Advances in Enzyme and Ionic Liquid Immobilization for Enhanced in MOFs for Biodiesel Production

Biodiesel is a promising candidate for sustainable and renewable energy and extensive research is being conducted worldwide to optimize its production process. The employed catalyst is an important parameter in biodiesel production. Metal–organic frameworks (MOFs), which are a set of highly porous materials comprising coordinated bonds between metals and organic ligands, have recently been proposed as catalysts. MOFs exhibit high tunability, possess high crystallinity and surface area, and their order can vary from the atomic to the microscale level. However, their catalytic sites are confined inside their porous structure, limiting their accessibility for biodiesel production. Modification of MOF structure by immobilizing enzymes or ionic liquids (ILs) could be a solution to this challenge and can lead to better performance and provide catalytic systems with higher activities. This review compiles the recent advances in catalytic transesterification for biodiesel production using enzymes or ILs. The available literature clearly indicates that MOFs are the most suitable immobilization supports, leading to higher biodiesel production without affecting the catalytic activity while increasing the catalyst stability and reusability in several cycles.     

Surface-Deactivated Core–Shell Metal–Organic Framework by Simple Ligand Exchange for Enhanced Size Discrimination in Aerobic Oxidation of Alcohols

Metal–organic frameworks (MOFs) are an attractive catalyst support for stable immobilization of the active sites in their scaffold due to the high tunability of organic ligands. The active site-functionalized ligands can be easily employed to construct MOFs as porous heterogeneous catalysts. However, the existence of active sites on the external surfaces as well as internal pores of MOFs seriously impedes the selective reaction in the pore. Herein, through a simple post-synthetic ligand exchange (PSE) method we synthesized surface-deactivated (only core-active) core–shell-type MOF catalysts, which contain 2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) groups on the ligand as active sites for aerobic oxidation of alcohols. The porous but catalytically inactive shell ensured the size-selective permeability by sieving effects and induced all reactions to take place in the pores of the catalytically active core. Because PSE is a facile and universal approach, this can be rapidly applied to a variety of MOF-based catalysts for enhancing reaction selectivity.     

Luminescent nanoscale metal–organic frameworks for chemical sensing

Metal–organic frameworks(MOFs) are a fascinating class of crystalline materials constructed from selfassembly of metal cations/clusters and organic ligands. Both metal and organic components can be used to generate luminescence, and can further interact via antenna effect to increase the quantum yield,providing a versatile platform for chemical sensing based on luminescence emission. Moreover, MOFs can be miniaturized to nanometer scale to form nano-MOF(NMOF) materials, which exhibit many advantages over conventional bulk MOFs in terms of the facile tailorability of compositions, sizes and morphologies, the high dispersity in a wide variety of medium, and the intrinsic biocompatibility. This review will detail the development of NMOF materials as chemical sensors, including the synthetic methodologies for designing NMOF sensory materials, their luminescent properties and potential sensing applications.     

Tritopic Triazatruxene Ligands for Multicomponent Metal‐Organic Frameworks

Multicomponent metal‐organic frameworks (MOFs) are built up from multiple ligands that are geometrically distinct. These ligands occupy specific positions in the MOF lattice. Installing different functionalities at precise locations in the framework is an important step in making MOFs for specific applications. This can be achieved by designing functionalized ligands for multicomponent MOFs. Here, we report a simple synthetic procedure for a new tritopic triazatruxene based tricarboxylic acid, H₃tat. We show that this ligand can be symmetrically derivatized with various substituents on its nitrogen centres. We report a new isoreticular series of well‐ordered quaternary MOFs based on these new triazatruxene ligands together with two linear carboxylate ligands and Zn₄O clusters. These MOFs are isostructural to the previously reported MUF‐77 series and show similar high surface areas and large pore volumes. Furthermore, H‐bonding between the NH sites of the incorporated triazatruxene ligands and guest molecules is employed to modify their fluorescence behavior.     

