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Gas storage and separation are closely associated with the alleviation of greenhouse effect, the widespread use of clean energy, the control of toxic gases, and various other aspects ...in human society. In this review, we highlight the recent advances in gas storage and separation using metal-organic frameworks (MOFs). In addition to summarizing the gas uptakes of some benchmark MOFs, we emphasize on the desired chemical properties of MOFs for different gas storage/separation scenarios. Greenhouse gases (CO2), energy-related gases (H2 and CH4), and toxic gases (CO and NH3) are covered in the review.
The ex vivo application of enzymes in various processes, especially via enzyme immobilization techniques, has been extensively studied in recent years in order to enhance the recyclability of ...enzymes, to minimize enzyme contamination in the product, and to explore novel horizons for enzymes in biomedical applications. Possessing remarkable amenability in structural design of the frameworks as well as almost unparalelled surface tunability, Metal-Organic Frameworks (MOFs) have been gaining popularity as candidates for enzyme immobilization platforms. Many MOF-enzyme composites have achieved unprecedented results, far outperforming free enzymes in many aspects. This review summarizes recent developments of MOF-enzyme composites with special emphasis on preparative techniques and the synergistic effects of enzymes and MOFs. The applications of MOF-enzyme composites, primarily in transferation, catalysis and sensing, are presented as well. The enhancement of enzymatic activity of the composites over free enzymes in biologically incompatible conditions is emphasized in many cases.
Metal–organic frameworks (MOFs) are an emerging class of porous materials with potential applications in gas storage, separations, catalysis, and chemical sensing. Despite numerous advantages, ...applications of many MOFs are ultimately limited by their stability under harsh conditions. Herein, the recent advances in the field of stable MOFs, covering the fundamental mechanisms of MOF stability, design, and synthesis of stable MOF architectures, and their latest applications are reviewed. First, key factors that affect MOF stability under certain chemical environments are introduced to guide the design of robust structures. This is followed by a short review of synthetic strategies of stable MOFs including modulated synthesis and postsynthetic modifications. Based on the fundamentals of MOF stability, stable MOFs are classified into two categories: high‐valency metal–carboxylate frameworks and low‐valency metal–azolate frameworks. Along this line, some representative stable MOFs are introduced, their structures are described, and their properties are briefly discussed. The expanded applications of stable MOFs in Lewis/Brønsted acid catalysis, redox catalysis, photocatalysis, electrocatalysis, gas storage, and sensing are highlighted. Overall, this review is expected to guide the design of stable MOFs by providing insights into existing structures, which could lead to the discovery and development of more advanced functional materials.
Stable metal–organic frameworks (MOFs) with high resistance to harsh chemical environments are reviewed with regard to recent progress in their research and development. Fundamental mechanisms of MOF stability, the design and synthesis of stable MOF architectures, and their latest applications are summarized, providing a fundamental outline for the discovery of new stable MOFs.
Prodrug activation, by exogenously administered enzymes, for cancer therapy is an approach to achieve better selectivity and less systemic toxicity than conventional chemotherapy. However, the short ...half‐lives of the activating enzymes in the bloodstream has limited its success. Demonstrated here is that a tyrosinase‐MOF nanoreactor activates the prodrug paracetamol in cancer cells in a long‐lasting manner. By generating reactive oxygen species (ROS) and depleting glutathione (GSH), the product of the enzymatic conversion of paracetamol is toxic to drug‐resistant cancer cells. Tyrosinase‐MOF nanoreactors cause significant cell death in the presence of paracetamol for up to three days after being internalized by cells, while free enzymes totally lose activity in a few hours. Thus, enzyme‐MOF nanocomposites are envisioned to be novel persistent platforms for various biomedical applications.
Covert delivery: Demonstrated here is activation of the prodrug paracetamol, by a tyrosinase‐MOF nanoreactor, in cancer cells in a long‐lasting manner. By generating reactive oxygen species and depleting glutathione, the product of the enzymatic conversion of paracetamol is toxic to drug‐resistant cancer cells. Tyrosinase‐MOF nanoreactors cause significant cell death in the presence of paracetamol for up to three days after being internalized by cells, while free enzymes lose activity in a few hours. MOF=metal–organic framework.
A major goal of metal-organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a ...challenge to construct MOFs with precisely customized pore apertures for specific applications. Herein, we present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragments by acid treatment. We demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.
Frozen soil was simulated at six seasonally frozen and seven permafrost stations over the northern Tibetan Plateau using the Variable Infiltration Capacity (VIC) model for the period of 1962–2009. ...The VIC model resolved the seasonal cycle and temporal evolution of the observed soil temperatures and liquid soil moisture well. The simulated long‐term changes during 1962–2009 indicated mostly positive trends for both soil temperature and soil moisture, and negative trends for soil ice content at annual and monthly time scales, although differences existed among the stations, soil layers, and seasons. Increases in soil temperature were due mainly to increases in daily air temperature maxima and internal soil heat conduction, while decreases in soil ice content were related to the warming of frozen soil. For liquid soil moisture, increases in the cold months can be attributed to increases in soil temperature and enhanced soil ice melt while changes in the warm months were the results of competition between positive precipitation and negative soil temperature effects. Precipitation and liquid soil moisture were strongly correlated with evapotranspiration and runoff but had various degrees of correlations with base flow during May–September. Seasonally frozen stations displayed longer and more active hydrological processes than permafrost stations. Slight enhancement of the surface hydrological processes at the study stations was indicated, due to the combined effects of precipitation changes, which were dominant, and frozen soil degradation.
