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.
In our recent study we showed that single-component emulsion drops, stabilized by proper surfactants, can spontaneously break symmetry and transform into various polygonal shapes during cooling [ Denkov Nature 2015 , 528 , 392 - 395 ]. This process involves the formation of a plastic rotator phase of self-assembled oil molecules beneath the drop surface. The plastic phase spontaneously forms a frame of plastic rods at the oil drop perimeter which supports the polygonal shapes. However, most of the common substances used in industry appear as mixtures of molecules rather than pure substances. Here we present a systematic study of the ability of multicomponent emulsion drops to deform upon cooling. The observed trends can be summarized as follows: (1) The general drop-shape evolution for multicomponent drops during cooling is the same as with single-component drops; however, some additional shapes are observed. (2) Preservation of the particle shape upon freezing is possible for alkane mixtures with chain length difference Δn ≤ 4; for greater Δn, phase separation within the droplet is observed. (3) Multicomponent particles prepared from alkanes with Δn ≤ 4 plastify upon cooling due to the formation of a bulk rotator phase within the particles. (4) If a compound, which cannot induce self-shaping when pure, is mixed with a certain amount of a compound which induces self-shaping, then drops prepared from this mixture can also self-shape upon cooling. (5) Self-emulsification phenomena are also observed for multicomponent drops. In addition to the three recently reported mechanisms of self-emulsification [ Tcholakova Nat. Commun. 2017 , ( 8 ), 15012 ], a new (fourth) mechanism is observed upon freezing for alkane mixtures with Δn > 4. It involves disintegration of the particles due to a phase separation of alkanes upon freezing.
Shape-anisotropic polymeric micro-and nanoparticles are of significant interest for the development of novel composite materials, lock-and-key assemblies, and drug carriers. Currently, syntheses require external confinement in microfluidic devices or lithographic techniques associated with significant infrastructure and low productivity, so new methods are necessary to scale-up such production efficiently. Here we report bottom-up polymerization of regular shape-anisotropic particles (polygonal platelets with different numbers of edges, with and without protruding asperities, and fibrilar particles with controllable aspect ratios), with size control over 4 orders of magnitude (~50 nm-1 mm). Polymerization also enables the study of much smaller shapes than could previously be studied in water suspensions and we study the fundamental limits of the self-shaping transition process driving these transformations for monomer oil droplets of stearyl methacrylate (SMA) monomer oil. We show the method is compatible with a variety of polymerizing monomers and functional modifications of the particles (e.g., composites with magnetic nanoparticles, oil soluble additives, etc). We also describe post-synthetic surface modifications that lead to hierarchical superstructures. The synthesis procedure has great potential in efficient nano-manufacturing as it can achieve scalable production of the above shapes in a wide range of sizes, with minimum infrastructure and process requirements, and little maintenance of the equipment.
In several recent studies, we showed that micrometer-sized oil-in-water emulsion droplets from alkanes, alkenes, alcohols, triglycerides, or mixtures of these components can spontaneously “self-shape” upon cooling into various regular shapes, such as regular polyhedrons, platelets, rods, and fibers (DenkovN. Denkov, N. Nature2015528392 CholakovaD. Cholakova, D. Adv. Colloid Interface Sci.201623590). These drop-shape transformations were explained by assuming that intermediate plastic rotator phase, composed of ordered multilayers of oily molecules, is formed beneath the drop surface around the oil-freezing temperature. An alternative explanation was proposed (GuttmanS. Guttman, S. Proc. Natl. Acad. Sci. USA2016113493 GuttmanS. Guttman, S. Langmuir2017331305), which is based on the assumption that the oil–water interfacial tension decreases to very low values upon emulsion cooling. Here, we present new results, obtained by differential scanning calorimetry (DSC), which quantify the enthalpy effects accompanying the drop-shape transformations. Using optical microscopy, we related the peaks in the DSC thermograms to the specific changes in the drop shape. Furthermore, from the enthalpies measured by DSC, we determined the fraction of the intermediate phase involved in the processes of drop deformation. The obtained results support the explanation that the drop-shape transformations are intimately related to the formation of ordered multilayers of alkane molecules with thickness varying between several and dozens of layers of alkane molecules, depending on the specific system. The new results provide the basis for a rational approach to the mechanistic explanation and to the fine control of this fascinating and industrially relevant phenomenon.
HypothesisMicrometer sized alkane-in-water emulsion drops, stabilized by appropriate long-chain surfactants, spontaneously break symmetry upon cooling and transform consecutively into series of regular shapes (Denkov et al., Nature 2015, 528, 392). Two mechanisms were proposed to explain this phenomenon of drop "self-shaping". One of these mechanisms assumes that thin layers of plastic rotator phase form at the drop surface around the freezing temperature of the oil.This mechanism has been supported by several indirect experimental findings but direct structural characterization has not been reported so far. ExperimentsWe combine small-and wide-angle X-ray scattering (SAXS/WAXS) with optical microscopy and DSC measurements of self-shaping drops in emulsions. FindingsIn the emulsions exhibiting drop self-shaping, the scattering spectra reveal the formation of intermediate, metastable rotator phases in the alkane drops before their crystallization. In addition, shells of rotator phase were observed to form in hexadecane drops, stabilized by C16EO10 surfactant. This rotator phase melts at ca. 16.6°C which is significantly lower than the melting temperature of crystalline hexadecane, 18°C. The scattering results are in a very good agreement with the complementary optical observations and DSC measurements.
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