Elastometry of deflated capsules: elastic moduli from shape and wrinkle analysis.

Elastic capsules, prepared from droplets or bubbles attached to a capillary (as in a pendant drop tensiometer), can be deflated by suction through the capillary. We study this deflation and show that a combined analysis of the shape and wrinkling characteristics enables us to determine the elastic properties in situ. Shape contours are analyzed and fitted using shape equations derived from nonlinear membrane-shell theory to give the elastic modulus, Poisson ratio and stress distribution of the membrane. We include wrinkles, which generically form upon deflation, within the shape analysis. Measuring the wavelength of wrinkles and using the calculated stress distribution gives the bending stiffness of the membrane. We compare this method with previous approaches using the Laplace-Young equation and illustrate the method on two very different capsule materials: polymerized octadecyltrichlorosilane (OTS) capsules and hydrophobin (HFBII) coated bubbles. Our results are in agreement with the available rheological data. For hydrophobin coated bubbles, the method reveals an interesting nonlinear behavior consistent with the hydrophobin molecules having a rigid core surrounded by a softer shell.

Wrinkling in the deflation of elastic bubbles.

The protein hydrophobin HFBII self-assembles into very elastic films at the surface of water; these films wrinkle readily upon compression. We demonstrate and study this wrinkling instability in the context of non-planar interfaces by forming HFBII layers at the surface of bubbles whose interfaces are then compressed by deflation of the bubble. By varying the initial concentration of the hydrophobin solutions, we are able to show that buckling occurs at a critical packing fraction of protein molecules on the surface. Independent experiments show that at this packing fraction the interface has a finite positive surface tension, and not zero surface tension as is usually assumed at buckling. We attribute this non-zero wrinkling tension to the finite elasticity of these interfaces. We develop a simple geometrical model for the evolution of the wrinkle length with further deflation and show that wrinkles grow rapidly near the needle (used for deflation) towards the mid-plane of the bubble. This geometrical model yields predictions for the length of wrinkles in good agreement with experiments independently of the rheological properties of the adsorbed layer.

Charge reversal by salt-induced aggregation in aqueous lactoferrin solutions.

We have observed salt-induced aggregation in lactoferrin solutions using dynamic light scattering (DLS). Aggregates start to form once the ionic strength exceeds 10 mM, and are of opposite charge to their monomer building blocks. The presence of aggregates was monitored by electrophoretic measurements, in which the change of isoelectric point in lactoferrin solutions was observed and found to depend on the concentration of background electrolyte. Complimentary atomic force microscopy (AFM) imaging of adsorbed lactoferrin films demonstrated that for negatively charged surfaces (mica, glass) the topography of the adsorbed film remains invariant to changes in ionic strength, whilst for positively charged surfaces (chitosan coated mica) we observed a salt-induced transition in deposited architecture, with approximately 100 nm aggregates being deposited together with monomers for ionic strengths in excess of 10 mM. The size of aggregates observed with AFM is consistent with those observed using DLS. These results suggest that negatively charged lactoferrin aggregates adsorb only onto positively charged surfaces, whereas isolated lactoferrin molecules are sufficiently amphiphilic and adsorb at surfaces of either charge, although without producing a charge inversion effect.