all types of organic framework applications and their food applications

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTMetal–Organic Framework Materials as Chemical SensorsLauren E. Kreno†, Kirsty Leong‡, Omar K. Farha†, Mark Allendorf*‡, Richard P. Van Duyne†, and Joseph T. Hupp*†View Author Information† Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States‡ Sandia National Laboratories, Mail Stop 9291, Livermore, California 94551-0969, United States*Phone: (925) 294-2895 (M.A.); (847) 491-3504 (J.T.H.). E-mail: [email protected] (M.A.); [email protected] (J.T.H.).Cite this: Chem. Rev. 2012, 112, 2, 1105–1125Publication Date (Web):November 9, 2011Publication History Received18 August 2011Published online9 November 2011Published inissue 8 February 2012https://pubs.acs.org/doi/10.1021/cr200324thttps://doi.org/10.1021/cr200324treview-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views71971Altmetric-Citations6186LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Luminescence,Metal organic frameworks,Molecules,Sensors,Thin films Get e-Alerts

Metal-organic frameworks (MOFs) display a wide range of luminescent behaviors resulting from the multifaceted nature of their structure. In this critical review we discuss the origins of MOF luminosity, which include the linker, the coordinated metal ions, antenna effects, excimer and exciplex formation, and guest molecules. The literature describing these effects is comprehensively surveyed, including a categorization of each report according to the type of luminescence observed. Finally, we discuss potential applications of luminescent MOFs. This review will be of interest to researchers and synthetic chemists attempting to design luminescent MOFs, and those engaged in the extension of MOFs to applications such as chemical, biological, and radiation detection, medical imaging, and electro-optical devices (141 references).

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTLuminescent Functional Metal–Organic FrameworksYuanjing Cui†‡, Yanfeng Yue‡, Guodong Qian*†, and Banglin Chen*‡View Author Information† State Key Laboratory of Silicon Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China‡ Department of Chemistry, University of Texas at San Antonio, San Antonio, Texas 78249-0698, United States*E-mail: [email protected] (G.Q.), [email protected] (B.C.).Cite this: Chem. Rev. 2012, 112, 2, 1126–1162Publication Date (Web):June 21, 2011Publication History Received30 March 2011Published online21 June 2011Published inissue 8 February 2012https://pubs.acs.org/doi/10.1021/cr200101dhttps://doi.org/10.1021/cr200101dreview-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views65410Altmetric-Citations5511LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Fluorescence,Ions,Lanthanides,Luminescence,Metal organic frameworks Get e-Alerts

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Metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) are open, crystalline supramolecular coordination architectures with porous facets. These chemically tailorable framework materials are the subject of intense and expansive research, and are particularly relevant in the fields of sensory materials and device engineering. As the subfield of MOF-based sensing has developed, many diverse chemical functionalities have been carefully and rationally implanted into the coordination nanospace of MOF materials. MOFs with widely varied fluorometric sensing properties have been developed using the design principles of crystal engineering and structure-property correlations, resulting in a large and rapidly growing body of literature. This work has led to advancements in a number of crucial sensing domains, including biomolecules, environmental toxins, explosives, ionic species, and many others. Furthermore, new classes of MOF sensory materials utilizing advanced signal transduction by devices based on MOF photonic crystals and thin films have been developed. This comprehensive review summarizes the topical developments in the field of luminescent MOF and MOF-based photonic crystals/thin film sensory materials.

Water adsorption in porous materials is important for many applications such as dehumidification, thermal batteries, and delivery of drinking water in remote areas. In this study, we have identified three criteria for achieving high performing porous materials for water adsorption. These criteria deal with condensation pressure of water in the pores, uptake capacity, and recyclability and water stability of the material. In search of an excellently performing porous material, we have studied and compared the water adsorption properties of 23 materials, 20 of which are metal-organic frameworks (MOFs). Among the MOFs are 10 zirconium(IV) MOFs with a subset of these, MOF-801-SC (single crystal form), -802, -805, -806, -808, -812, and -841 reported for the first time. MOF-801-P (microcrystalline powder form) was reported earlier and studied here for its water adsorption properties. MOF-812 was only made and structurally characterized but not examined for water adsorption because it is a byproduct of MOF-841 synthesis. All the new zirconium MOFs are made from the Zr6O4(OH)4(-CO2)n secondary building units (n = 6, 8, 10, or 12) and variously shaped carboxyl organic linkers to make extended porous frameworks. The permanent porosity of all 23 materials was confirmed and their water adsorption measured to reveal that MOF-801-P and MOF-841 are the highest performers based on the three criteria stated above; they are water stable, do not lose capacity after five adsorption/desorption cycles, and are easily regenerated at room temperature. An X-ray single-crystal study and a powder neutron diffraction study reveal the position of the water adsorption sites in MOF-801 and highlight the importance of the intermolecular interaction between adsorbed water molecules within the pores.

Functionalization of hydrogen-bonded organic frameworks (HOFs) for specific applications has been a long-lasting challenge in HOF materials. Here, an efficient way to integrate functional species in the HOF structure through constructing an anionic framework is presented. The obtained HOFs, taking PFC-33 (PFC = porous materials from FJIRSM,CAS) as an example, integrate a porphyrin photosensitizer as a porous backbone and a commercial biocide as counterions in the structure. The permanent channels and the electrostatic interaction between the framework and the counterions provide PFC-33 ion-responsive biocide-release behavior in various physiological environments, thus exhibiting synergistic photodynamic and chemical antimicrobial efficiency. The unbonded carboxyl groups residing on the HOF surface further allow for manipulating the interfacial interaction between the PFC-33 and the polymer matrix for membrane fabrication. Therefore, a polyHOF membrane with high stability, desired flexibility, and good permeability is obtained, which demonstrates noticeable bacterial inhibition toward Escherichia coli. This study may shed light on the functionalization of HOF materials for broad application potentials.

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Food safety is a prevalent concern around the world. As such, detection, removal, and control of risks and hazardous substances present from harvest to consumption will always be necessary. Metal-organic frameworks (MOFs), a class of functional materials, possess unique physical and chemical properties, demonstrating promise in food safety applications. In this review, the synthesis and porosity of MOFs are first introduced by some representative examples that pertain to the field of food safety. Following that, the application of MOFs and MOF-based materials in food safety monitoring, food processing, covering preservation, sanitation, and packaging is overviewed. Future perspectives, as well as potential opportunities and challenges faced by MOFs in this field will also be discussed. This review aims to promote the development and progress of MOF chemistry and application research in the field of food safety, potentially leading to novel solutions.

