No abstract

Porous materials provide a plethora of technologically important applications that encompass molecular separations, catalysis, and adsorption. The majority of research in this field involves network solids constructed from multitopic constituents that, when assembled either covalently or ionically, afford macromolecular arrangements with micro- or meso-porous apertures. Recently, porous solids fabricated from discrete organic cages have garnered much interest due to their ease of handling and solution processability. Although this class of materials is a promising alternative to network solids, fundamental studies are still required to elucidate critical structure-function relationships that govern microporosity. Here, we report a systematic investigation of the effects of building block shape-persistence on the porosity of molecular cages. Alkyne metathesis and edge-specific postsynthetic modifications afforded three organic cages with alkynyl, alkenyl, and alkyl edges, respectively. Nitrogen adsorption experiments conducted on rapidly crystallized and slowly crystallized solids illustrated a general trend in porosity: alkynyl > alkenyl > alkyl. To understand the molecular-scale origin of this trend, we investigated the short and long time scale molecular motions of the molecular cages using ab initio molecular dynamics (AIMD) and classical molecular dynamics (MD) simulations. Our combined experimental and computational results demonstrate that the microporosity of molecular cages directly correlates with shape persistence. These findings discern fundamental molecular requirements for rationally designing porous molecular solids.

Recent applications of ultrasound to the production of nanostructured materials are reviewed. Sonochemistry permits the production of novel materials or provides a route to known materials without the need for high bulk temperatures, pressures, or long reaction times. Both chemical and physical phenomena associated with high-intensity ultrasound are responsible for the production or modification of nanomaterials. Most notable are the consequences of acoustic cavitation: the formation, growth, and implosive collapse of bubbles, and can be categorized as primary sonochemistry (gas-phase chemistry occurring inside collapsing bubbles), secondary sonochemistry (solution-phase chemistry occurring outside the bubbles), and physical modifications (caused by high-speed jets, shockwaves, or inter-particle collisions in slurries).

Spray-coating using ultrasonic nebulization is reported for depositing nanoparticles on a TEM grid without many of the drying artifacts that are often associated with dropcasting. Spray-coating is suitable for preparing TEM samples on fragile support materials, such as suspended single-layer graphene, that rupture when samples are prepared by dropcasting. Additionally, because ultrasonic nebulization produces uniform droplets, nanoparticles deposited by spray-coating occur on the TEM grid in clusters, whose size is dependent on the concentration of the nanoparticle dispersion, which may allow the concentration of nanoparticle dispersions to be estimated using TEM.

Household items coated with various metals or titanium compounds can be heated to produce colorful films with nanoscale thicknesses.