Coil-helix transition in poly(L-glutamic acid): Evidence for a 3-state non-cooperative process.

A careful analysis of measurements of circular dichroism of poly(L-glutamic acid) (PGA) shows that the data can be very accurately described by introducing a third state for the PGA configuration, in addition to the helix and coil ones, and considering a simple equilibrium between these three states, without cooperativity. The third state is more conspicuous when high molecular weight polyethyleneglycol (PEG) is added. Excluded-volume effects shown by differences in the presence of short and long PEG chains suggest a direct interaction of PEG and PGA rather than an osmotic effect.

Crowding effect on helix-coil transition: beyond entropic stabilization.

We report circular dichroism measurements on the helix-coil transition of poly(L-glutamic acid) in solution with polyethylene glycol (PEG) as a crowding agent. The PEG solutions have been characterized by small angle neutron scattering and are well described by the picture of a network of mesh size ξ, usual for semi-dilute chains in good solvent. We show that the increase of PEG concentration stabilizes the helices and increases the transition temperature. But more unexpectedly, we also notice that the increase of concentration of crowding agent reduces the mean helix extent at the transition, or in other words reduces its cooperativity. This result cannot be taken into account for by an entropic stabilization mechanism. Comparing the mean length of helices at the transition and the mesh size of the PEG network, our results strongly suggest two regimes: helices shorter or longer than the mesh size.

Pink noise of ionic conductance through single artificial nanopores revisited.

We report voltage-clamp measurements through single conical nanopore obtained by chemical etching of a single ion track in polyimide film. Special attention is paid to the pink noise of the ionic current (i.e., 1/f noise) measured with different filling liquids. The relative pink-noise amplitude is almost independent of concentration and pH for KCl solutions, but varies strongly using ionic liquids. In particular, we show that depending on the ionic liquid, the transport of charge carriers is strongly facilitated (low noise and higher conductivity than in the bulk) or jammed. These results show that the origin of the pink noise can be ascribed neither to fluctuations of the pore geometry nor to the pore wall charges, but rather to a cooperative effect on ions motion in confined geometry.

Fluctuations of ionic current through lipid bilayers at the onset of peptide attacks and pore formation.

Voltage-clamp measurements on lipid bilayers at the onset of peptide attacks before pore formation are reported. With four different peptides [alamethicin, melittin, and two synthetic peptides of the leucine (L)-lysine(K) copolymers (LK series)], correlations of conductivity fluctuations slowly decay over four decades in time. This slow dynamics is interpreted as being due to fluctuations of peptide concentration at the crowded surface of the bilayer and found to be compatible with the t(-1/2) relaxation of the RSA model.

Scaling and continuum percolation model for enzyme-catalyzed gel degradation.

Enzyme-catalyzed gel degradation is inherently controlled by diffusion of enzymes in the gel. We report kinetics measurements on the gelatin-thermolysin system, varying solvent viscosity as well as gel and enzyme concentrations. Scaling relations and reduced variables are proposed which are shown to account for the experimental results. Finally, we argue that the nontrivial experimental dependence on enzyme concentration for the degradation time demonstrates that enzyme random walk is self-attracting, leading to a continuum percolation model for gel degradation.