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Food contains a variety of poisonous and harmful substances that have an impact on human health. Therefore, food safety is a worldwide public concern. Food detection approaches must ensure the safety of food at every step of the food supply chain by monitoring and evaluating all hazards from every single step of food production. Therefore, early detection and determination of trace-level contaminants in food are one of the most crucial measures for ensuring food safety and safeguarding consumers' health. In recent years, various methods have been introduced for food safety analysis, including classical methods and biomolecules-based sensing methods. However, most of these methods are laboratory-dependent, time-consuming, costly, and require well-trained technicians. To overcome such problems, developing rapid, simple, accurate, low-cost, and portable food sensing techniques is essential. Metal-organic frameworks (MOFs), a type of porous materials that present high porosity, abundant functional groups, and tunable physical and chemical properties, demonstrates promise in large-number applications. In this regard, MOF-based sensing techniques provide a novel approach in rapid and efficient sensing of pathogenic bacteria, heavy metals, food illegal additives, toxins, persistent organic pollutants (POPs), veterinary drugs, and pesticide residues. This review focused on the rapid screening of MOF-based sensors for food safety analysis. Challenges and future perspectives of MOF-based sensors were discussed. MOF-based sensing techniques would be useful tools for food safety evaluation owing to their portability, affordability, reliability, sensibility, and stability. The present review focused on research published up to 7 years ago. We believe that this work will help readers understand the effects of food hazard exposure, the effects on humans, and the use of MOFs in the detection and sensing of food hazards.

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Investigation on food safety and preservation is essential to provide high quality and safe food for human beings, including accurate determination and efficient removal of inorganic heavy metal ions and organic contaminants, as well as regulation of food postharvest ripening and intelligent sterilization. In the last two decades, metal-organic frameworks (MOFs), as functionalized porous materials, have aroused interests of researchers because of their advantages of high porosity, large specific surface area, flexible structure properties, and abundant binding sites for guest molecules. MOFs have shown great potentials in practical applications in food and related fields. In this overview, we summarized the MOF crystallization mechanisms, synthesis routes and methods, stability, as well as the applications in food contamination including removal of heavy metal ions, dyes, and antibiotics, and food preservation including regulation of fruit and vegetable ripening, removal of moisture and oxygen, and high-efficiency sterilization. Finally, two perspectives focusing on the development of MOFs for innovative food research, i.e., food-grade MOFs and MOF composites are suggested based on our understanding.

Food safety has attracted attention worldwide, and how to detect various kinds of hazardous substances in an efficient way has always been a focus. Metal-Organic Frameworks (MOFs) are a class of hybrid porous materials formed by organic ligand and metal ions. Nanoscale MOFs (NMOFs) exhibit great potential in serving as fluorescence sensors for food safety due to their superior properties including high accuracy, great stability, fast response, etc. In this review, we focus on the recent development of NMOFs sensing for food safety. Several typical methods of NMOFs synthesis are presented. NMOFs-based fluorescence sensors for contaminants and adulterants, such as antibiotics, food additives, ions and mycotoxin etc. are summarized, and the sensing mechanisms are also presented. We explore these challenges in detail and provide suggestions about how they may be surmounted. This review could help the exploration of NMOFs sensors in food related work.

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Comprehensive Summary Nitrofuran antibiotics threaten human health and the environment due to their toxicity and persistence. Their detection is challenging due to low concentrations and interference, while fluorescence sensing offers superior sensitivity and selectivity for effective monitoring. In this work, a novel halogen‐bonded organic framework, XOF‐TPEM , was introduced, constructed using an imidazole‐based ligand AIE molecule, TPEM . The framework was successfully characterized by various techniques, including 1 H NMR, PXRD, XPS, FT‐IR, HRTEM, SAED, SEM and EDS, confirming its excellent crystalline structure. As TPEM is an electron‐donating AIE fluorophore, the fluorescent XOF‐TPEM demonstrates potential as a selective sensor for electron‐deficient nitrofuran antibiotics. Experimental results show that it exhibits high sensitivity and selectivity for detecting nitrofurans such as NFT, FZD, FLD, and NFZ, with LODs of 9.7 ppb, 11.0 ppb, 19.7 ppb, and 236.1 ppb, respectively. Mechanistic studies indicate that the outstanding fluorescence detection performance is attributed to the inner‐filter effect occurring between XOF‐TPEM and the nitrofuran antibiotics. Through comparison with the sensing performance of a pyridine‐based XOF, the superiority of imidazole ligands in constructing XOFs is demonstrated. This study presents a novel luminescent halogen‐bonded organic framework and highlights the superiority of imidazole‐based halogen‐bonded organic frameworks, underscoring their significant potential for expanding their functional applications.

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The static labels presently prevalent on the food market are confronted with challenges due to the assumption that a food product only undergoes a limited range of predefined conditions, which cause elevated safety risks or waste of perishable food products. Hence, integrated systems for measuring food freshness in real time have been developed for improving the reliability, safety, and sustainability of the food supply. However, these systems are limited by poor sensitivity and accuracy. Here, a metal-organic framework mixed-matrix membrane and deep learning technology were combined to tackle these challenges. UiO-66-OH and polyvinyl alcohol were impregnated with six chromogenic indicators to prepare sensor array composites. The sensors underwent color changes after being exposed to ammonia at different pH values. The limit of detection of 80 ppm for trimethylamine was obtained, which was practically acceptable in the food industry. Four state-of-the-art deep convolutional neural networks were applied to recognize the color change, endowing it with high-accuracy freshness estimation. The simulation test for chicken freshness estimation achieved accuracy up to 98.95% by the WISeR-50 algorithm. Moreover, 3D printing was applied to create a mold for possible scale-up production, and a portable food freshness detector platform was conceptually built. This approach has the potential to advance integrated and real-time food freshness estimation.

