Current research fields of metal-organic frameworks (MOFs), which are being developed in the last 5-10 years by Russian scientific institutions and universities, are generalized. The review encompasses the design, synthesis, topological description, and prediction of MOF properties, the development of methods for their chemical engineering and modification, their investigation by modern physicochemical techniques, and the creation of functional materials based on porous frameworks (heterogeneous catalysts, highly efficient and highly selective sorbents of the new generation, conducting materials, systems for the target drug delivery).
Zeolite imidazolate framework-8 (ZIF-8) is a promising platform for drug delivery, and information regarding the stability of ZIF-8 nanoparticles in cell culture media is essential for proper interpretation of in vitro experimental results. In this work, we report a quantitative investigation of the ZIF-8 nanoparticle’s stability in most common cell culture media. To this purpose, ZIF-8 nanoparticles containing sterically shielded nitroxide probes with high resistance to reduction were synthesized and studied using electron paramagnetic resonance (EPR). The degradation of ZIF-8 in cell media was monitored by tracking the cargo leakage. It was shown that nanoparticles degrade at least partially in all studied media, although the degree of cargo leakage varies widely. We found a strong correlation between the amount of escaped cargo and total concentration of amino acids in the environment. We also established the role of individual amino acids in ZIF-8 degradation. Finally, 2-methylimidazole preliminary dissolved in cell culture media partially inhibits the degradation of ZIF-8 nanoparticles. The guidelines for choosing the proper cell culture medium for the in vitro study of ZIF-8 nanoparticles have been formulated.
Two new isostructural microporous coordination frameworks [Mn3(Hpdc)2(pdc)2] (1) and [Mg3(Hpdc)2(pdc)2] (2) (pdc2– = pyridine-2,4-dicarboxylate) showing primitive cubic (pcu) topology have been prepared and characterized. The pore aperture of the channels is too narrow for the efficient adsorption of N2; however, both compounds demonstrate substantially higher uptake of CO2 (119.9 mL·g–1 for 1 and 102.5 mL·g–1 for 2 at 195 K, 1 bar). Despite of their structural similarities, 2 shows a typical reversible type I isotherm for adsorption/desorption of CO2, while 1 features a two-step adsorption process with a very broad hysteresis between the adsorption and desorption curves. This behavior can be explained by a combination of density functional theory calculations, sorption, and X-ray diffraction analysis and gives insights into the further development of new sorbents showing adsorption/desorption hysteresis.
Probes sensitive to mechanical stress are in demand for the analysis of pressure distribution in materials, and the design of pressure sensors based on metal–organic frameworks (MOFs) is highly promising due to their structural tunability. We report a new pressure-sensing material, which is based on the UiO-66 framework with trace amounts of a spin probe (0.03 wt%) encapsulated in cavities. To obtain this material, we developed an approach for encapsulation of stable nitroxide radical TEMPO ((2,2,6,6-tetramethylpiperidin-1-yl)oxyl) into the micropores of UiO-66 during its solvothermal synthesis. Pressure read-out using electron paramagnetic resonance (EPR) spectroscopy allows monitoring the degradation of the defected MOF structure upon pressurization, where full collapse of pores occurs at as low a pressure as 0.13 GPa. The developed methodology can be used in and ex situ and provides sensitive tools for non-destructive mapping of pressure effects in various materials.
Probes sensitive to mechanical stress are in high demand for analyzing pressure distributions in materials. Metal–organic frameworks (MOFs) are especially promising for designing pressure sensors due to their structural tunability. In this work, using classical molecular dynamics (MD) simulations, we clarified the mechanism of exceptional pressure sensitivity of the material based on the UiO-66 framework with a trace amount of spin probes encapsulated in cavities. The role of defects in the MOF structure has been revealed using a combination of electron paramagnetic resonance (EPR) spectroscopy and MD calculations, and potential degradation pathways under mechanical stress have been proposed. The combined MD and EPR study provides valuable insights for further development of new MOF-based sensors applicable for non-destructive pressure mapping in various materials.