Benign by Design: Green and Scalable Synthesis of Zirconium UiO-Metal–Organic Frameworks by Water-Assisted Mechanochemistry

We present a solvent-free, green, and rapid mechanochemical route for the synthesis of a series of zirconium metal–organic frameworks (MOFs) composed of Zr6 cluster nodes, UiO-66, UiO-66-NH2, MOF-801, and MOF-804, both on a laboratory scale and by scalable and flow mechanochemical processing. The methodology, based on the use of a nonconventional zirconium dodecanuclear acetate cluster and a minute amount of water as an additive, affords high-quality MOFs in less than 1 h of milling, with minimal requirements for workup processing and eliminating the need for conventional hazardous solvents, such as dimethylformamide. Moreover, the use of a dodecanuclear zirconium acetate precursor circumvents the need for modulators resulting in acetic acid as the only byproduct of the reaction, which does not harm these acid-resistant materials. The porosity, thermal and chemical stability, as well as catalytic activity of mechanochemically prepared Zr-based MOFs are similar to those of solvothermally synthesized counterparts. Finally, the synthesis is readily applicable on a 10 g scale by using a planetary mill, and is also performed by solid-state flow synthesis using twin-screw extrusion (TSE), affording more than 100 g of catalytically active UiO-66-NH2 material in a continuous process at a rate of 1.4 kg/h

FIGO statement: Fertility preservation.

editorial reviewedFertility preservation is a growing field in reproductive medicine that may raise ethical questions. Preservation of fertility must be discussed with the patient if gonadotoxic treatment is required, whether in the case of benign or malignant pathology, or in the management of transgender identity. As a result, surgery or chemotherapy that has fewer adverse impacts on fertility should be proposed if this does not alter the prognosis of the disease. If the risk of infertility persists, then fertility cryopreservation should be proposed for children and adults of reproductive age. Sperm, oocytes, and gonadal tissue can be cryopreserved for many years. FIGO wishes to emphasize the importance of fertility preservation in the medical and surgical management of patients, and the importance of a specialized, multidisciplinary approach

Isolating the Role of the Node-Linker Bond in the Compression of UiO-66 Metal-Organic Frameworks

Understanding the mechanical properties of metal–organic frameworks (MOFs) is essential to the fundamental advancement and practical implementations of porous materials. Recent computational and experimental efforts have revealed correlations between mechanical properties and pore size, topology, and defect density. These results demonstrate the important role of the organic linker in the response of these materials to physical stresses. However, the impact of the coordination bond between the inorganic node and organic linker on the mechanical stability of MOFs has not been thoroughly studied. Here, we isolate the role of this node–linker coordination bond to systematically study the effect it plays in the compression of a series of isostructural MOFs, M-UiO-66 (M = Zr, Hf, or Ce). The bulk modulus (i.e. the resistance to compression under hydrostatic pressure) of each MOF is determined by in situ diamond anvil cell (DAC) powder X-ray diffraction measurements and density functional theory (DFT) simulations. These experiments reveal distinctive behavior of Ce-UiO-66 in response to pressures under one GPa. In situ DAC Raman spectroscopy and DFT calculations support the observed differences in compressibility between Zr-UiO-66 and the Ce- analogue. Monitoring changes in bond lengths as a function of pressure through DFT simulations provides a clear picture of those which shorten more drastically under pressure and those which resist compression. This study demonstrates that changes to the node–linker bond can have significant ramifications on the mechanical properties of MOFs

Investigating the mechanical stability of flexible metal–organic frameworks

Abstract As we continue to develop metal–organic frameworks (MOFs) for potential industrial applications, it becomes increasingly imperative to understand their mechanical stability. Notably, amongst flexible MOFs, structure-property relationships regarding their compressibility under pressure remain unclear. In this work, we conducted in situ variable pressure powder X-ray diffraction (PXRD) measurements up to moderate pressures (<1 GPa) using a synchrotron source on two families of flexible MOFs: (i) NU-1400 and NU-1401, and (ii) MIL-88B, MIL-88B-(CH3)2, and MIL-88B-(CH3)4. In this project scope, we found a positive correlation between bulk moduli and degree of flexibility, where increased rigidity (e.g., smaller swelling or breathing amplitude) arising from steric hindrance was deleterious, and observed reversibility in the unit cell compression of these MOFs. This study serves as a primer for the community to begin to untangle the factors that engender flexible frameworks with mechanical resilience