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A metal–organic framework hybrid-based nanoenzyme is developed for dual-mode sensitive detection of pesticide chlorpyrifos and its bioaccumulation . • A MOF-sealed hybrid nanoenzyme system is designed for sensing pesticide chlorpyrifos. • A dual-mode sensing strategy is realized sensitively and selectively. • The sensor showed a detection limit of chlorpyrifos with 0.2 ng mL −1 by fluorescence. • The bioaccumulation of chlorpyrifos in vegetables is determined. • The strategy can be extended as a general analysis platform against pesticide. Developing efficient and intelligent method for analyzing harmful agrochemicals like organophosphorus pesticides plays a crucial role in food and environmental safety surveillance. Herein, a metal–organic framework (MOF)-sealed heterogeneous nanoenzyme was designed for monitoring the bioaccumulation of chlorpyrifos in vegetables. The hybrid named CeO x @fZIF was sequentially prepared through cerium oxide (CeO x ) as the core, and Cu(II)-centered zeolitic imidazolate framework (ZIF) as shell, which encapsulated fluorescence dye. The fluorescence from the encapsulated dye and the colorimetric signal from the catalytic product by the inner nanoenzyme CeO x were synchronously blocked by the outer ZIF shell of CeO x @fZIF. Under the alkaline phosphatase (ALP) enzyme-mediated reduction of Cu(II) in the ZIF shell, the obstruction of shell was relieved with the shell collapse. The enzymatic capability of inner CeO x for colorimetric catalysis and the dye fluorescence were synergistically recovered in a controllable way. Accompanied with the chlorpyrifos-inhibited capability for ALP, a fluorescence/colorimetric dual-signal sensor was fabricated. The dual-mode signal of CeO x @fZIF-based nanosystem exhibited a strong linear correlation with chlorpyrifos concentrations, achieving the detection limit of 0.2 ng/mL in fluorescence and 15 ng/mL in colorimetric. This strategy was assessed across various food matrices and had an outstanding reaction with a high percentage of recovery. Furthermore, the nanoenzyme system was employed to determine chlorpyrifos accumulation in pakchoi. The presented nanosystem exploited the feasibility of MOF-controlled nanoenzyme sensor and lighted up a facile pathway to prepare dual-mode sensor of pesticide monitoring for food and ecological environment safety.

Abstract The unambiguous detection and classification of volatile organic compounds (VOCs) are crucial in many fields. For using VOC‐sensing to explore the alteration and spoilage of food, very inexpensive sensors are desired. Simple colorimetric sensors seem highly attractive for these applications. Here, a label‐free, colorimetric sensor array made of metal‐organic‐framework‐based (MOF‐based) Fabry‐Pérot (FP) films is presented where the signal read‐out is performed either by their optical spectra or by pictures taken with a smartphone camera. Exposing the FP‐MOF‐films to various VOCs causes a reversible shift of the photonic pattern, where the magnitude of the shift depends on the VOC type, its concentration, and the MOF structure. The application of machine‐ learning‐ algorithms on the sensor data allows to identify the VOCs with a high classification accuracy (92% at 100 ppm). It is shown that the sensor array read‐out can also be performed with a common smartphone camera, also precisely classifying the VOC analytes. Moreover, fresh and spoiled food, like milk and meat, is distinguished by its head space. Thus, the study presents a very inexpensive platform of small colorimetric sensors that allow determining the quality, alteration, and spoilage of food, and it may contribute to realizing smart labels and intelligent packaging.

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Luminescent Tb3+ functionalized metal–organic frameworks (MOFs) are prepared and act as food preservatives sensor and water scavenger for NO2–. Classical metal–organic frameworks with uncoordinated N atoms in pores are elected as carrier to encapsulate Tb3+ ions. This Tb3+ incorporated material reveals excellent characteristic green luminescence of Tb3+ and good fluorescence stability in water. Subsequently, we choose this probe for sensing NO2– among several food preservative compounds, showing a highly sensitive capability for detection of NO2–; it is then proved that the Dexter energy transfer (DET) causes the luminescent quenching between Tb3+ and NO2–, achieving the detection of NO2–. This probe is also employed to detect the NO2– in real water samples and act as water scavenger to remove the NO2– in drinking water, showing a good removal capacity 3.45 mg (75.0 μmol) of NO2– per gram of particles.

Two Co-based fluorescent MOFs are reported to detect biogenic amines in protein rich foods like fish and cheese.

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Developing sensitive practical sensors for monitoring pesticide residues in edible foods and environmental samples is vital for food safety and environmental protection. Enzyme-inhibited biosensors offer effective alternative sensing strategies by using the inherent characteristics of pesticides. To further improve the degradation function of pesticide sensors, here, a target-triggered porphyrin metal-organic framework (MOF)-based nanosystem was designed with the synergetic bifunction of sensitive detection and controllable degradation of the triazophos pesticide. As a result of triazophos-inhibited glutathione consumption, the MOF collapsed and released the ligand porphyrin, leading to the recovery of fluorescence and photosensitization of the free porphyrin. The fluorescence recovery resulted in a sensitive detection limit of 0.6 ng mL^-1 for triazophos, which was also applied for the determination of contaminated samples and bioaccumulation in rice. Furthermore, the target-activated photocatalytic ability of porphyrin endowed the system with the ability to effectively generate reactive oxygen species for degrading triazophos with a removal rate of ∼85%, achieving eco-friendly synergetic detection and photodegradation in a controllable way. Therefore, the intelligent multifunctional MOF system demonstrated the potential of programmable systems for jointly controllable tracking and elimination of pesticide residues in the environment and opened a new avenue for designing a precise mechanism for stimulus-triggered degradation of pesticide residues accompanied by sensitive detection for environmental friendliness and food safety.

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Carbendazim (CBZ), a well-known benzimidazole pesticide, is utilized in agriculture to prevent and cure plant diseases caused by fungi. Residual CBZ in food poses serious threat to human health. Herein, a fluorescent two-dimensional terbium-based metal-organic framework (2D Tb-MOF) nanosheet sensor was developed for the rapid and ultrasensitive detection of CBZ. The 2D Tb-MOF nanosheets, prepared with Tb³⁺ ions and 5-borono-1,3-benzenedicarboxylic acid (BBDC) as the precursors, exhibited excellent optical properties. Upon the addition of CBZ, the fluorescence of Tb-MOF nanosheets was quenched because of the inner filter effect (IFE) and dynamic quenching. The fluorescence sensor offered two linear ranges of 0.06-4 and 4-40 µg/mL with a low detection limit of 17.95 ng/mL. Furthermore, the proposed sensing platform was successfully applied to assay CBZ in apples and tea, and satisfactory results were obtained. This study provides an effective alternative strategy for the qualitative and quantitative determination of CBZ to ensure food safety.

