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A computational and experimental screening of hypothetical and real compounds exhibiting different degrees of ethylenediamine grafted to the CPO-27-Mg or Mg-DOBDC skeleton is performed in order to determine the target composition that optimizes the CO2 adsorption properties under flue gas and air filtering conditions. On the basis of the [Mg2(dobdc)] formula, eighteen hypothetical models involving 15–100% of functionalization of the coordinatively unsaturated sites (CUS) were considered by means of Grand Canonical Monte Carlo simulations to evaluate the CO2 adsorption at 298 K. In addition, post-synthesis modification was applied to CPO-27-Mg leading to three kinds of samples exhibiting 15, 50, and 60% of CUS functionalization with ethylenediamine, named CPO-27-Mg-a, CPO-27-Mg-b and CPO-27-Mg-c. Compounds were characterized using elemental analysis, TGA, FTIR spectroscopy, PXRD and DSC. Finally, bare and functionalized CPO-27-Mg materials were evaluated using gas adsorption and microcalorimetry in the 0.001–1 bar range, which is pertinent for the mentioned applications. Valuable information related to design criteria for synthesis of tuned CO2 adsorbents is derived through this computational and experimental investigation. [ABSTRACT FROM AUTHOR]

MicroRNAs (miRNAs) are small noncoding RNAs that are critical for the regulation of multiple physiological and pathological processes, thus holding great clinical potential. However, the therapeutic applications of miRNAs are severely limited by their biological instability and poor intracellular delivery. Herein, we describe a dual-layers surface engineering strategy to design an efficient miRNA delivery nanosystem based on metal-organic frameworks (MOFs) incorporating lipid coating. The resulting nanoparticle system was demonstrated to protect miRNA from ribonuclease degradation, enhance cellular uptake and facilitate lysosomal escape. These ensured effective miRNA mediated gene therapy, which synergized with MOF-specific photodynamic therapy and pre-encapsulated doxorubicin (Dox) chemotherapy to provide a multifunctional with therapeutic effectiveness against cencer cells The mechanisms of miRNA binding and Dox loading were revealed, demonstrating the potential of the present MOFs surface-engineered strategy to overcome their inherent pore-size restriction for macromolecular miRNA carrying, enableefficient co-delivery. In vitro studies revealed the potential of our multifunctional system for miRNA delivery and the demonstrated the therapeutic effectiveness against cancer cells, thereby providing a versatile all-in-one MOFs strategy for delivery of nucleic acids and diverse therapeutic molecules in synergistic therapy., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Conventional microporous zeolitic imidazolate frameworks (ZIFs) face limitations in mass transfer and pore accessibility when dealing with large guest molecules. Here, we describe a technique for the synthesis of mesoporous ZIFs (MesoZIFs) using a strategy we term directed reticular chemistry. MesoZIF-8 was prepared through solvent evaporation-induced coassembly of polystyrene- block -poly(ethylene oxide) (PS- b -PEO), ZIF-8 building blocks, and acetic acid (AcOH), followed by amine-facilitated crystallization of ZIF-8 in the interstices of PS- b -PEO micelles. AcOH prevents the fast coordination of ZIF-8 building blocks, avoiding phase separation during coassembly. The employed amine plays a crucial role in neutralizing the crystallization environment and further deprotonating the 2-methlyimizale linker to coordinate with zinc ions. Ink bottle-shaped mesopores with tunable mesopore sizes were created by adjusting the molecular weight of PS- b -PEO. Compared to microporous ZIF-8, MesoZIF-8 exhibited enhanced performance in Knoevenagel condensation reactions involving large reactants and hydrogen storage capacity. With this study, we establish an efficient approach for synthesizing MesoZIFs with highly accessible mesopores to enhance ZIF performance in targeted applications.

