Robert Bradbury

Effect of charge on the mechanical properties of surfactant bilayers

Charge effects on the mechanical properties of surfactant bilayers have been measured, for a system with a low ionic strength, using small-angle neutron scattering and neutron spin echo spectroscopy. We report that, not only does increasing the surface charge density lead to greater structural ordering and a stiffening of the membrane, which is consistent with classical theory of charge effects on membranes, but also that the relaxation rate of the membrane thickness fluctuations decreases without affecting the fluctuation amplitude. From the relaxation rate we demonstrate, using recent theory, that the viscosity of the surfactant membrane is increased with surface charge density, which suggests that the amount of charge controls the diffusion behavior of inclusions inside the membrane. The present results confirm that the thickness fluctuation relaxation rate and amplitude are tuned independently since the membrane viscosity is only influencing the relaxation rate. This work demonstrates that charge stabilization of lamellar bilayers is not merely affected by intermembrane interactions and structural ordering but that intramembrane dynamics also have a significant contribution.

Probing Elastic and Viscous Properties of Phospholipid Bilayers Using Neutron Spin Echo Spectroscopy

The elastic and viscous properties of self-assembled amphiphilic membranes dictate the intricate hierarchy of their structure and dynamics ranging from the diffusion of individual molecules to the large-scale deformation of the membrane. We previously demonstrated that neutron spin echo spectroscopy measurements of model amphiphilic membranes can access the naturally occurring submicrosecond membrane motions, such as bending and thickness fluctuations. Here we show how the experimentally measured fluctuation parameters can be used to determine the inherent membrane properties and demonstrate how membrane viscosity and compressibility modulus are influenced by lipid composition in a series of simple phosphatidylcholine bilayers with different tail lengths as a function of temperature. This approach highlights the interdependence of the bilayer elastic and viscous properties and the collective membrane dynamics and opens new avenues to investigating the mechanical properties of more complex and biologically inspired systems.

Effect of interlamellar interactions on shear induced multilamellar vesicle formation

Shear-induced multilamellar vesicle (MLV) formation has been studied by coupling the small-angle neutron scattering (SANS) technique with neutron spin echo (NSE) spectroscopy. A 10% mass fraction of the nonionic surfactant pentaethylene glycol dodecyl ether (C12E5) in water was selected as a model system for studying weak inter-lamellar interactions. These interactions are controlled either by adding an anionic surfactant, sodium dodecyl sulfate, or an antagonistic salt, rubidium tetraphenylborate. Increasing the charge density in the bilayer induces an enhanced ordering of the lamellar structure. The charge density dependence of the membrane bending modulus was determined by NSE and showed an increasing trend with charge. This behavior is well explained by a classical theoretical model. By considering the Caillé parameters calculated from the SANS data, the layer compressibility modulus B¯ is estimated and the nature of the dominant inter-lamellar interaction is determined. Shear flow induces MLV formation around a shear rate of 10 s-1, when a small amount of charge is included in the membrane. The flow-induced layer undulations are in-phase between neighboring layers when the inter-lamellar interaction is sufficiently strong. Under these conditions, MLV formation can occur without significantly changing the inter-lamellar spacing. On the other hand, in the case of weak inter-lamellar interactions, the flow-induced undulations are not in-phase, and greater steric repulsion leads to an increase in the inter-lamellar spacing with shear rate. In this case, MLV formation occurs as the amplitude of the undulations gets larger and the steric interaction leads to in-phase undulations between neighboring membranes.