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Antibiotic residues in food are contaminants from transfer across the food chain, starting from livestock, which pose health and safety concerns. Detecting them is of current need and can be accomplished using materials like metal–organic-frameworks.

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A novel magnetic metal–organic framework (MOF-199/dithiocarbamate modified magnetite nanoparticles composite) was synthesized and utilized for speciation analysis of inorganic arsenic.

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The improvement of food safety and the reduction of food loss and waste require the development of new bioanalytical tools that provide chemical information about the composition of food that is of great value for improving traceability and extending the shelf life of food. Herein, a Cu-based metal-organic framework has been synthesized and immobilized onto cellulose paper disks for colorimetric and fluorescent detection and quantification of biogenic amines in food. The color of the nano metal-organic framework changes from green to brown in the presence of low amounts of biogenic amine vapors. Also, the fluorescence emission of the nano metal-organic framework greatly decreases after exposing the cellulose disks to amine vapors. The developed sensing paper disk exhibits a quick response to the presence of volatile biogenic amines, very low detection limits, and great selectivity. Also, the paper sensor was used for real-time monitoring of biogenic amines in bass samples at different temperature conditions, being a highly valuable method for evaluating food freshness and safeguarding food safety.

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Fluorescence nanomaterial sensors have exhibited excellent application potential in biothiols analyses. The fluorescence sensor arrays constructed from upconversion luminescence metal-organic frameworks nanocomposites (LMOFs) can provide impressive discrimination and exquisite fingerprinting capabilities for extremely similar analytes. Herein, an upconversion fluorescence sensor array based on LMOFs featuring UiO-type metal-organic frameworks-functionalized lanthanide-doped upconversion nanoparticles was proposed, wherein Cu²⁺ can make the fluorescence quenching of LMOFs and preferentially bind biothiols to recover fluorescence in different degrees forming unique fingerprinting. The fluorescence sensor array displayed an excellent pattern recognition for five biothiols (glutathione, homocysteine, N-acetylcysteine, and L/D-cysteine) even at 50 µM by linear discriminant analysis, and the discernment for the enantiomers of L/D-cysteine, as well as the accurate identification (90.0% accuracy) of biothiols in food samples (tea beverage and white wine). Such fluorescence sensor array might provide a simple and efficient detection method for biothiols.

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Functional nanoprobes which detect specific food hazards quickly and simply are still in high demand in the field of food-safety inspection research. In the present work, a dual-emission metal-organic framework-based ratiometric fluorescence probe was integrated to detect Cu²⁺ and Pb²⁺ with rapidness and ease. Specifically, quantum dots (QDs) and carbon quantum dots (CQDs) were successfully embedded into zeolitic imidazolate framework-67 (ZIF-67) to function as a novel ratiometric fluorescent sensing composite. The ratiometric fluorescence signal of CQDs/QDs@ZIF-67 was significantly aligned with the concentration of metal ions to give an extremely low detection limit of 0.3324 nM. The highly sensitive and selective CQDs/QDs@ZIF-67 composite showed potential for the rapid and cost-effective detection of two metal ions.

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Metal-organic frameworks (MOFs) have been attracting tremendous attention owing to their great structural diversity and functional tunability. Despite numerous inherent merits and big progress in the fundamental research (synthesizing new compounds, discovering new structures, testing associated properties, etc.), poor chemical stability of most MOFs severely hinders their involvement in practical applications, which is the final goal for developing new materials. Therefore, constructing new stable MOFs or stabilizing extant labile MOFs is quite important. As with them, some "potential" applications would come true and a lot of new applications under harsh conditions can be explored. Efficient strategies are being pursued to solve the stability problem of MOFs and thereby achieve and expand their applications.In this Account, we summarize the research advance in the design and synthesis of chemically stable MOFs, particularly those stable in acidic, basic, and aqueous systems, as well as in the exploration of their applications in several expanding fields of environment, energy, and food safety, which have been dedicated in our lab over the past decade. The strategies for accessing stable MOFs can be classified into: (a) assembling high-valent metals (hard acid, such as Zr⁴⁺, Al³⁺) with carboxylate ligands (hard base) for acid-stable MOFs; (b) combining low-valent metals (soft acid, such as Co²⁺, Ni²⁺) and azolate ligands (soft base, such as pyrazolate) for alkali-resistant MOFs; (c) enhancing the connectivity of the building unit; (d) contracting or rigidifying the ligand; (e) increasing the hydrophobicity of the framework; and (f) substituting liable building units with stable ones (such as metal metathesis) to obtain robust MOFs. In addition, other factors, including the geometry and symmetry of building units, framework-framework interaction, and so forth, have also been taken into account in the design and synthesis of stable MOFs. On the basis of these approaches, the stability of resulting MOFs under corresponding conditions has been remarkably enhanced.With high chemical stability achieved, the MOFs have found many new and significant applications, aiming at addressing global challenges related to environmental pollution, energy shortage, and food safety.A series of stable MOFs have been constructed for detecting and eliminating contaminations. Various fluorescent MOFs were rationally customized to be powerful platforms for sensing hazardous targets in food and water, such as dioxins, antibiotics, veterinary drugs, and heavy metal ions. Some hydrophobic MOFs even showed effective and specific capture of low-concentration volatile organic compounds.Novel MOFs with record-breaking acid/base/nucleophilic regent resistance have expanded their application scope under harsh conditions. BUT-8(Cr)A, as the most acid-stable MOF yet, showed reserved structural integrity in concentrated H₂SO₄ and recorded high proton conductivity; the most alkali-resistant MOF, PCN-601, retained crystallinity even in boiling saturated NaOH aqueous solution, and such base-stable MOFs composed of non-noble metal clusters and poly pyrazolate ligands also demonstrated great potential in heterogeneous catalysis in alkaline/nucleophilic systems for the first time.It is believed that this Account will provide valuable references on stable MOFs' construction as well as application expansion toward harsh conditions, thereby being helpful to promote MOF materials to step from fundamental research to practical applications.