This work presents a straightforward, room-temperature synthesis of a robust {[Fe(atrz) 3 ](OTs) 2 } n monolith. This approach offers a green alternative to traditional nanoparticle synthesis for manipulating spin crossover (SCO) behaviour. The monolith exhibits a more gradual SCO transition at lower temperatures compared to the bulk material, aligning with observations in smaller particle systems. Notably, the synthesis employs a solvent- and surfactant-free approach, simplifying the process and potentially reducing environmental impact, aligning with the principles of green chemistry.

The development of nanoparticle (NP)-based drug carriers has presented an exciting opportunity to address challenges in oncology. Among the 100,000 available possibilities, zirconium-based metal-organic frameworks (MOFs) have emerged as promising candidates in biomedical applications. Zr-MOFs can be easily synthesized as small-size NPs compatible with intravenous injection, whereas the ease of decorating their external surfaces with functional groups allows for targeted treatment. Despite these benefits, Zr-MOFs suffer degradation and aggregation in real, in vivo conditions, whereas the loaded drugs will suffer the burst effect-i.e., the fast release of drugs in less than 48 h. To tackle these issues, we developed a simple but effective bilayer coating strategy in a generic, two-step process. In this work, bilayer-coated MOF NU-901 remained well dispersed in biologically relevant fluids such as buffers and cell growth media. Additionally, the coating enhances the long-term stability of drug-loaded MOFs in water by simultaneously preventing sustained leakage of the drug and aggregation of the MOF particles. We evaluated our materials for the encapsulation and transport of pemetrexed, the standard-of-care chemotherapy in mesothelioma. The bilayer coating allowed for a slowed release of pemetrexed over 7 days, superior to the typical 48 h release found in bare MOFs. This slow release and the related performance were studied in vitro using both A549 lung cancer and 3T mesothelioma cells. Using high-resolution microscopy, we found the successful uptake of bilayer-coated MOFs by the cells with an accumulation in the lysosomes. The pemetrex-loaded NU-901 was indeed cytotoxic to 3T and A549 cancer cells. Finally, we demonstrated the general approach by extending the coating strategy using two additional lipids and four surfactants. This research highlights how a simple yet effective bilayer coating provides new insights into the design of promising MOF-based drug delivery systems., Competing Interests: The authors declare the following competing financial interest(s): D.F.-J. has commercial interests in Vector Bioscience Cambridge, a spin-out for the commercialization of MOFs in healthcare applications., (© 2024 The Authors. Published by American Chemical Society.)

The chemistry of metal-organic frameworks (MOFs) continues to expand rapidly, providing materials with diverse structures and properties. The reticular chemistry approach, where well-defined structural building blocks are combined together to form crystalline open framework solids, has greatly accelerated the discovery of new and important materials. However, its full potential toward the rational design of MOFs relies on the availability of highly connected building blocks because these greatly reduce the number of possible structures. Toward this, building blocks with connectivity greater than 12 are highly desirable but extremely rare. We report here the discovery of novel 18-connected, trigonal prismatic, ternary building blocks ( tbb 's) and their assembly into unique MOFs, denoted as Fe- tbb -MOF- x ( x : 1, 2, 3), with hierarchical micro- and mesoporosity. The remarkable tbb is an 18-c supertrigonal prism, with three points of extension at each corner, consisting of triangular (3-c) and rectangular (4-c) carboxylate-based organic linkers and trigonal prismatic [Fe 3 (μ 3 -Ο)(-COO) 6 ] + clusters. The tbb 's are linked together by an 18-c cluster made of 4-c ligands and a crystallographically distinct Fe 3 (μ 3 -Ο) trimer, forming overall a 3-D (3,4,4,6,6)-c five nodal net. The hierarchical, highly porous nature of Fe- tbb -MOF- x ( x : 1, 2, 3) was confirmed by recording detailed sorption isotherms of Ar, CH 4 , and CO 2 at 87, 112, and 195 K, respectively, revealing an ultrahigh BET area (4263-4847 m 2 g -1 ) and pore volume (1.95-2.29 cm 3 g -1 ). Because of the observed ultrahigh porosities, the H 2 and CH 4 storage properties of Fe- tbb -MOF- x were investigated, revealing well-balanced high gravimetric and volumetric deliverable capacities for cryoadsorptive H 2 storage (11.6 wt %/41.4 g L -1 , 77 K/100 bar-160 K/5 bar), as well as CH 4 storage at near ambient temperatures (367 mg g -1 /160 cm 3 STP cm -3 , 5-100 bar at 298 K), placing these materials among the top performing MOFs. The present work opens new directions to apply reticular chemistry for the construction of novel MOFs with tunable porosities based on contracted or expanded tbb analogues.

