Where are those lipid nano rings?

Highly curved toroidal micelles with diameters as small as 100 nm have been successfully constructed by self-assembly of amphiphilic block copolymers. These structures may have potential applications in gene or drug delivery. Experimental observations suggest that toroidal micelles likely originate from spherical or disc-like micelles which are tricked into forming toroidal micelles upon external stimuli ('smart' materials). Since self-assembly of polymeric and lipid surfactants is guided by the same physical principles, we hypothesize that 'smart' lipid surfactants can be equivalently tricked into forming highly curved toroidal micelles that are tenfold smaller (≃10 nm diameter). Paradoxically, these 'nano rings' have never been observed. Using coarse-grained molecular dynamics (MD) simulations in conjunction with a state-of-the-art free energy calculation method (a string method), we illustrate how a thermo-responsive lipid surfactant is able to form toroidal micelles. These micelles originate from disc-like micelles that are spontaneously perforated upon heat shocking, thereby supporting a longstanding hypothesis on the possible origin of polymeric toroidal micelle phases observed in experiments. We illustrate that kinetically stable 'nano rings' are substantially shorter lived than their tenfold larger polymeric analogs. The estimated life-time (milliseconds) is in fact similar to the characteristic breaking time of the corresponding worm-like micelle. Finally, we resolve the characteristic finger print which 'nano rings' leave in time-resolved X-ray spectra and illustrate how the uptake of small DNA fragments may enhance their stability. Despite a shared kinetics of self-assembly, length scale dependent differences in the life-time of surfactant phases can occur when phases are kinetically rather than thermodynamically stable. This results in the apparent absence or presence of toroidal micelle phases on different length scales. Our theoretical work precisely illustrates that the universality of surfactants nevertheless remains conserved even at different length scales.