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The practical applications of moisture sensitive metal-organic frameworks (MOFs) in the extraction technique are faced with avoided challenges related to competitive adsorption and hydrostability. The target analytes cannot be effectively extracted under humid conditions because of the competitive moisture adsorption and/or framework structure collapse of MOFs. In this Letter, metal-organic framework (MOF)@microporous organic network (MON) hybrid materials were explored for the first time as fiber coatings for solid-phase microextraction (SPME). Microporous materials with a hydrophobic surface was formed by coating the MOFs (MIL-101 and MOF-5) with MON through a sonogashira coupling reaction. MON acted as a hydrophobic "shield" to hinder the competitive moisture adsorption and improve moisture resistance and stability of the fiber. The sorbent exhibited higher enrichment factors (1215-3805) toward PAHs than other analytes in the water samples. An SPME method using MOF@MON-based fiber was developed to quantitatively determine PAHs. The proposed method was successfully applied to analyze PAHs in environmental water, particulate matter (PM_2.5), and food samples. A successful technique is proposed to chemically control MOF for applications in solid-phase sorption-based extraction techniques.

Due to increasing food-safety issues, exploiting efficient approaches for food quality assessment and instrumentation has attracted concerns worldwide. Herein, a smart evaluation system based on a fluorescent metal-organic framework (MOF) is developed for real-time visual monitoring of food freshness. Via post-synthetic modification, a ratiometric fluorescent MOF probe is constructed by covalently coupling fluorescein 5-isothiocyanate (5-FITC) with NH₂ -rich lanthanide MOF. The probes exhibit a dual-emissive-responsive to biogenic amine, resulting in an increase in FITC emission along with a decrease in Eu³⁺ emission accompanied by a clear distinguishable color transition from orange red to green. After doping the probes on a flexible substrate, the obtained MOF composite film can be integrated with a smartphone-based portable platform easily. It is proved that this smart evaluation system can be used for on-site inspection of the freshness of raw fish samples. This work develops a fluorescent MOF-based smart evaluation system as a novel platform for application in food monitoring, which not only has enormous economic value but also holds great public health significance.

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Porous metal-organic frameworks (MOFs) have been studied in the context of a wide variety of applications, particularly in relation to molecular storage and separation sciences. Recently, we reported a green, renewable framework material composed of γ-cyclodextrin (γ-CD) and alkali metal salts--namely, CD-MOF. This porous material has been shown to facilitate the separation of mixtures of alkylaromatic compounds, including the BTEX mixture (benzene, toluene, ethylbenzene, and the regioisomers of xylene), into their pure components, in both the liquid and gas phases, in an energy-efficient manner which could have implications for the petrochemical industry. Here, we report the ability of CD-MOF to separate a wide variety of mixtures, including ethylbenzene from styrene, haloaromatics, terpinenes, pinenes and other chiral compounds. CD-MOF retains saturated compounds to a greater extent than their unsaturated analogues. Also, the location of a double bond within a molecule influences its retention within the extended framework, as revealed in the case of the structural isomers of pinene and terpinine, where the isomers with exocyclic double bonds are more highly retained than those with endocyclic double bonds. The ability of CD-MOF to separate various mono- and disubstituted haloaromatic compounds appears to be controlled by both the size of the halogen substituents and the strength of the noncovalent bonding interactions between the analyte and the framework, an observation which has been confirmed by molecular simulations. Since CD-MOF is a homochiral framework, it is also able to resolve the enantiomers of chiral analytes, including those of limonene and 1-phenylethanol. These findings could lead to cheaper and easier-to-prepare stationary phases for HPLC separations when compared with other chiral stationary phases, such as CD-bonded silica particles.

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In many industries, including biomedical, diagnostics, agriculture, food safety, and others, color change detection plays a crucial role as an analytical tool. A colorimetric system identifies the color of a sample by analysing the proportions of red, green, and blue (RGB) light that is transmitted through the reagents. Quantitative analysis of color can be conducted using expensive optical devices such as webcams, smartphones, and cameras. In this study, we present the preliminary findings of a cost-effective, portable RGB sensor that utilizes nanometal-organic frameworks (nanoMOFs) to ensure food safety. It consists of eight pairs of white light-emitting diodes (LEDs), eight digital color sensors, and another eight wells for holding the samples and blanks. The viability of the RGB sensor has been proven for quantifying amines.

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Antibiotic residues have become a significant challenge in food safety, threatening both ecosystem integrity and human health. To combat this problem, we developed an innovative photo-powered, self-powered aptasensor that employs a novel carbon-doped three-dimensional graphitic carbon nitride (3D-CN) combined with a metal-organic framework composed of N-doped copper(I) oxide-carbon (Cu₂O@C) skeletons. The 3D-CN serves as the photoanode, offering stable photocurrent production due to its three-dimensional open framework structure. The N-doped Cu₂O@C acts as the photocathode, providing oxidation protection for the metal core and enhancing light absorption due to its metal-organic framework structure. A key feature of our work is exploiting the Fermi level difference between the n-type photoanode and p-type photocathode, which facilitates faster migration of photogenerated electrons toward the photocathode, thereby enhancing the sensor's self-powered effect. Experimental results reveal that upon aptamer loading, the sensor can linearly detect tetracycline (TC) within a range of 0.5 pmol/L to 300 nmol/L, with a detection limit as low as 0.13 pmol/L. It also demonstrates excellent selectivity, stability, and reproducibility, making it applicable to real samples such as milk and river water. Consequently, our research provides a highly efficient and sensitive method for monitoring TC in food, with significant practical implications and profound impacts on food safety.

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The pervasive application of organophosphorus pesticides (OPPs) in agriculture underscores the critical need for sensitive and reliable analytical techniques to safeguard food safety. Addressing this challenge, this work presents a rigorous comparative evaluation of two engineered sorbents for dispersive micro-solid phase extraction (D-μ-SPE) prior to gas chromatography-mass spectrometry (GC-MS): Bimetallic Fe/Co-MIL-88A and a novel Bimetallic Fe/Co-MIL-88A-on-MIL-88B composite. While both sorbents demonstrated high and statistically comparable extraction efficiencies, the composite was selected for its exceptional reusability and sustained performance over five consecutive cycles. Leveraging a design of experiments (DoE) approach, key extraction parameters were optimized for both sorbents, achieving remarkable sensitivity and precision. The method demonstrates an impressive linear dynamic range (LDR) of 0.07-900 ng mL^-1, with detection limits as low as 0.02-0.09 ng mL^-1, alongside high enrichment factors (up to 67) and excellent reproducibility (RSDs 3.16-4.35 %). Analysis of vegetable and fruit juice samples yielded robust recoveries (93.5-103.6 %) with precision (RSDs 4.37-6.33 %), affirming the method's reliability for routine monitoring. This work not only advances analytical capabilities for OPP detection but also contributes significantly to food safety surveillance, ensuring enhanced consumer protection.