Fabrication of Microporous Metal–Organic Frameworks in Uninterrupted Mesoporous Tunnels: Hierarchical Structure for Efficient Trypsin Immobilization and Stabilization

Hierarchically porous metal–organic frameworks (HP‐MOFs) are promising in various applications. Most reported HP‐MOFs are prepared based on the generation of mesopores in microporous frameworks, and the formed mesopores are connected by microporous channels, limiting the accessibility of mesopores for bulky molecules. A hierarchical structure is formed by constructing microporous MOFs in uninterrupted mesoporous tunnels. Using the confined space in as‐prepared mesoporous silica, highly dispersed metal precursors for MOFs are coated on the internal surface of mesoporous tunnels. Ligand vapor‐induced crystallization is employed to enable quantitative formation of MOFs in situ, in which sublimated ligands diffuse into mesoporous tunnels and react with metal precursors. The obtained hierarchically porous composites exhibit record‐high adsorption capacity for the bulky molecule trypsin. The thermal and storage stability of trypsin is improved upon immobilization on the composites.     

离子液体功能化金属/共价-有机框架材料在催化反应中应用

离子液体（ILs）功能化的金属有机框架（MOFs）和共价有机框架（COFs）材料兼具离子液体和MOFs/COFs的优点，是一种极具潜力的复合催化材料。MOFs和COFs材料固定的孔结构及较大的比表面积为负载高分散催化中心提供了天然的物理空间；多孔结构促使催化剂与反应物充分接触；丰富的孔道有利于运输催化反应底物和产物，进而实现催化反应的高效进行。特别是离子液体片段的引入，可以作为催化活性中心的配体（稳定剂）或分散剂，同时能够有效改善MOFs和COFs材料孔道和活性中心周围的微环境。此外，还可以充分利用离子液体片段在适当的反应条件下转化为氮杂环卡宾配体的特点，在MOFs和COFs材料中引入氮杂环卡宾有机金属配合物。因此，我们对近几年来离子液体功能化的MOFs或COFs催化体系在CO2环加成、CO2还原、C-C偶联、羰基化以及其它有机转化反应中的研究应用进行简要综述。并对复合材料在催化领域的发展进行总结和展望。     

Terpyridine-Based 3D Metal–Organic-Frameworks: A Structure–Property Correlation

Design, synthesis, and applications of metal–organic frameworks (MOFs) are among the most salient fields of research in modern inorganic and materials chemistry. As the structure and physical properties of MOFs are mostly dependent on the organic linkers or ligands, the choice of ligand system is of utmost importance in the design of MOFs. One such crucial organic linker/ligand is terpyridine (tpy), which can adopt various coordination modes to generate an enormous number of metal–organic frameworks. These frameworks generally carry physicochemical characteristics induced by the π-electron-rich (basically N-electron-rich moiety) terpyridines. In this minireview, the construction of 3D MOFs associated with symmetrical terpyridines is discussed. These ligands can be easily derivatized at the lateral phenyl (4′-phenyl) position and incorporate additional organic functionalities. These functionalities lead to some different binding modes and form higher dimensional (3D) frameworks. Therefore, these 3D MOFs can carry multiple features along with the characteristics of terpyridines. Some properties of these MOFs, like photophysical, chemical selectivity, photocatalytic degradation, proton conductivity, and magnetism, etc. have also been discussed and correlated with their frameworks.     

Continuous synthesis for zirconium metal-organic frameworks with high quality and productivity via microdroplet flow reaction

A series of Zr-based metal-organic frameworks were continuously synthesized with high quality and high productivity through microdroplet flow reaction.     

Fabrication of Microporous Metal–Organic Frameworks in Uninterrupted Mesoporous Tunnels: Hierarchical Structure for Efficient Trypsin Immobilization and Stabilization

Hierarchically porous metal–organic frameworks (HP-MOFs) are promising in various applications. Most reported HP-MOFs are prepared based on the generation of mesopores in microporous frameworks, and the formed mesopores are connected by microporous channels, limiting the accessibility of mesopores for bulky molecules. A hierarchical structure is formed by constructing microporous MOFs in uninterrupted mesoporous tunnels. Using the confined space in as-prepared mesoporous silica, highly dispersed metal precursors for MOFs are coated on the internal surface of mesoporous tunnels. Ligand vapor-induced crystallization is employed to enable quantitative formation of MOFs in situ, in which sublimated ligands diffuse into mesoporous tunnels and react with metal precursors. The obtained hierarchically porous composites exhibit record-high adsorption capacity for the bulky molecule trypsin. The thermal and storage stability of trypsin is improved upon immobilization on the composites.     