Orthogonal Synthesis of Highly Porous Zr-MOFs Assembled from Simple Building Blocks for Oxygen Storage

The last decade has witnessed significant advances in the scale-up synthesis of metal–organic frameworks (MOFs) using commercially available and affordable organic linkers. However, the synthesis of MOFs using elongated and/or multitopic linkers to access MOFs with large pore volume and/or various topologies can often be challenging due to multi-step organic syntheses involved for linker preparation.In this report, a orthogonal MOF synthesis strategy is developed by utilizing the coordination and covalent bonds formation in one-pot where monoacid-based ligands reacted to form ditopic ligands which then assembled into a 3-D MOF with Zr6 clusters. Chemical stability of the resulting materials was significantly enhanced through converting the imine bond into robust linkage via cycloaddition with phenylacetylene. Oxygen storage capacities of the MOFs were measured, and enhanced volumetric O2 uptake was observed for the stabilized MOF, NU-401-Q.<br /

Self-Recognizing π-π Stacking Interactions Designed for the Generation of Ultrastable Mesoporous Hydrogen-Bonded Organic Frameworks

Creating crystalline porous materials with large pores is typically challenging due to undesired interpen-etration, staggered stacking, or weakened framework stability. Here, we report a pore size expansion strategy by self-recognizing π-π stacking interactions in a series of two-dimensional (2D) hydrogen–bonded organic frameworks (HOFs), HOF-10x (x=0,1,2), self-assembled from pyrene-based tectons with systematic elongation of π-conjugated molecular arms. This strategy successfully avoids interpene-tration or staggered stacking and expands the pore size of HOF materials to access mesoporous HOF-102, which features a surface area of ~ 2,500 m2/g and the largest pore volume (1.3 cm3/g) to date among all reported HOFs. More importantly, HOF-102 shows significantly enhanced thermal and chemical stability as evidenced by powder x-ray diffraction and N2 isotherms after treatments in chal-lenging conditions. Such stability enables the adsorption of dyes and cytochrome c from aqueous media by HOF-102 and affords a processible HOF-102/fiber composite for the efficient photochemical detox-ification of a mustard gas simulant

Evaluating Thin-Layer Sediment Placement as a Tool for Enhancing Tidal Marsh Resilience: a Coordinated Experiment Across Eight US National Estuarine Research Reserves

Thin-layer sediment placement (TLP) is a promising management tool for enhancing tidal marsh resilience to rising seas. We conducted a 3-year experiment at eight US National Estuarine Research Reserves using a standardized implementation protocol and subsequent monitoring to evaluate effects of sediment placement on vegetation in low and high marsh, and compared this to control and reference plots. Sediments added to experimental plots were sourced from nearby quarries, were sandier than ambient marsh soils, and had more crab burrowing, but proved effective, suggesting that terrestrial sources can be used for tidal marsh restoration. We found strong differences among sites but detected general trends across the eight contrasting systems. Colonization by marsh plants was generally rapid following sediment addition, such that TLP plot cover was similar to control plots. While we found that 14-cm TLP plots were initially colonized more slowly than 7-cm plots, this difference largely disappeared after three years. In the face of accelerated sea-level rise, we thus recommend adding thicker sediment layers. Despite rapid revegetation, TLP plots did not approximate vegetation characteristics of higher elevation reference plots. Thus, while managers can expect fairly fast revegetation at TLP sites, the ultimate goal of achieving reference marsh conditions may be achieved slowly if at all. Vegetation recovered rapidly in both high and low marsh; thus, TLP can serve as a climate adaptation strategy across the marsh landscape. Our study illustrates the value of conducting experiments across disparate geographies and provides restoration practitioners with guidance for conducting future TLP projects