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A novel core-shell metal-organic framework coated with a dummy template molecularly imprinted polymer (MOF@DMIP) was synthesized by one-pot bulk polymerization for the detection of pyrraline in food samples. The pyrraline analogue pyrrolidine-3-carboxylic acid was used as the template because of its lower cost, and MIL-101 was used as the MOF core owing to its numerous inherent advantages, including high chemical and hydrothermal stabilities. MIL-101@DMIP was used to detect trace pyrraline in foods by solid-phase extraction combined with high-performance liquid chromatography. It exhibited the advantages of faster mass transport, excellent sensitivity, and selectivity. Under optimum conditions, the detection limit of this system was 40.7 μg L^-1, and a linear range was from 5 × 10^-7 to 2 × 10^-3 mol L^-1, within relative standard deviations of 4.46-6.87%. The recoveries ranged from 92.23 to 103.87%, indicating the excellent ability of the prepared MIL-101@DMIP to recognize pyrraline in complex food matrices and its potential for application in pyrraline detection.

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Although metal-organic frameworks (MOFs) or porous coordination polymers have been widely studied, their antimicrobial activities have not yet been fully investigated. In this work, antifungal activity of copper-based benzene-tricarboxylate MOF (Cu-BTC MOF), which is water stable and industrially interesting, is investigated against <i>Candida albicans</i>, <i>Aspergillus niger</i>, <i>Aspergillus oryzae</i> and <i>Fusarium oxysporum</i>. The Cu-BTC MOF can effectively inhibit the growth rate of <i>C. albicans</i> and remarkably inhibit the spore growth of <i>A. niger</i>, <i>A. oryzae</i> and <i>F. oxysporum</i>. This finding shows the potential of using Cu-BTC MOF as a strong biocidal material against representative yeasts and moulds that are commonly found in the food and agricultural industries.

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In this study, a novel monolithic capillary column based on a NH₂-MIL-53(Al) metal-organic framework (MOF) incorporated in poly (3-acrylamidophenylboronic acid/methacrylic acid-co-ethylene glycol dimethacrylate) (poly (AAPBA/MAA-co-EGDMA)) was prepared using an in situ polymerization method. The characteristics of the MOF-polymer monolithic column were investigated by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffractometry, Brunauer-Emmett-Teller analysis, and thermogravimetric analysis. The prepared MOF-polymer monolithic column showed good permeability, high extraction efficiency, chemical stability, and good reproducibility. The MOF-polymer monolithic column was used for in-tube solid-phase microextraction (SPME) to efficiently adsorb trace sulfonamides from food samples. A novel method combining MOF-polymer-monolithic-column-based SPME with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was successfully developed. The linear range was from 0.015 to 25.0 µg/L, with low limits of detection of 1.3-4.7 ng/L and relative standard deviations (RSDs) of < 6.1%. Eight trace sulfonamides in fish and chicken samples were determined, with recoveries of the eight analytes ranging from 85.7% to 113% and acceptable RSDs of < 7.3%. These results demonstrate that the novel MOF-polymer-monolithic-column-based SPME coupled with UHPLC-MS/MS is a highly sensitive, practical, and convenient method for monitoring trace sulfonamides in food samples previously extracted with an adequate solvent.

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Catechin (CA) is a natural polyphenol with antioxidant activity. However, it is difficult to maintain stability and easy to release rapidly in active films. Novel zein edible films containing nano-sized CA/α-, β-, γ-cyclodextrin-metal-organic frameworks (CD-MOFs) were developed, and their physicochemical properties, antioxidant stability and release behavior were characterized. FT-IR revealed the CA/CD-MOFs and film matrix formed intermolecular hydrogen bonding interactions. XRD analysis detected that the film matrix was successfully embedded by CA/CD-MOFs. With the incorporation of CA/CD-MOFs, the microstructure of zein film was more compact, and significantly improved the water resistance, barrier and mechanical properties of zein film. Zein film containing CA/β-CD-MOFs showed good physical properties because of good compatibility of the CA/β-CD-MOFs with zein. Compared with zein film containing free CA, zein-CA/CD-MOFs films still have higher antioxidant capacity after 80 days of storage. Since CA was encapsulated into the porous structure of CD-MOFs by intermolecular force, the release of CA from zein films was controlled. These results suggest that the developed nanoedible films have potential application value as food packaging, which can be directly in contact with foods, and the longer active ingredient availability can effectively extend the food shelf life.

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Bio-nanocomposites-based packaging materials have gained significance due to their prospective application in rising areas of packaged food. This research aims to fabricate biodegradable packaging films based upon polyvinyl alcohol (PVA) and starch integrated with metal-organic frameworks (MOFs) or organic additives. MOFs offer unique features in terms of surface area, mechanical strength, and chemical stability, which make them favourable for supporting materials used in fabricating polymer-based packaging materials. zeolitic imidazolate frameworks (ZIFs) are one of the potential candidates for this application due to their highly conductive network with a large surface area and high porosity. Present research illustrates a model system based on ZIF-67 (C₈H₁₀N₄Co) bearing 2-10 wt.% loading in a matrix of PVA/starch blend with or without pyrolysis to probe the function of intermolecular interaction in molecular packing, tensile properties, and glass transition process. ZIF-67 nanoparticles were doped in a PVA/starch mixture, and films were fabricated using the solution casting method. It was discovered through scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR) that addition of ZIF-67 and pyrolyzed ZIF-67 changed and enhanced the thermal stability of the membrane. Moreover, 2-10 wt.% loading of ZIF-67 effected the thermal stability, owing to an interlayer aggregation of ZIF-67. The membranes containing pyrolyzed ZIF-67 showed mechanical strength in the order of 25 MPa in a moderate loading of pyrolyzed ZIF-67 (i.e., at 4 wt.%). The crystallinity enhanced by an increment in ZIF-67 loading. On the other hand, pyrolyzed ZIF-67 carbon became amorphous because of the inert environment and elevated temperature. The surface area also increased after the pyrolysis, which helped to increase the strength of the composite films.