Direct Visualization of Atomic Structure in Multivariate Metal-Organic Frameworks (MOFs) for Guiding Electrocatalysts Design

The direct utilization of metal–organic frameworks (MOFs) for electrocatalytic oxygen evolution reaction (OER) has attracted increasing interests. Herein, we employ the low-dose integrated differential phase contrast-scanning transmission electron microscopy (iDPC-STEM) technique to visualize the atomic structure of multivariate MOFs (MTV-MOFs) for guiding the structural design of bulk MOFs for efficient OER. The iDPC-STEM images revealed that incorporating Fe³⁺ or 2-aminoterephthalate (ATA) into Ni-BDC (BDC: benzenedicarboxylate) can introduce inhomogeneous lattice strain that weaken the coordination bonds, which can be selectively cleaved via a mild heat treatment to simultaneously generate coordinatively unsaturated metal sites, conductive Ni@C and hierarchical porous structure. Thus, excellent OER activity with current densities of 10 and 100 mA cm⁻² are achieved over the defective MOFs at small overpotentials of 286 mV and 365 mV, respectively, which is superior to the commercial RuO₂ catalyst and most of the bulk MOFs.     

Multicomponent Assembly of Fluorescent‐Tag Functionalized Ligands in Metal–Organic Frameworks for Sensing Explosives

Detection of trace amounts of explosive materials is significantly important for security concerns and pollution control. Four multicomponent metal–organic frameworks ( MOFs‐12 , 13 , 23 , and 123 ) have been synthesized by employing ligands embedded with fluorescent tags. The multicomponent assembly of the ligands was utilized to acquire a diverse electronic behavior of the MOFs and the fluorescent tags were strategically chosen to enhance the electron density in the MOFs. The phase purity of the MOFs was established by PXRD, NMR spectroscopy, and finally by single‐crystal XRD. Single‐crystal structures of the MOFs‐12 and 13 showed the formation of three‐dimensional porous networks with the aromatic tags projecting inwardly into the pores. These electron‐rich MOFs were utilized for detection of explosive nitroaromatic compounds (NACs) through fluorescence quenching with high selectivity and sensitivity. The rate of fluorescence quenching for all the MOFs follows the order of electron deficiency of the NACs. We also showed the detection of picric acid (PA) by luminescent MOFs is not always reliable and can be misleading. This attracts our attention to explore these MOFs for sensing picryl chloride (PC), which is as explosive as picric acid and used widely to prepare more stable explosives like 2,4,6‐trinitroaniline from PA. Moreover, the recyclability and sensitivity studies indicated that these MOFs can be reused several times with parts per billion (ppb) levels of sensitivity towards PC and 2,4,6‐trinitrotoluene (TNT).     

Metal–Organic Framework Disintegrants: Enzyme Preparation Platforms with Boosted Activity

An enzyme formulation using customized enzyme activators (metal ions) to directly construct metal–organic frameworks (MOFs) as enzyme protective carriers is presented. These MOF carriers can also serve as the disintegrating agents to simultaneously release enzymes and their activators during biocatalysis with boosted activities. This highly efficient enzyme preparation combines enzyme immobilization (enhanced stability, easy operation) and homogeneous biocatalysis (fast diffusion, high activity). The MOF serves as an ion pump that continuously provides metal ion activators that greatly promote the enzymatic activities (up to 251 %). This MOF–enzyme composite demonstrated an excellent protective effect against various perturbation environments. A mechanistic investigation revealed that the spontaneous activator/enzyme release and ion pumping enable enzymes to sufficiently interact with their activators owing to the proximity effects, leading to a boost in biocatalytic performance.     

Metal–Organic Framework Disintegrants: Enzyme Preparation Platforms with Boosted Activity

An enzyme formulation using customized enzyme activators (metal ions) to directly construct metal–organic frameworks (MOFs) as enzyme protective carriers is presented. These MOF carriers can also serve as the disintegrating agents to simultaneously release enzymes and their activators during biocatalysis with boosted activities. This highly efficient enzyme preparation combines enzyme immobilization (enhanced stability, easy operation) and homogeneous biocatalysis (fast diffusion, high activity). The MOF serves as an ion pump that continuously provides metal ion activators that greatly promote the enzymatic activities (up to 251 %). This MOF–enzyme composite demonstrated an excellent protective effect against various perturbation environments. A mechanistic investigation revealed that the spontaneous activator/enzyme release and ion pumping enable enzymes to sufficiently interact with their activators owing to the proximity effects, leading to a boost in biocatalytic performance.     

