Oil-water Pickering emulsions of about 200 nm were stabilized by nanosized hydrophilic silica after a simple surface treatment method. We have modified the aqueous silica nanoparticle dispersions by simple adsorption of oleic acid to their surfaces, improving the hydrophobicity of the particles while maintaining their charge and stability. The adsorption was monitored by small-angle X-ray scattering and electrophoretic measurements to estimate the interparticle interactions and surface charges. The effect of various parameters, such as nanoparticle concentration, amount of oleic acid, ionic strength, and pH, on the droplets' size and stability was investigated by dynamic light scattering. Furthermore, the ability of these modified silica nanoparticles to stabilize long-chain alkanes, liquid paraffin, and liquid-crystalline phases was examined.
Thymine (Thy) or 2,6-diamino-1,3,5-triazine (DAT) end-groups were efficiently installed on well-defined polyethylenes (PEs) synthesized by catalyzed chain growth (CCG) polymerization. Mono-and bifunctional low-molar mass PEs (1200−1500 g•mol −1 ) formed lamellar morphologies with long-range order upon cooling from the melt due to microphase segregation of polar supramolecular units and apolar PE chains. Crystallization of Thy functions into rigid planes at 180 °C induced very long-range lamellar order in Thy-functionalized PEs and dramatically suppressed PE crystallization (from 67% to 19%). DAT-functionalized PEs, whose end-groups do not crystallize, showed slightly reduced PE crystallinity (62%) and less long-range order, since assembly was instead driven by PE crystallization. Mechanical analysis of the bifunctional PEs demonstrated high moduli roughly proportional to PE crystallinity but low strains at break due to the absence of chain entanglements and/or tie chains between crystalline lamellae. This work offers important insights for designing supramolecular systems with tunable thermal and mechanical properties.
Transfer of lipids between droplets in Pickering emulsions has been studied by time-resolved small-angle X-ray scattering (SAXS). The special features of self-assembled liquid-crystalline phases have been applied to examine the kinetics of internal phase reorganization imposed by lipid release and uptake by the droplets. The findings reveal faster transfer kinetics in Pickering emulsions than in emulsions stabilized with Pluronic F127. It is shown that the transfer kinetics can be accelerated by adding free surfactant to the dispersions and that this acceleration becomes more dominant when micelles are formed. The effect of immobilization of the droplets has been studied by incorporating them into the appropriate hydrogel network. The droplets are arrested, and the transfer slows down significantly at high enough concentrations of the hydrogel where nonergodic systems are obtained.
Copper indium sulfide nanocrystals with sizes of 3–4 nm were synthesized from metal xanthates in a hot injection reaction. After ligand exchange, their performance as acceptors in polymer/nanocrystal hybrid solar cells was evaluated.
The transfer kinetics of lipids between internally self-assembled droplets of O/W emulsions is studied. The droplets (isasomes) consist of various liquid-crystalline phases or W/O microemulsions stabilized by a polymeric stabilizer F127. The various internal phases were identified by the relative peak positions in the small-angle X-ray scattering (SAXS) curves. An arrested system composed of isasomes embedded in a gel matrix actually provides an additional possibility to control these systems in terms of the release of various host molecules. These experiments have been applied to examine the kinetics of the internal phase reorganization imposed by the lipids' release and uptake by the droplets embedded in a κ-carrageenan (KC) hydrogel network. Increasing the concentration of the gelling agent slows down the transfer from one droplet to the other through the aqueous phase. We examined the region where the free diffusion is stopped. i.e., the point where the system changes from the ergodic to the nonergodic state and the kinetics is essentially slowed down. This effect can be balanced by the addition of small amounts of free polymeric stabilizer, which speeds up the kinetics. This is even possible in the case of highly arrested dynamics of the emulsion droplets, as found for the highest KC hydrogel concentrations forming nonergodic systems.
Monoglycerides form lipophilic liquid-crystalline (LC) phases when mixed with water. The corresponding LC nanostructures coexist with excess water, which is a necessary condition for the formation of internally nanostructured dispersed particles. These nanostructures comprise bicontinuous cubic phases, inverted hexagonal phases, and inverted micellar cubic phases. The dispersed particles are therefore named cubosomes, hexosomes, or micellar cubosomes. Such dispersions are usually stabilized by hydrophilic high-molecular-weight triblock (TB) copolymers. Another way to stabilize such dispersions is by forming the so-called Pickering or Ramsden emulsions using nanoparticles as stabilizers. In this contribution, we explore the possibility of forming and stabilizing inverted or reverse systems, that is, dispersions of hydrophilic LC phases in an excess oil phase like tetradecane. Our aim was to change from oil-in-water emulsions to water-in-oil emulsions, where the water phase is a LC phase in equilibrium with excess oil and where the oil is nonpolar, for example, an alkane. This work consists of three parts: (1) to find a hexagonal hydrophilic LC phase that can not only incorporate a certain amount of tetradecane but can also coexist with excess tetradecane in the case of higher oil concentration, (2) to find a suitable stabilizer-either polymeric or nanoparticle type-that can stabilize the emulsion without destroying the hexagonal LC phase, and finally (3) to check the stability of this reverse hexosome emulsion. We discovered that it is possible to create a hexagonal hydrophilic LC phase with short-chain nonionic surfactants such as polyethylene glycol alkyl ethers or with high-molecular-weight TB copolymers of type A-B-A. Furthermore, it is possible to successfully stabilize the reverse hexosomes with low hydrophilic-lipophilic balance TB copolymers-either synthesized in our laboratory or commercially available ones-as well as with hydrophobized, commercially available silica nanoparticles.
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