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The development of biodegradable active packaging films with hydrophobic characteristics is vital for extending the shelf life of food and reducing the reliance on petroleum-based plastics. In this study, novel hydrophobic cerium-based metal-organic framework (Ce-MOF) nanoparticles were successfully synthesized. The Ce-MOF nanoparticles were then incorporated into the cassava starch matrix at varying concentrations (0.5 %, 1.5 %, 3 %, and 4 % w/w of total solid) to fabricate cassava-based active packaging films via the solution casting technique. The influence of Ce-MOF on the morphology, thermal attributes, and physicochemical properties of the cassava film was subsequently determined through further analyses. Biomedical analysis including antioxidant activity and the cellular morphology evaluation in the presence of the films was also conducted. The results demonstrated that the consistent dispersion of Ce-MOF nanofillers within the cassava matrix led to a significant enhancement in the film's crystallinity, thermal stability, antioxidant activity, biocompatibility, and hydrophobicity. The introduction of Ce-MOF also contributed to the film's reduced water solubility. Considering these outcomes, the developed cassava/Ce-MOF films undoubtedly have significant potential for active food packaging applications.

Abstract Malachite green (MG) abuse in aquaculture has caused food safety issues and surface‐enhanced Raman scattering (SERS) can be utilized to monitor MG residues in aquatic products. However, the sensitivity and accuracy of SERS detection are limited by food matrix interference. Therefore, in this study, SERS active MNP@Au@MIL‐100(Fe) substrates were developed by utilizing magnetic nanoparticle (MNP) as the core, which was evenly decorated with Au nanoparticles (AuNPs), and then coated with metal–organic frameworks (MOFs) shell of MIL‐100(Fe), which acted as a filter to only allow molecules with appropriate sizes to approach the inner AuNPs, thus avoiding food matrix interference and improving the identification ability to analytes. Experiments in detecting MG residues in prawns was realized with the limit of detection (LOD) of 1.32 × 10 −10 M, showing great potential for its use as a reliable SERS substrate for monitoring food contaminants.

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Currently, there is a rising need for smart packaging materials that can be applied for the real-time visual monitoring of food freshness. In this work, new Co-based MOF (Co-ATMP) nanocrystals with ammonia-sensitivity function were prepared and then blended with polyvinyl alcohol (PVA) matrix to construct smart active packaging materials. The effect of Co-ATMP nanofiller upon structure, physical, and functional performances of the PVA films were then analyzed in detail. Results demonstrate that nano Co-ATMP fillers are distributed well within the PVA matrix through the formation of new hydrogen-bonding interaction, which make an obvious increase in the ductility, moisture permeability, and UV-blocking ability of the PVA film. Besides, the prepared PVA/Co-ATMP blend films present high antibacterial activity, ammonia-sensitivity as well as color stability. Ultimately, the PVA/Co-ATMP blend films were successfully employed for indicating the deterioration of shrimp through noticeable color variations. Therefore, the PVA/Co-ATMP blend films have great potential for utilization in smart active packaging area.

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Antibiotics play an essential role in the treatment of various diseases. However, the overuse of antibiotics has led to the pollution of water bodies and food safety, affecting human health. Herein, we report a dual-emission MOF-based flexible sensor for the detection of antibiotics in water, which was prepared by first encapsulating rhodamine B (RhB) by a zeolite imidazolium ester skeleton (ZIF-8) and then blending it with polyvinylidene difluoride (PVDF). The luminescent properties, structural tunability, and flexible porosity of the MOF-based composites were combined with the processability and flexibility of polymers to prepare luminescent membranes. The sensor is capable of dual-emission ratiometric fluorescence sensing of nitrofurantoin (NFT) and oxytetracycline (OTC), exhibiting sensitive detection of fluorescence burst and fluorescence enhancement, respectively, with detection limits of 0.012 μM and 8.9 nM. With the advantages of visual detection, high sensitivity, short detection time, and simplicity, the highly sensitive ratiometric fluorescent flexible sensor has great potential for detecting antibiotics in an aqueous environment. It will further stimulate interest in luminescent MOF-based mixed matrix membranes and their sensing applications.

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Abstract Single‐atom nanozyme materials have demonstrated exceptional specific catalytic activity due to the atomic‐level dispersion of their active centers. However, the exploration of catalytic mechanisms for single‐atom catalysts is so far limited to the 2D surfaces of nanozymes. In this study, porous single‐atom Fe nanozyme (psaFeN) is successfully prepared through a straightforward coordination‐assisted polymerization‐assembly strategy. The psaFeN composite nanospheres are uniformly sized, exhibiting excellent dispersibility with well‐organized pore channels extending from the center to the surface. Density functional theory calculations reveal that in the psaFeN nanozyme, the (010) facets serve as the primary active surface, where Fe atoms form tri‐coordinated or tetra‐coordinated structures with doped nitrogen atoms. The (100) facets act as auxiliary reactive surfaces with tetra‐coordinated Fe─N as the active center. psaFeN exhibits excellent POD‐like activity ( K m = 1.77 mM; V max = 173.53 × 10 − ⁸ M s −1 ). Given this exceptional bioactivity, a portable colorimetric biosensor is constructed for distinguishing artificially ripened fruits from naturally ripened ones. The sensor achieves precise discrimination with a detection limit as low as 310 nmol L −1 . This study is anticipated to offer valuable insights into understanding the 3D catalytic mechanisms of single‐atom nanozymes, promoting their application in the development of robust biosensors for food safety.

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Gluten, known as the major allergen in wheat, has gained increasing concerns in industrialized countries, resulting in an urgent need for accurate, high-sensitive, and on-site detection of wheat gluten in complex food systems. Herein, we proposed an AgNPs/MOF substrate-based surface-enhanced Raman scattering (SERS) sensor for the high-sensitive on-site detection of wheat gluten. The detection occurred on the newly in-situ synthesized AgNPs/MOF-modified SERS substrate, providing an enhancement factor (EF) of 1.89×10⁵. Benefitting from the signal amplification function of AgNPs/MOF and the superiority of SERS, this sensor represented high sensitivity performance and a wide detection range from 1×10^-15 to 2×10^-6 M with a detection limit of 1.16×10^-16 M, which allowed monitoring the trace of wheat gluten in complex food system without matrix interference. This reliable sandwich SERS sensor may provide a promising platform for high-sensitive, accurate, and on-site detection of allergens in the field of food safety.

