The development of a comprehensive toolbox based on multi-level, high-throughput screening of MOFs for CO/N2 separations.

The separation of CO/N2 mixtures is a challenging problem in the petrochemical sector due to the very similar physical properties of these two molecules, such as size, molecular weight and boiling point. To solve this and other challenging gas separations, one requires a holistic approach. The complexity of a screening exercise for adsorption-based separations arises from the multitude of existing porous materials, including metal-organic frameworks. Besides, the multivariate nature of the performance criteria that needs to be considered when designing an optimal adsorbent and a separation process - i.e. an optimal material requires fulfillment of several criteria simultaneously - makes the screening challenging. To address this, we have developed a multi-scale approach combining high-throughput molecular simulation screening, data mining and advanced visualization, as well as process system modelling, backed up by experimental validation. We have applied our recent advances in the engineering of porous materials' morphology to develop advanced monolithic structures. These conformed, shaped monoliths can be used readily in industrial applications, bringing a valuable strategy for the development of advanced materials. This toolbox is flexible enough to be applied to multiple adsorption-based gas separation applications.

"Explosive" synthesis of metal-formate frameworks for methane capture: an experimental and computational study.

In this work, we show a solvent-free "explosive" synthesis (SFES) method for the ultrafast and low-cost synthesis of metal-formate frameworks (MFFs). A combination of experiments and in-depth molecular modelling analysis - using grand canonical Monte Carlo (GCMC) simulations - of the adsorption performance of the synthesized nickel-formate framework (Ni-FA) revealed extremely high quality products with permanent porosity, prominent CH4/N2 selectivity (ca. 6.0), and good CH4 adsorption capacity (ca. 0.80 mmol g-1 or 33.97 cm3 cm-3) at 1 bar and 298 K. This performance is superior to those of many other state-of-the-art porous materials.

Drug delivery and controlled release from biocompatible metal-organic frameworks using mechanical amorphization.

We have used a family of Zr-based metal-organic frameworks (MOFs) with different functionalized (bromo, nitro and amino) and extended linkers for drug delivery. We loaded the materials with the fluorescent model molecule calcein and the anticancer drug α-cyano-4-hydroxycinnamic acid (α-CHC), and consequently performed a mechanical amorphization process to attempt to control the delivery of guest molecules. Our analysis revealed that the loading values of both molecules were higher for the MOFs containing unfunctionalized linkers. Confocal microscopy showed that all the materials were able to penetrate into cells, and the therapeutic effect of α-CHC on HeLa cells was enhanced when loaded (20 wt%) into the MOF with the longest linker. On one hand, calcein release required up to 3 days from the crystalline form for all the materials. On the other hand, the amorphous counterparts containing the bromo and nitro functional groups released only a fraction of the total loaded amount, and in the case of the amino-MOF a slow and progressive release was successfully achieved for 15 days. In the case of the materials loaded with α-CHC, no difference was observed between the crystalline and amorphous form of the materials. These results highlight the necessity of a balance between the pore size of the materials and the size of the guest molecules to accomplish a successful and efficient sustained release using this mechanical ball-milling process. Additionally, the endocytic pathway used by cells to internalize these MOFs may lead to diverse final cellular locations and consequently, different therapeutic effects. Understanding these cellular mechanisms will drive the design of more effective MOFs for drug delivery applications.