In Situ Enzyme Immobilization by Covalent Organic Frameworks

Enzyme immobilization is a widely reported method to favor the applicability of enzymes by enhancing their stability and re-usability. Among the various existing solid supports and immobilization strategies, the in situ encapsulation of enzymes within crystalline porous matrices is a powerful tool to design biohybrids with a stable and protected catalytic activity. However, to date, only a few metal–organic frameworks (MOFs) and hydrogen-bonded organic frameworks (HOFs) have been reported. Excitingly, for the first time, Y. Chen and co-workers expanded the in situ bio-encapsulation to a new class of crystalline porous materials, namely covalent organic frameworks (COFs). The enzyme@COF materials not only exhibited high enzyme loading with minimal leaching, high catalytic activity and selectivity, chemical and long-term stability and recyclability but could also be scaled up to a few grams. Undoubtedly, this work opens new striking opportunities for enzymatic immobilization and will stimulate new research on COF-based matrices.     

Exploring the Performance Improvement of the Oxygen Evolution Reaction in a Stable Bimetal–Organic Framework System

Despite wide applications of bimetallic electrocatalysis in oxygen evolution reaction (OER) owing to their superior performance, the origin of the improved performance remains elusive. The underlying mechanism was explored by designing and synthesizing a series of stable metal–organic frameworks (MOFs: NNU‐21–24 ) based on trinuclear metal carboxylate clusters and tridentate carboxylate ligands. Among the examined stable MOFs, NNU‐23 exhibits the best OER performance; particularly, compared with monometallic MOFs, all the bimetallic MOFs display improved OER activity. DFT calculations and experimental results demonstrate that introduction of the second metal atom can improve the activity of the original atom. The proposed model of bimetallic electrocatalysts affecting their OER performance can facilitate design of efficient bimetallic catalysts for energy storage and conversion, and investigation of the related catalytic mechanisms.     

A miniaturized arrayed assay format for detecting small molecule-protein interactions in cells

Background: Two complementary approaches to studying the cellular function of proteins involve alteration of function either by mutating protein-encoding genes or by binding a small molecule to the protein. A mutagen can generate millions of genetic mutations; correspondingly, split-pool synthesis can generate millions of unique ligands attached to individual beads. Genetic screening of mutations is relatively straightforward but, in contrast, split-pool synthesis presents a challenge to current methods of screening for compounds that alter protein function. The methods used to screen natural products are not feasible for large libraries composed of covalently immobilized compounds on synthesis beads. The sheer number of compounds synthesized by split-pool synthesis, and the small quantity of individual compound attached to each bead require assay miniaturization for efficient screening.Results: We present a miniaturized cell-based technique for the screening of ligands prepared by split-pool synthesis. Spatially defined droplets with uniform volumes of approximately 50–150 nanoliters (depending on well dimensions) are arrayed on plastic devices prepared using a combination of photolithography and polymer molding. Using this microtechnology, approximately 6,500 assays using either yeast cells or mammalian tissue culture can be performed within the dimensions of a standard 10 cm petri dish. We demonstrate that the biological effect of a small molecule prepared by split-pool synthesis can be detected in this format following its photorelease from a bead.Conclusions: The miniaturized format described here allows uniformly sized nanodroplets to be arrayed on plastic devices. The design is amenable to a large number of biological assays and the spatially arrayed format ensures uniform and controlled ligand concentrations and should facilitate automation of assays. The screening method presented here provides an efficient means of rapidly screening large numbers of ligands made by split-pool synthesis in both yeast and mammalian cells.     

