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.

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.

No abstract

Microparticle adsorption and self-assembly at fluid interfaces are strongly affected by the particle three-phase contact angle θ. On the single-particle level, θ can be determined by several techniques, including colloidal-probe AFM, the gel-trapping technique (GTT) and the freeze-fracture shadow-casting (FreSCa) method. While GTT and FreSCa provide contact angle distributions measured over many particles, colloidal-probe AFM measures the wettability of an individual (specified) particle attached onto an AFM cantilever. In this paper, we extract θ for smooth microparticles through the analysis of force-distance curves upon particle approach and retraction from the fluid interface. From each retraction curve, we determine: (i) the maximal force, Fmax; (ii) the detachment distance, Dmax; and (iii) the work for quasistatic detachment, W. To relate Fmax, Dmax and W to θ, we developed a detailed theoretical model based on the capillary theory of flotation. The model was validated in three different ways. First, the contact angles, evaluated from Fmax, Dmax and W, are all close in value and were used to calculate the entire force-distance curves upon particle retraction without any adjustable parameters. Second, the model was successfully applied to predict the experimental force-distance curve of a truncated sphere, whose cut is positioned below the point of particle detachment from the interface. Third, our theory was confirmed by the excellent agreement between the particle contact angles obtained from the colloidal-probe AFM data and the ensemble-average contact angles measured by both GTT and FreSCa. Additionally, we devised a very accurate closed-form expression for W (representing the energy barrier for particle detachment), thus extending previous results in the literature.