The adsorption and reaction behaviors of HF on the α-Al(2)O(3)(0001) surface are systematically investigated using density functional theory method. By increasing the number of HF molecules in a p(2 × 1) α-Al(2)O(3)(0001) slab, we find that HF is chemically dissociated at low coverage; while both physical and dissociative adsorption occurs at a 3/2 monolayer (ML) coverage. At the same coverage (1.0 ML), diverse configurations of the dissociated HF are obtained in the p(2 × 1) model; while only one is observed in the p(1 × 1) slab due to its smaller surface area compared with the former one. Preliminary fluorination reaction study suggests that the total energy of two dissociated HF in the p(2 × 1) slab increases by 1.00 and 0.72 eV for the formation and desorption of water intermediate, respectively. The coadsorption behaviors of HF and H(2)O indicate that the pre-adsorbed water is unfavorable for the fluorination of Al(2)O(3), which is well consistent with the experimental results. The calculated density of states show that the peak of σ(H-F) disappears, while the peaks of σ(H-O) and σ(Al-F) are observed at -8.4 and -5 to -3 eV for the dissociated HF. Charge density difference analysis indicates that the dissociated F atom attracts electrons, while no obvious changes on electrons are observed for the surface Al atoms.

Owing to the high surface area and porosity, metal− organic frameworks (MOFs) could be utilized as both nanocarriers of biopharmaceuticals and nanoreactors to organize cascade biological reactions with great potential in cancer treatment. However, nanoscale MOFs suitable for biomedical applications rely on harsh preparation conditions. Here, we utilized tryptophan to modulate the morphology and optical properties of zeolitic imidazolate framework-8 (ZIF-8) as nanocarrier to efficiently encapsulate the enzyme and mRNA. Under room temperature in an aqueous solution, tryptophan would coordinate with zinc ions to form ZIF-8:Trp with a decreased size from the μm range to sub-200 nm. In addition, cargo release could be monitored in real time via fluorescence red-shift effects. Besides being used as nanocarriers of biomolecules, ZIF-8:Trp could also be utilized as nanoreactors to induce cascade reactions to produce reactive oxygen and nitrogen species. Overall, this nanosized ZIF-8:Trp could provide a new strategy for preparation of cascade bioreactions and provide new insight for gas therapy.

In this work, we have successfully prepared core–shell nanoparticles (Fe3O4@PDA) wrapped with Ag using a simple and green synthesis method.

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