Many amphiphile–water mixtures will self-assemble into three-dimensional soft condensed structures known as inverse bicontinuous cubic phases. These structures are found in nature and have applications in nanotechnology. Here we show that by systematically varying amphiphile chain splay, we are able to control the relative stability of the inverse bicontinuous phases in a homologous series of monoglycerides in a predictable manner. In particular, we demonstrate that decreasing chain splay leads to the appearance of the primitive bicontinuous cubic phase while increasing chain splay reduces the channel size of the remaining two bicontinuous phases and tends to destabilize them with respect to the more curved inverse micellar and inverse hexagonal phases. These observations are consistent with a model in which the energetic stability of these phases is principally governed by the competing demands for homogeneous interfacial curvature and uniform chain packing and points to straightforward rules for engineering these self-assembling nanostructures.

The membrane protein bacteriorhodopsin (bR) can be reconstituted into the membrane of the lipid 1-monoolein (MO). This lipid forms a lyotropic liquid crystalline phase whose membrane has hyperbolic interfacial curvature. Using optical absorption spectroscopy and small angle X-ray scattering we have observed retinal unbinding from bR that is correlated with the degree of membrane interfacial curvature. The evidence suggests that bR is susceptible to membrane induced saddle splay for modest perturbations from equilibrium, but for more extreme distortions becomes stiff and resists membrane induced curvature.

The inverse bicontinuous cubic phases that form in some lipid–water mixtures are both important structural elements in cells and emerging vehicles for nanotechnological applications. We model the relative phase behaviour of the three known inverse bicontinuous cubic lyotropic phases as the sum of the curvature elastic and chain packing energy of the membrane, under the assumption that the membranes form interfaces of constant mean curvature. The model correctly predicts a number of apparently universal, qualitative features of the relative phase behaviour of the gyroid (QGII), double diamond (QDII) and primitive (QPII) inverse bicontinuous cubic phases. These are: the phase sequence QGII → QDII → QPII with increasing water composition; the absence in certain cases of QPII from the phase diagram; the destabilisation of QPII with an increase in the temperature and the negative slope of phase boundaries with respect to temperature. Unexpectedly the model predicts the potential existence of a re-entrant QGII at high water dilutions that swells indefinitely. This has yet to be reported, which may reflect the difficulty of stabilising and then detecting such swollen, fluid interfacial structures. However, in the model the presence of the highly swollen QGII phase causes the adjacent phase to exhibit an almost vertical phase boundary, a phenomenon which should be more readily detectable.

The lyotropic phase behaviour of two analogues of dioctadecyl dimethylammonium chloride was investigated. Both the inclusion of ester groups and subsequent minor structural rearrangement of the interfacial region of the surfactant were found to increase the chain melting temperature, although the overall phase behaviour remained similar for both compounds. Both of the two analogues were found to underswell, due to the formation of multi-lamellar vesicles. We also found that the inclusion of these ester linkages substantially reduced the metastability of the ‘gel phase’ in which the surfactants usually reside, accelerating the rate of collapse to a coagel state. This occurred via a nucleation-growth mechanism, where the growth was found to be one-dimensional, i.e. needle-like.

We show that we can manipulate the stability of a metastable gel phase, either to enhance its transitory nature or to “lock” it in. Using simple additives such as salt and fatty alcohol we were able to examine both the long-range effect, acting between charged bilayers, and short-range effects on the metastability. We found that the addition of salt to the cationic surfactant diethanolamine ester dimethyl ammonium chloride destabilized the gel phase, and at high concentrations it was able to decrease the length of time taken for the gel phase to revert to a hydrated solid “coagel” phase by an order of magnitude. The growth of the coagel phase was also found to be affected by increasing salt concentration, changing from needle-like (1D) to spherical growth. In contrast to the marked destabilization of the gel phase by salt, the addition of 1-octadecanol was found to prolong the lifetime of the gel phase almost indefinitely by disrupting the short-range packing between the surfactant molecules. This suggests that counterion binding plays a major role in the stability of metastable lamellar gel phases.