Hydrogen storage by cryoadsorption on porous materials has the advantages of low material cost, safety, fast kinetics, and high cyclic stability. The further development of this technology requires reliable data on the H 2 uptake of the adsorbents, however, even for activated carbons the values between different laboratories show sometimes large discrepancies. So far no reference material for hydrogen cryoadsorption is available. The metal-organic framework ZIF-8 is an ideal material possessing high thermal, chemical, and mechanical stability that reduces degradation during handling and activation. Here, we distributed ZIF-8 pellets synthesized by extrusion to 9 laboratories equipped with 15 different experimental setups including gravimetric and volumetric analyzers. The gravimetric H 2 uptake of the pellets was measured at 77 K and up to 100 bar showing a high reproducibility between the different laboratories, with a small relative standard deviation of 3-4 % between pressures of 10-100 bar. The effect of operating variables like the amount of sample or analysis temperature was evaluated, remarking the calibration of devices and other correction procedures as the most significant deviation sources. Overall, the reproducible hydrogen cryoadsorption measurements indicate the robustness of the ZIF-8 pellets, which we want to propose as a reference material., (© 2024 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

Photodynamic therapy (PDT), an emergent noninvasive cancer treatment, is largely dependent on the presence of efficient photosensitizers (PSs) and a sufficient oxygen supply. However, the therapeutic efficacy of PSs is greatly compromised by poor solubility, aggregation tendency, and oxygen depletion within solid tumors during PDT in hypoxic microenvironments. Despite the potential of PS-based metal-organic frameworks (MOFs), addressing hypoxia remains challenging. Boron dipyrromethene (BODIPY) chromophores, with excellent photostability, have exhibited great potential in PDT and bioimaging. However, their practical application suffers from limited chemical stability under harsh MOF synthesis conditions. Herein, we report the synthesis of the first example of a Zr-based MOF, namely, 69-L 2 , exclusively constructed from the BODIPY-derived ligands via a single-crystal to single-crystal post-synthetic exchange, where a direct solvothermal method is not applicable. To increase the PDT performance in hypoxia, we modify 69-L 2 with fluorinated phosphate-functionalized methoxy poly(ethylene glycol). The resulting 69-L 2 @F is an oxygen carrier, enabling tumor oxygenation and simultaneously acting as a PS for reactive oxygen species (ROS) generation under LED irradiation. We demonstrate that 69-L 2 @F has an enhanced PDT effect in triple-negative breast cancer MDA-MB-231 cells under both normoxia and hypoxia. Following positive results, we evaluated the in vivo activity of 69-L 2 @F with a hydrogel, enabling local therapy in a triple-negative breast cancer mice model and achieving exceptional antitumor efficacy in only 2 days. We envision BODIPY-based Zr-MOFs to provide a solution for hypoxia relief and maximize efficacy during in vivo PDT, offering new insights into the design of promising MOF-based PSs for hypoxic tumors.

