This work investigates the temperature-dependent micelle formation as well as the micellar structure of the saponin aescin. The critical micelle concentration ( c m c ) of aescin is determined from the concentration-dependent autofluorescence (AF) of aescin. Values between c m c aescin , AF (10 ∘ C) = 0.38 ± 0.09 mM and c m c aescin , AF (50 ∘ C) = 0.32 ± 0.13 mM were obtained. The significance of this method is verified by tensiometry measurements. The value determined from this method is within the experimental error identical with values obtained from autofluorescence ( c m c aescin , T ( WP ) (23 ∘ C) = 0.33 ± 0.02 mM). The structure of the aescin micelles was investigated by small-angle X-ray scattering (SAXS) at 10 and 40 ∘ C. At low temperature, the aescin micelles are rod-like, whereas at high temperature the structure is ellipsoidal. The radii of gyration were determined to ≈31 Å (rods) and ≈21 Å (ellipsoid). The rod-like shape of the aescin micelles at low temperature was confirmed by transmission electron microscopy (TEM). All investigations were performed at a constant pH of 7.4, because the acidic aescin has the ability to lower the pH value in aqueous solution.

Vesicle shape and bilayer parameters are studied by small-angle X-ray (SAXS) and small-angle neutron (SANS) scattering in the presence of the saponin aescin. We confirm successful incorporation of aescin molecules by analysis of the radii of gyration RG and study furthermore the impact of aescin incorporation on bilayer thickness parameters from the neutron and X-ray perspective. Additionally, the bending elasticity (κ) of these 1,2-dimyristoyl-sn-glycero-3-phosphocholine vesicle bilayers is studied in the presence of aescin. Neutron spin-echo spectroscopy (NSE) allows to detect subtle changes in the dynamics and κ of lipid membranes. Changes of κ are detectable at temperatures below and above the main phase transition temperature Tm of the lipid. The impact of aescin is much more significant below Tm. It has been found that below Tm the addition of aescin to the vesicles decreases the value of κ and softens the bilayer. Above Tm the value of κ increases with increasing aescin content and the bilayer becomes more rigid. Altogether, we demonstrate by analysis of the structure and dynamics of the vesicles that the impact of aescin strongly depends on the lipid state. Below Tm the membrane becomes fluidized and softer, above Tm solidified and stiffer compared to a DMPC membrane without additive at similar conditions.

This review discusses recent progress in physicochemical understanding of the action of the saponin β -aescin (also called β -escin), the biologically active component in the seeds of the horse chestnut tree Aesculus hippocastanum. β -Aescin is used in pharmacological and cosmetic applications showing strong surface activity. In this review, we outline the most important findings describing the behavior of β -aescin in solution (e.g., critical micelle concentration ( c m c ) and micelle shape) and special physicochemical properties of adsorbed β -aescin monolayers at the air–water and oil–water interface. Such monolayers were found to posses very special viscoelastic properties. The presentation of the experimental findings is complemented by discussing recent molecular dynamics simulations. These simulations do not only quantify the predominant interactions in adsorbed monolayers but also highlight the different behavior of neutral and ionized β -aescin molecules. The review concludes on the interaction of β -aescin with phospholipid model membranes in the form of bilayers and Langmuir monolayers. The interaction of β -aescin with lipid bilayers was found to strongly depend on its c m c . At concentrations below the c m c , membrane parameters are modified whereas above the c m c , complete solubilization of the bilayers occurs, depending on lipid phase state and concentration. In the presence of gel-phase phospholipids, discoidal bicelles form; these are tunable in size by composition. The phase behavior of β -aescin with lipid membranes can also be modified by addition of other molecules such as cholesterol or drug molecules. The lipid phase state also determines the penetration rate of β -aescin molecules into lipid monolayers. The strongest interaction was always found in the presence of gel-phase phospholipid molecules.

Mixtures of the phospholipid 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and the saponin β-aescin spontaneously form monodisperse, bilayered discoidal micelles (also known as "bicelles" or "nanodisks") in aqueous solution. Such bicelles form below the melting temperature of DMPC when the phospholipids are in the rigid L β′ state and are precursors of spontaneously formed vesicles. The aescin concentration must be far above the cmc aescin (≈0.3−0.4 mM). It was found that the shape and size of the bicelles are tunable by composition. High amounts of aescin decrease the size of the bicelles from diameters of ∼300 Å at 7 mol % to ∼120 Å at 30 mol % β-aescin. The structures are scrutinized by complementary small-angle X-ray and neutron scattering experiments. The scattering curves are subsequently analyzed by a model-independent (indirect Fourier transform analysis) and a model-based approach where bicelles are described as polydisperse bilayer disks encircled by a β-aescin rim. Moreover, the monomodal distribution and low polydispersity of the samples were confirmed by photon correlation spectroscopy. The discoidal structures were visualized by transmission electron microscopy.