than those for the fumed silica suspensions.