Key Points
Frozen soil is warming in the northern Tibetan Plateau
Surface hydrology enhancement is dominated by precipitation change
Frozen soil degradation plays secondary role in surface hydrology enhancement
The controlled synthesis of multicomponent metal–organic frameworks (MOFs) allows for the precise placement of multiple cooperative functional groups within a framework, leading to emergent ...synergistic effects. Herein, we demonstrate that turn‐on fluorescence sensors can be assembled by combining a fluorophore and a recognition moiety within a complex cavity of a multicomponent MOF. An anthracene‐based fluorescent linker and a hemicyanine‐containing CN−‐responsive linker were sequentially installed into the lattice of PCN‐700. The selective binding of CN− to hemicyanine inhibited the energy transfer between the two moieties, resulting in a fluorescence turn‐on effect. Taking advantage of the high tunability of the MOF platform, the ratio between anthracene and the hemicyanine moiety could be fine‐tuned in order to maximize the sensitivity of the overall framework. The optimized MOF‐sensor had a CN−‐detection limit of 0.05 μm, which is much lower than traditional CN− fluorescent sensors (about 0.2 μm).
An anthracene‐based fluorescent linker and a hemicyanine‐containing CN−‐responsive linker were sequentially installed into the lattice of the metal–organic framework PCN‐700. The proximity and periodic arrangement of the anthracene and hemicyanine linkers facilitated efficient energy transfer between the two components, causing fluorescence quenching. The binding of CN− to hemicyanine inhibited this energy transfer, resulting in fluorescence.
The method of backfill in underground mining is important for ground control as well as material recycling and energy efficiency. Even though extensive testing and field studies of backfill have been ...conducted, less is known about the detailed damage and fracturing that occurs directly at the rock/backfill interface. In this paper, cylindrical specimens containing an inner diameter of backfill and an outer diameter of rock (RB) were tested under triaxial compression. Acoustic emissions (AE) were used throughout testing, and X-ray computed tomography (CT) scanning was conducted before loading was applied and after the specimens had failed. The high-resolution CT images were then converted into point clouds to isolate the fractures and visualize them in three dimensions. The point clouds clearly show that fracturing occurred both in the rock and along with the contact between rock and backfill, while very little fracturing was found to occur in the backfill. Based on the point cloud and AE results, a unique evolution of fracturing is found to occur that includes two stages of shear fracturing in the rock, tensile fracturing along with the rock/backfill interface, and final tensile fracturing in the rock after delamination from the backfill, all of which contributed to the nonlinear stress–strain response. This paper presents a novel approach for investigating the initiation and propagation of 3D fractures in laboratory testing and can offer a useful reference for further studies on the mechanics of bi-material structures.
Crystal engineering of metal-organic frameworks (MOFs) has allowed the construction of complex structures at atomic precision, but has yet to reach the same level of sophistication as organic ...synthesis. The synthesis of complex MOFs with multiple organic and/or inorganic components is ultimately limited by the lack of control over framework assembly in one-pot reactions. Herein, we demonstrate that multi-component MOFs with unprecedented complexity can be constructed in a predictable and stepwise manner under simple kinetic guidance, which conceptually mimics the retrosynthetic approach utilized to construct complicated organic molecules. Four multi-component MOFs were synthesized by the subsequent incorporation of organic linkers and inorganic clusters into the cavity of a mesoporous MOF, each composed of up to three different metals and two different linkers. Furthermore, we demonstrated the utility of such a retrosynthetic design through the construction of a cooperative bimetallic catalytic system with two collaborative metal sites for three-component Strecker reactions.
The continuous variation of the lattice metric in metal–organic frameworks (MOFs) allows precise control over their chemical and physical properties. This has been realized herein by a series of ...mixed-linker and Zr6-cluster-based MOFs, namely, continuously variable MOFs (CVMOFs). Similar to the substitutional solid solutions, organic linkers with different lengths and various ratios were homogeneously incorporated into a framework rather than being allowed to form separate phases or domains, which was manifested by single-crystal X-ray diffraction, powder X-ray diffraction, fluorescence quenching experiments, and molecular simulations. The unit cell dimension, surface area, and pore size of CVMOFs were precisely controlled by adopting different linker sets and linker ratios. We demonstrate that CVMOFs allow the continuous and fine tailoring of cell-edge lengths from 17.83 to 32.63 Å, Brunauer–Emmett–Teller (BET) surface areas from 585 to 3791 m2g–1, and pore sizes up to 15.9 Å. Furthermore, this synthetic strategy can be applied to other MOF systems with various metal nodes thus allowing for a variety of CVMOFs with unprecedented tunability.
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