Space cooling and heating, ventilation, and air conditioning (HVAC) accounts for roughly 10% of global electricity use and are responsible for ca. 1.13 gigatonnes of CO 2 emissions annually. Adsorbent-based HVAC technologies have long been touted as an energy-efficient alternative to traditional refrigeration systems. However, thus far, no suitable adsorbents have been developed which overcome the drawbacks associated with traditional sorbent materials such as silica gels and zeolites. Metal-organic frameworks (MOFs) offer order-of-magnitude improvements in water adsorption and regeneration energy requirements. However, the deployment of MOFs in HVAC applications has been hampered by issues related to MOF powder processing. Herein, three high-density, shaped, monolithic MOFs (UiO-66, UiO-66-NH 2 , and Zr-fumarate) with exceptional volumetric gas/vapor uptake are developed-solving previous issues in MOF-HVAC deployment. The monolithic structures across the mesoporous range are visualized using small-angle X-ray scattering and lattice-gas models, giving accurate predictions of adsorption characteristics of the monolithic materials. It is also demonstrated that a fragile MOF such as Zr-fumarate can be synthesized in monolithic form with a bulk density of 0.76 gcm -3 without losing any adsorption performance, having a coefficient of performance (COP) of 0.71 with a low regeneration temperature (≤ 100 °C)., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Despite the enormous advancements in nanomedicine research, a limited number of nanoformulations are available on the market, and few have been translated to clinics. An easily scalable, sustainable, and cost-effective manufacturing strategy and long-term stability for storage are crucial for successful translation. Here, we report a system and method to instantly formulate NF achieved with a nanoscale polyelectrolyte coacervate-like system, consisting of anionic pseudopeptide poly(l-lysine isophthalamide) derivatives, polyethylenimine, and doxorubicin (Dox) via simple "mix-and-go" addition of precursor solutions in seconds. The coacervate-like nanosystem shows enhanced intracellular delivery of Dox to patient-derived multidrug-resistant (MDR) cells in 3D tumor spheroids. The results demonstrate the feasibility of an instant drug formulation using a coacervate-like nanosystem. We envisage that this technique can be widely utilized in the nanomedicine field to bypass the special requirement of large-scale production and elongated shelf life of nanomaterials.

Metal-organic polyhedra featuring non-Archimedean/Platonic architectures with multiple kinds of vertices have aroused great attention for their fascinating structures and properties but are yet challenging to achieve. Here, we report a combinatorial strategy to make such nonclassic polyhedral cages by combining kinetically labile metal ions with non-planar organic linkers instead of the usual only inert metal centers and planar ligands. This facilitates the synthesis of an enantiopure twisted tetra(3-pyridyl)-based TADDOL (TADDOL = tetraaryl-1,3-dioxolane-4,5-dimethanol) ligand ( L ) capable of binding Ni(II) ions to produce a regular convex cage, Ni 6 L 8 , with two mixed metal/organic vertices and three rarely reported concave cages Ni 14 L 8 , Ni 18 L 12 , and Ni 24 L 16 with three or four mixed vertices. Each of the cages has an amphiphilic cavity decorated with chiral dihydroxyl functionalities and packs into a three-dimensional structure. The enantioselective adsorption and separation performances of the cages are strongly dependent on their pore structure features. Particularly, Ni 14 L 8 and Ni 18 L 12 with wide openings can be solid adsorbents for the adsorptive and solid-phase extractive separation of a variety of racemic spirodiols with up to 98% ee, whereas Ni 6 L 8 and Ni 24 L 16 with smaller pore apertures cannot adsorb the racemates. The combination of single-crystal X-ray diffraction analysis of the host-guest adduct and GCMC simulation indicates that the enantiospecific recognition capabilities originate from the well-organized chiral inner sphere as well as multiple interactions within the chiral microenvironment. This work therefore provides an attractive strategy for the rational design of polyhedral cages, showing geometrically fascinating structures with properties different from those of classic assemblies.

