Revealing the chemical and physical mechanisms underlying symmetry breaking and shape transformations is key to understanding morphogenesis. If we are to synthesize artificial structures with similar control and complexity to biological systems, we need energy- and material-efficient bottom-up processes to create building blocks of various shapes that can further assemble into hierarchical structures. Lithographic top-down processing allows a high level of structural control in microparticle production but at the expense of limited productivity. Conversely, bottom-up particle syntheses have higher material and energy efficiency, but are more limited in the shapes achievable. Linear hydrocarbons are known to pass through a series of metastable plastic rotator phases before freezing. Here we show that by using appropriate cooling protocols, we can harness these phase transitions to control the deformation of liquid hydrocarbon droplets and then freeze them into solid particles, permanently preserving their shape. Upon cooling, the droplets spontaneously break their shape symmetry several times, morphing through a series of complex regular shapes owing to the internal phase-transition processes. In this way we produce particles including micrometre-sized octahedra, various polygonal platelets, O-shapes, and fibres of submicrometre diameter, which can be selectively frozen into the corresponding solid particles. This mechanism offers insights into achieving complex morphogenesis from a system with a minimal number of molecular components.

The general mechanisms of structure and form generation are the keys to understanding the fundamental processes of morphogenesis in living and non-living systems. In our recent study (Denkov et al., Nature 528 (2015) 392) we showed that micrometer sized n-alkane drops, dispersed in aqueous surfactant solutions, can break symmetry upon cooling and "self-shape" into a series of geometric shapes with complex internal structure. This phenomenon is important in two contexts, as it provides: (a) new, highly efficient bottom-up approach for producing particles with complex shapes, and (b) remarkably simple system, from the viewpoint of its chemical composition, which exhibits the basic processes of structure and shape transformations, reminiscent of morphogenesis events in living organisms. In the current study, we show for the first time that drops of other chemical substances, such as long-chain alcohols, triglycerides, alkyl cyclohexanes, and linear alkenes, can also evolve spontaneously into similar non-spherical shapes. We demonstrate that the main factors which control the drop "self-shaping", are the surfactant type and chain length, cooling rate, and initial drop size. The studied surfactants are classified into four distinct groups, with respect to their effect on the "self-shaping" phenomenon. Coherent explanations of the main experimental trends are proposed. The obtained results open new prospects for fundamental and applied research in several fields, as they demonstrate that: (1) very simple chemical systems may show complex structure and shape shifts, similar to those observed in living organisms; (2) the molecular self-assembly in frustrated confinement may result in complex events, governed by the laws of elasto-capillarity and tensegrity; (3) the surfactant type and cooling rate could be used to obtain micro-particles with desired shapes and aspect ratios; and (4) the systems studied serve as a powerful toolbox to investigate systematically these phenomena.

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Two recent studies (Denkov et al., Nature 2015, 528, 392 and Guttman et al. Proc. Natl. Acad. Sci. U.S.A.2016, 113, 493) demonstrated that micrometer-sized n-alkane drops, dispersed in aqueous surfactant solutions, can break their spherical symmetry upon cooling and self-shape into a variety of regular shapes, such as fluid polyhedra, platelet-shaped hexagons, triangles, rhomboids, toroids, and submicrometer-diameter fibers. In the first study, the observed phenomenon was explained by a mechanism involving the formation of interfacial multilayer of self-assembled alkane molecules in the so-called rotator phases, templated by the frozen surfactant adsorption layer. Such phases are known to form in alkane droplets under similar conditions and are sufficiently strong to deform the droplets against the capillary pressure of a finite interfacial tension of several mN/m. The authors of the second study proposed a different explanation, namely, that the oil-water interfacial tension becomes ultralow upon cooling, which allows for surface extension and drop deformation at negligible energy penalty. To reveal which of these mechanisms is operative, we measure in the current study the temperature dependence of the interfacial tensions of several systems undergoing such drop-shape transitions. Our results unambiguously show that drop self-shaping is not related to ultralow oil-water interfacial tension, as proposed by Guttmann et al. These results support the mechanism proposed by Denkov et al., which implies that the large bending moment, required to deform an oil-water interface with an interfacial tension of 5 to 10 mN/m, is generated by an interfacial multilayer of self-assembled alkane molecules.

In self-emulsification higher-energy micrometre and sub-micrometre oil droplets are spontaneously produced from larger ones and only a few such methods are known. They usually involve a one-time reduction in oil solubility in the continuous medium via changing temperature or solvents or a phase inversion in which the preferred curvature of the interfacial surfactant layer changes its sign. Here we harness narrow-range temperature cycling to cause repeated breakup of droplets to higher-energy states. We describe three drop breakup mechanisms that lead the drops to burst spontaneously into thousands of smaller droplets. One of these mechanisms includes the remarkable phenomenon of lipid crystal dewetting from its own melt. The method works with various oil–surfactant combinations and has several important advantages. It enables low surfactant emulsion formulations with temperature-sensitive compounds, is scalable to industrial emulsification and applicable to fabricating particulate drug carriers with desired size and shape.