Self-assembled structures having a regular hollow icosahedral form (such as those observed for proteins of virus capsids) can occur as a result of biomineralization processes, but are extremely rare in mineral crystallites. Compact icosahedra made from a boron oxide have been reported, but equivalent structures made of synthetic organic components such as surfactants have not hitherto been observed. It is, however, well known that lipids, as well as mixtures of anionic and cationic single chain surfactants, can readily form bilayers that can adopt a variety of distinct geometric forms: they can fold into soft vesicles or random bilayers (the so-called sponge phase) or form ordered stacks of flat or undulating membranes. Here we show that in salt-free mixtures of anionic and cationic surfactants, such bilayers can self-assemble into hollow aggregates with a regular icosahedral shape. These aggregates are stabilized by the presence of pores located at the vertices of the icosahedra. The resulting structures have a size of about one micrometre and mass of about 1010 daltons, making them larger than any known icosahedral protein assembly or virus capsid. We expect the combination of wall rigidity and holes at vertices of these icosahedral aggregates to be of practical value for controlled drug or DNA release.
The simplest, single-component biological membrane challenges accepted models of macromolecular interactions: lipid lamellar phases swell when immersed in monovalent salt solutions. Moreover, typical of a Hofmeister series, Br salts swell multilayers more than Cl salts, offering an excellent opportunity to investigate long-standing questions of ionic specificity. In accord with earlier measurements of liposome mobilities in electric fields, we find an added electrostatic repulsion of membranes due to anion binding, with a much stronger Br binding compared with Cl. However, contrary to the expectation that electrostatic repulsion should vanish in high salinity, swelling of lipid multilayers is monotonic with increasing salt concentration for both Br and Cl salts. The apparent contradiction is resolved by recognizing that although the electrostatic repulsion is progressively screened by increasing salt concentration, so is the van der Waals (vdW) attraction. Negligible in low salt, weakening of vdW forces becomes significant by the time electrostatic forces vanish. The result is a smooth monotonic swelling curve with no apparent distinction between low and high salt concentration regimes. Furthermore, when compared with theoretical predictions, measured vdW forces decay much too slowly with added salt. However, by accounting for the recently measured salt deficit near lipid bilayers, the expected scaling with Debye screening length is recovered. The combination of ion-specific binding and nonspecific ionic screening of lowfrequency fluctuations explains salt effects on lipid membrane interactions and, by extension, explains specific (Hofmeister) effects at macromolecular interfaces between low and high dielectric.electrostatics ͉ halides ͉ ion binding ͉ van der Waals ͉ hydration
From simple micelles in water, nearly spherical aggregates of amphiphilic molecules, to bicontinuous microemulsions, oil and water microheterogeneous mixtures stabilised by a surfactant film with both local and large-scale disordered structures, the world of surfactant-containing systems is fascinating. Depending on a subtle balance of attractive and repulsive interactions between molecules at interfaces, an extraordinarily rich polymorphism of aggregated structures can be observed. After summarising the basic general constraints controlling surfactant aggregation and the formation of interfaces, different structures of micelles and microemulsions are reviewed and related to interfacial film properties and the intermolecular interactions inside them. With such systems, both static (time-averaged) and dynamic properties control structures equally well. Structures of very different systems can be described in simple ways in terms of surfactant film average curvatures and flexibility.
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