Zr-oxide secondary building units construct metal-organic framework (MOF) materials with excellent gas adsorption properties and high mechanical, thermal, and chemical stability. These attributes have led Zr-oxide MOFs to be well-recognized for a wide range of applications, including gas storage and separation, catalysis, as well as healthcare domain. Here, we report structure search methods within the Cambridge Structural Database (CSD) to create a curated subset of 102 Zr-oxide MOFs synthesized to date, bringing a unique record for all researchers working in this area. For the identified structures, we manually corrected the proton topology of hydroxyl and water molecules on the Zr-oxide nodes and characterized their textural properties, Brunauer-Emmett-Teller (BET) area, and topology. Importantly, we performed systematic periodic density functional theory (DFT) calculations comparing 25 different combinations of basis sets and functionals to calculate framework partial atomic charges for use in gas adsorption simulations. Through experimental verification of CO 2 adsorption in selected Zr-oxide MOFs, we demonstrate the sensitivity of CO 2 adsorption predictions at the Henry's regime to the choice of the DFT method for partial charge calculations. We characterized Zr-MOFs for their CO 2 adsorption performance via high-throughput grand canonical Monte Carlo (GCMC) simulations and revealed how the chemistry of the Zr-oxide node could have a significant impact on CO 2 uptake predictions. We found that the maximum CO 2 uptake is obtained for structures with the heat of adsorption values >25 kJ/mol and the largest cavity diameters of ca. 6-7 Å. Finally, we introduced augmented reality (AR) visualizations as a means to bring adsorption phenomena alive in porous adsorbents and to dynamically explore gas adsorption sites in MOFs.

As rationally designable materials, the variety and number of synthesised metal-organic cages (MOCs) and organic cages (OCs) are expected to grow in the Cambridge Structural Database (CSD). In this regard, two of the most important questions are, which structures are already present in the CSD and how can they be identified? Here, we present a cage mining methodology based on topological data analysis and a combination of supervised and unsupervised learning that led to the derivation of - to the best of our knowledge - the first and only MOC dataset of 1839 structures and the largest experimental OC dataset of 7736 cages, as of March 2022. We illustrate the use of such datasets with a high-throughput screening of MOCs and OCs for xenon/krypton separation, important gases in multiple industries, including healthcare., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We are currently witnessing the dawn of hydrogen (H 2 ) economy, where H 2 will soon become a primary fuel for heating, transportation, and long-distance and long-term energy storage. Among diverse possibilities, H 2 can be stored as a pressurized gas, a cryogenic liquid, or a solid fuel via adsorption onto porous materials. Metal-organic frameworks (MOFs) have emerged as adsorbent materials with the highest theoretical H 2 storage densities on both a volumetric and gravimetric basis. However, a critical bottleneck for the use of H 2 as a transportation fuel has been the lack of densification methods capable of shaping MOFs into practical formulations while maintaining their adsorptive performance. Here, we report a high-throughput screening and deep analysis of a database of MOFs to find optimal materials, followed by the synthesis, characterization, and performance evaluation of an optimal monolithic MOF ( mono MOF) for H 2 storage. After densification, this mono MOF stores 46 g L -1 H 2 at 50 bar and 77 K and delivers 41 and 42 g L -1 H 2 at operating pressures of 25 and 50 bar, respectively, when deployed in a combined temperature-pressure (25-50 bar/77 K → 5 bar/160 K) swing gas delivery system. This performance represents up to an 80% reduction in the operating pressure requirements for delivering H 2 gas when compared with benchmark materials and an 83% reduction compared to compressed H 2 gas. Our findings represent a substantial step forward in the application of high-density materials for volumetric H 2 storage applications.

The application of metal-organic frameworks (MOFs) in drug delivery has advanced rapidly over the past decade, showing huge progress in the development of novel systems. Although a large number of versatile MOFs that can carry and release multiple compounds have been designed and tested, one of the main limitations to their translation to the clinic is the limited biological understanding of their interaction with cells and the way they penetrate them. This is a crucial aspect of drug delivery, as MOFs need to be able not only to enter into cells but also to release their cargo in the correct intracellular location. While small molecules can enter cells by passive diffusion, nanoparticles (NPs) usually require an energy-dependent process known as endocytosis. Importantly, the fate of NPs after being taken up by cells is dependent on the endocytic pathways they enter through. However, no general guidelines for MOF particle internalization have been established due to the inherent complexity of endocytosis as a mechanism, with several factors affecting cellular uptake, namely NP size and surface chemistry. In this review, we cover recent advances regarding the understanding of the mechanisms of uptake of nano-sized MOFs (nanoMOFs)s, their journey inside the cell, and the importance of biological context in their final fate. We examine critically the impact of MOF physicochemical properties on intracellular trafficking and successful cargo delivery. Finally, we highlight key unanswered questions on the topic and discuss the future of the field and the next steps for nanoMOFs as drug delivery systems.

Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer-Emmett-Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro- and mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already-measured raw adsorption isotherms were provided to sixty-one labs, who were asked to calculate the corresponding BET areas. This round-robin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called "BET surface identification" (BETSI), expands on the well-known Rouquerol criteria and makes an unambiguous BET area assignment possible., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Metal-organic frameworks (MOFs) are one of the most researched designer materials today, as their high tunability offers scientists a wide space to imagine all kinds of possible structures. Their uniquely flexible customisability spurred the creation of hypothetical datasets and the syntheses of more than 100 000 MOFs officially reported in the Cambridge Structural Database. To scan such large numbers of MOFs, computational high-throughput screenings (HTS) have become the customary method to identify the most promising structure for a given application, and/or to spot useful structure-property relationships. However, despite all these data-mining efforts, only a fraction of HTS studies have identified synthesisable top-performing MOFs that were then further investigated in the lab. In this perspective, we review these specific cases and suggest possible steps to push future HTS more systematically towards synthesisable structures., Competing Interests: D. F.-J. and A. L. have a financial interest in the start-up company Immaterial, which is seeking to commercialise metal–organic frameworks. The remaining authors declare no competing interests., (This journal is © The Royal Society of Chemistry.)

Controlling the pressure at which liquids intrude (wet) and extrude (dry) a nanopore is of paramount importance for a broad range of applications, such as energy conversion, catalysis, chromatography, separation, ionic channels, and many more. To tune these characteristics, one typically acts on the chemical nature of the system or pore size. In this work, we propose an alternative route for controlling both intrusion and extrusion pressures via proper arrangement of the grains of the nanoporous material. To prove the concept, dynamic intrusion-extrusion cycles for powdered and monolithic ZIF-8 metal-organic framework were conducted by means of water porosimetry and in operando neutron scattering. We report a drastic increase in intrusion-extrusion dynamic hysteresis when going from a fine powder to a dense monolith configuration, transforming an intermediate performance of the ZIF-8 + water system (poor molecular spring) into a desirable shock-absorber with more than 1 order of magnitude enhancement of dissipated energy per cycle. The obtained results are supported by MD simulations and pave the way for an alternative methodology of tuning intrusion-extrusion pressure using a macroscopic arrangement of nanoporous material.

Nanocarriers have emerged as one of the most promising approaches for drug delivery. Although several nanomaterials have been approved for clinical use, the translation from lab to clinic remains challenging. However, by implementing rational design strategies and using relevant models for their validation, these challenges are being addressed. This work describes the design of novel immunocompatible polymer nanocarriers made of melanin-mimetic polydopamine and Pluronic F127 units. The nanocarrier preparation was conducted under mild conditions, using a highly reproducible method that was tuned to provide a range of particle sizes (<100 nm) without changing the composition of the carrier. A set of in vitro studies were conducted to provide a comprehensive assessment of the effect of carrier size (40, 60 and 100 nm) on immunocompatibility, viability and uptake into different pancreatic cancer cells varying in morphological and phenotypic characteristics. Pancreatic cancer is characterised by poor treatment efficacy and no improvement in patient survival in the last 40 years due to the complex biology of the solid tumour. High intra- and inter-tumoral heterogeneity and a dense tumour microenvironment limit diffusion and therapeutic response. The Pluronic-polydopamine nanocarriers were employed for the delivery of irinotecan active metabolite SN38, which is used in the treatment of pancreatic cancer. Increased antiproliferative effect was observed in all tested cell lines after administration of the drug encapsulated within the carrier, indicating the system's potential as a therapeutic agent for this hard-to-treat cancer.