Recent Advances of Metal-Organic Frameworks-based Nanozymes for Bio-applications

Artificial nanoenzymes with enzyme-like catalytic activity have gradually become an alternative to natural enzymes due to their low production cost, high stability, and good tolerance. In recent years, various enzyme mimics have emerged with the rapid development of nano-teclnology. Metal-organic frameworks(MOFs) are a novel class of porous inorganic-organic hybrid materials made from metal ions/clusters and organic ligands, and MOFs-based nanozymes show great prospect in biosensing, biocatalysis, biomedical imaging, and therapeutic applications, due to unique properties, such as high specific surface area, high porosity, tunable morphology, and excellent biocatalytic properties. In this paper, the recent progresses concerning MOFs-based nanozymes are systematically summarized, including the synthesis, design strategies and related applications, which are divided into two major categories, namely, MOFs structured nanoenzymes and MOFs composite structured nanoenzymes. Meanwhile, the applications of various classifications of MOFs research are introduced. At the end, current challenges and future perspectives of MOFs-based nanozymes are also discussed. It is highly expected that this review on this important area can provide a meaningful guidance for tumor therapy, biosensing and other aspects.     

Synergistic Catalysis of Enzymes and Biomimetic MOFs:Immobilizing Cyt c on Two-dimensional MOFs to Enhance the Performance of Peroxidase

Metal-organic frameworks(MOFs) have been widely regarded as promising carriers for enzyme immobilization owing to their advantages in improving loading and regulating interaction with enzymes. However, they are still suffering from the problems of slow mass transfer and compromising activity. In this paper, the active two-dimensional(2D) MOF of Cu-TCPP(Fe)[TCPP=tetrakis(4-carboxy-phenyl)porphyrin], which possesses the biomimetic architecture of peroxidase, was adopted to anchor cytochrome(Cyt c) for the enhancement of catalytic activity. The atomic/nanometer thickness and micrometer lateral dimension of 2D MOFs can ensure the full exposure of immobilized enzymes and a shorter diffusion distance for the reactant molecules. Besides, the active carrier can provide synergistic catalysis and activity compensation during the reaction. When tested in the decomposition reaction of H₂O₂, Cyt c/Cu-TCPP(Fe) exhibited nearly twice catalytic activity and an accelerated catalytic rate compared to free Cyt c.     

Competing Roles of Two Kinds of Ligand during Nonclassical Crystallization of Pillared-Layer Metal-Organic Frameworks Elucidated Using Microfluidic Systems

To diversify metal-organic frameworks (MOFs), multi-component MOFs constructed from more than two kinds of bridging ligand have been actively investigated due to the high degree of design freedom afforded by the combination of multiple ligands. Predicting the synthesis conditions for such MOFs requires an understanding of the crystallization mechanism, which has so far remained elusive. In this context, microflow systems are efficient tools for capturing non-equilibrium states as they facilitate precise and efficient mixing with reaction times that correspond to the distance from the mixing point, thus enabling reliable control of non-equilibrium crystallization processes. Herein, we prepared coordination polymers with pillared-layer structures and observed the intermediates in the syntheses with an in-situ measurement system that combines microflow reaction with UV/Vis and X-ray absorption fine-structure spectroscopies, thereby enabling their rapid nucleation to be monitored. Based on the results, a three-step nonclassical nucleation mechanism involving two kinds of intermediate is proposed.     

A photochemical method for patterning the immobilization of ligands and cells to self-assembled monolayers

This work describes a chemically well defined method for patterning ligands to self-assembled monolayers (SAMs) of alkanethiolates on gold. This method begins with monolayers presenting a nitroveratryloxycarbonyl (NVOC)-protected hydroquinone which is photochemically irradiated to reveal a hydroquinone group. The resulting hydroquinone is then oxidized to the corresponding benzoquinone, providing a site for the Diels-Alder mediated immobilization of ligands. The rate constant for the photochemical deprotection is 0.032 s(-1) (with an intensity of approximately 100 mW/cm(2) between 355 and 375 nm), corresponding to a half-life of 21 s. The hydroquinone is oxidized to the benzoquinone using either electrochemical or chemical oxidation and then functionalized by reaction with a cyclopentadiene-tagged ligand. Two methods for patterning the immobilization of ligands are described. In the first, the substrate is illuminated through a mask to generate a pattern of hydroquinone groups, which are elaborated with ligands. In the second method, an optical microscope fit with a programmable translational stage is used to write patterns of deprotection which are then again elaborated with ligands. This technique is characterized by the use of well-defined chemical reactions to control the regions and densities of ligand immobilization and will be important for a range of applications that require patterned ligands for biospecific interactions.