Mesoporous organohydrogels from thermogelling photocrosslinkable nanoemulsions

We report the formation of mesoporous organohydrogels from oil-in-water nanoemulsions containing an end-functionalized oligomeric gelator in the aqueous phase. The nanoemulsions exhibit an abrupt thermoreversible transition from a low-viscosity liquid to a fractal-like colloidal gel of droplets with mesoscale porosity and solid-like viscoelasticity with moduli approaching 100 kPa, possibly the highest reported for an emulsion-based system. We hypothesize that gelation is brought about by temperature-induced interdroplet bridging of the gelator, as shown by its dependence on the gelator chemistry. The use of photocrosslinkable gelators enables the freezing of the nanoemulsion’s microstructure into a soft hydrogel nanocomposite containing a large fraction of dispersed liquid hydrophobic compartments, and we show its use in the encapsulation and release of lipophilic biomolecules. The tunable structural, mechanical and optical properties of these organohydrogels make them a robust material platform suitable for a wide range of applications.

Reconfigurable self-assembly through chiral control of interfacial tension

Charged nanoparticles as supramolecular surfactants for controlling the growth and stability of microcrystals

Microcrystals of desired sizes are important in a range of processes and materials, including controlled drug release^{1, 2}, production of pharmaceutics and food^{3, 4}, bio-⁵ and photocatalysis⁶, thin-film solar cells⁷ and antibacterial fabrics⁸. The growth of microcrystals can be controlled by a variety of agents, such as multivalent ions⁹, charged small molecules¹⁰, mixed cationic–anionic surfactants^{11, 12}, polyelectrolytes^{13, 14} and other polymers¹⁵, micropatterned self-assembled monolayers^{16, 17}, proteins¹⁸ and also biological organisms during biomineralization^{19, 20}. However, the chief limitation of current approaches is that the growth-modifying agents are typically specific to the crystalizing material. Here, we show that oppositely charged nanoparticles can function as universal surfactants that control the growth and stability of microcrystals of monovalent or multivalent inorganic salts, and of charged organic molecules. We also show that the solubility of the microcrystals can be further tuned by varying the thickness of the nanoparticle surfactant layers and by reinforcing these layers with dithiol crosslinks.

Self-limited plasmonic welding of silver nanowire junctions

Nanoscience provides many strategies to construct high-performance materials and devices, including solar cells, thermoelectrics, sensors, transistors, and transparent electrodes. Bottom-up fabrication facilitates large-scale chemical synthesis without the need for patterning and etching processes that waste material and create surface defects. However, assembly and contacting procedures still require further development. Here, we demonstrate a light-induced plasmonic nanowelding technique to assemble metallic nanowires into large interconnected networks. The small gaps that form naturally at nanowire junctions enable effective light concentration and heating at the point where the wires need to be joined together. The extreme sensitivity of the heating efficiency on the junction geometry causes the welding process to self-limit when a physical connection between the wires is made. The localized nature of the heating prevents damage to low-thermal-budget substrates such as plastics and polymer solar cells. This work opens new avenues to control light, heat and mass transport at the nanoscale.

Colloidal Synthesis of Wurtzite Cu₂ZnSnS₄ Nanorods and Their Perpendicular Assembly

The quaternary copper chalcogenide Cu₂ZnSnS₄ is an important emerging material for the development of low-cost and sustainable solar cells. Here we report a facile solution synthesis of stoichiometric Cu₂ZnSnS₄ in size-controlled nanorod form (11 nm × 35 nm). The monodisperse nanorods have a band gap of 1.43 eV and can be assembled into perpendicularly aligned arrays by controlled evaporation from solution.