At its core, reticular chemistry has translated the precision and expertise of organic and inorganic synthesis to the solid state. While initial excitement over metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) was undoubtedly fueled by their unprecedented porosity and surface areas, the most profound scientific innovation of the field has been the elaboration of design strategies for the synthesis of extended crystalline solids through strong directional bonds. In this contribution we highlight the different classes of reticular materials that have been developed, how these frameworks can be functionalized, and how complexity can be introduced into their backbones. Finally, we show how the structural control over these materials is being extended from the molecular scale to their crystal morphology and shape on the nanoscale, all the way to their shaping on the bulk scale., (© 2021 Wiley-VCH GmbH.)

Carbon dioxide (CO 2 ) is both a primary contributor to global warming and a major industrial impurity. Traditional approaches to carbon capture involve corrosive and energy-intensive processes such as liquid amine absorption. Although adsorptive separation has long been a promising alternative to traditional processes, up to this point there has been a lack of appropriate adsorbents capable of capturing CO 2 whilst maintaining low regeneration energies. In the context of CO 2 capture, metal-organic frameworks (MOFs) have gained much attention in the past two decades as potential materials. Their tuneable nature allows for precise control over the pore size and chemistry, which allows for the tailoring of their properties for the selective adsorption of CO 2 . While many candidate materials exist, the amount of research into material shaping for use in industrial processes has been limited. Traditional shaping strategies such as pelletisation involve the use of binders and/or mechanical processes, which can have a detrimental impact on the adsorption properties of the resulting materials or can result in low-density structures with low volumetric adsorption capacities. Herein, we demonstrate the use of a series of monolithic MOFs ( mono UiO-66, mono UiO-66-NH 2 & mono HKUST-1) for use in gas separation processes.

Mesothelioma is an aggressive cancer that is associated with exposure to asbestos. Although asbestos is banned in several countries, including the UK, an epidemic of mesothelioma is predicted to affect middle-income countries during this century owing to their heavy consumption of asbestos. The prognosis for patients with mesothelioma is poor, reflecting a failure of conventional chemotherapy that has ultimately resulted from an inadequate understanding of its biology. However, recent work has revolutionised the study of mesothelioma, identifying genetic and pathophysiological vulnerabilities, including the loss of tumour suppressors, epigenetic dysregulation and susceptibility to nutrient stress. We discuss how this knowledge, combined with advances in immunotherapy, is enabling the development of novel targeted therapies., (© 2021. The Author(s).)

Metal-organic framework nanoparticles (nanoMOFs) have been widely studied in biomedical applications. Although substantial efforts have been devoted to the development of biocompatible approaches, the requirement of tedious synthetic steps, toxic reagents, and limitations on the shelf life of nanoparticles in solution are still significant barriers to their translation to clinical use. In this work, we propose a new postsynthetic modification of nanoMOFs with phosphate-functionalized methoxy polyethylene glycol (mPEG-PO 3 ) groups which, when combined with lyophilization, leads to the formation of redispersible solid materials. This approach can serve as a facile and general formulation method for the storage of bare or drug-loaded nanoMOFs. The obtained PEGylated nanoMOFs show stable hydrodynamic diameters, improved colloidal stability, and delayed drug-release kinetics compared to their parent nanoMOFs. Ex situ characterization and computational studies reveal that PEGylation of PCN-222 proceeds in a two-step fashion. Most importantly, the lyophilized, PEGylated nanoMOFs can be completely redispersed in water, avoiding common aggregation issues that have limited the use of MOFs in the biomedical field to the wet form-a critical limitation for their translation to clinical use as these materials can now be stored as dried samples. The in vitro performance of the addition of mPEG-PO 3 was confirmed by the improved intracellular stability and delayed drug-release capability, including lower cytotoxicity compared with that of the bare nanoMOFs. Furthermore, z -stack confocal microscopy images reveal the colocalization of bare and PEGylated nanoMOFs. This research highlights a facile PEGylation method with mPEG-PO 3 , providing new insights into the design of promising nanocarriers for drug delivery.