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The development of an effective food packaging material is essential for safeguarding against infections and preventing chemical, physical, and biological changes during food storage and transportation. In the present study, we successfully synthesized an innovative food packaging material by combining chitosan (CH), nanocellulose (NC), and a gallic acid-based metal-organic framework (MOF). The CH films were prepared using different concentrations of NC (5 and 10%) and MOFs (1.5, 2.5, and 5%). Various properties of prepared films, including water solubility (WS), moisture content (MC), swelling degree, oxygen permeability, water vapor permeability (WVP), mechanical property, color analysis, and light transmittance, were studied. The chitosan film with a 5% NC and 1.5% MOF (CH-5% NC-1.5% MOF) exhibited the least water solubility, moisture content, and water vapor permeability, indicating the overall stability of the film. Additionally, this film demonstrated low oxygen permeability, as indicated by a peroxide value of 18.911 ± 4.009, ensuring the effective preservation of packaged contents. Notably, this synthesized film exhibited high antioxidant activity, resulting in an extended duration of 52 days. This antioxidant activity was further validated by the preservation of apple slices for 9 days in a CH-5% NC-1.5% MOF film. The findings of the study suggest that the developed films can provide a promising and environmentally friendly solution for active food packaging.

The fast and economical detection of trace polychlorinated dibenzo-p-dioxins (PCDDs) in food samples by current mass spectrum-based methods is hindered by tedious sample preparation and bulky & expensive analytical instruments. Surface-enhanced Raman spectroscopy (SERS) successfully detects many organic pollutants in foods but not dioxins because the employed metal nanoparticles weakly adsorb hydrophobic PCDDs. Herein, we report the detection of PCDDs in milk with SERS for the first time using a bifunctional substrate consisting of Au nanoparticles embedded in a zirconium-based metal-organic framework shell (AuNP/Zr-MOF). 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD), as the most toxic PCDD, is detected as low as 1.2 parts per trillion (ppt) in real milk samples with massive interfering substances in 30 min, which is the lowest among all reported methods. The aromatic rings of Zr-MOF promote the smart accumulation of TCDD through π-π interactions, and Au-Cl interactions drive TCDD onto Au surfaces. Zr-MOF shells with pore sizes of 12.7 and 20 Å block the accessibility of larger interfering molecules. A one-step apparatus and protocol are established to be superior to traditional methods in terms of time and cost. This work provides new insight into a rational screening method for the detection of persistent organic pollutants in a real sample matrix.

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PLLA‐15% ZIF‐8 MOF composites were fabricated by melt compounding followed by injection molding for active packaging applications. The injection‐molded discs were then converted into films by compression molding. The samples were morphological and thermally characterized. Migration studies using Atomic Absorption Spectrometry were conducted on the successful produced PLLA and PLLA‐15% MOF films incubated at 40°C for 240 h with two simulants, Simulant A: aqueous and acidic foods with 10% ethanol, and Simulant B: low and high alcoholic foods with 50% ethanol as per the U.S. Food and Drug Administration guidelines for packaging application testing. After 240 h Zn 2+ ion concentrations in Simulants A and B were 354 and 166 mg L −1 , respectively. Higher Zn 2+ ion migration observed in Simulant A can be ascribed to the decomposition of the ZIF‐8 MOF under acidic environment. Thermo‐gravimetric studies indicated that the thermal stability of PLLA dropped from 338°C to 207°C with the addition of ZIF‐8 MOF, which may be credited to the catalytic depolymerization effect of the MOF. Due to high migration, the studied composite films are not suitable for direct food contact applications in their present form. Future work must be directed to explore how to engineer these composites for food contact applications.

The development of novel biocompatible and cost effective cryogel membrane which shows enhanced antimicrobial properties in order to use for several approaches such as wound dressing, scaffold or food packaging was aimed in this study. A super macro porous lysozyme imprinted cryogel membranes showing antibacterial effect against both Gram-positive and Gram-negative bacteria were prepared by using molecular imprinting technique. N-methacryloyl-(L)-histidine methyl ester (MAH) was used as the pseudo specific ligand and complexed with Cu⁺⁺ in order to provide metal ion coordination between MAH and template molecule (lysozyme). Comparing the antibacterial activity of different lysozyme concentrations, cryogel membranes were prepared in three different concentrations. To synthesize Poly (hydroxyethyl methacrylate-N-methacryloyl-(L)-histidine methylester) P(HEMA-MAH) cryogel membrane, free radical polymerization initiated by N, N, N', N'-tetramethylene diamine (TEMED) and ammonium persulfate (APS) was carried out at -12 °C. The characterization of the lysozyme imprinted cryogel membrane was accomplished by using scanning electron microscopy (SEM), swelling degree measurements and Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) spectroscopy. The cytotoxicity test of produced membrane was performed by using mouse fibroblast cell line L929. The antibacterial activity of P(HEMA-MAH) lysozyme molecular imprinted [P(HEMA-MAH) Lyz-MIP] cryogel membranes against <i>Staphylococcus aureus</i> (<i>S. aureus</i>) and <i>Escherichia coli</i> (<i>E. coli</i>) were determined by Kirby-Bauer membranes diffusion and viable cell counting methods. When the antibacterial effect of P(HEMA-MAH) Lyz-MIP cryogel membranes were evaluated, it was found that P(HEMA-MAH) Lyz-MIP cryogel membranes had stronger antibacterial effects against Gram-negative <i>E. coli</i> bacteria even in low lysozyme concentrations. In addition, 100% bacterial inhibition was detected for both of two bacteria at increasing lysozyme concentrations.

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Biosensors with high sensitivity, selectivity and a low limit of detection, reaching nano/picomolar concentrations of biomolecules, are important to the medical sciences and healthcare industry for evaluating physiological and metabolic parameters. Over the last decade, different nanomaterials have been exploited to design highly efficient biosensors for the detection of analyte biomolecules. The discovery of graphene has spectacularly accelerated research on fabricating low-cost electrode materials because of its unique physical properties, including high specific surface area, high carrier mobility, high electrical conductivity, flexibility, and optical transparency. Graphene and its oxygenated derivatives, including graphene oxide (GO) and reduced graphene oxide (rGO), are becoming an important class of nanomaterials in the field of biosensors. The presence of oxygenated functional groups makes GO nanosheets strongly hydrophilic, facilitating chemical functionalization. Graphene, GO and rGO nanosheets can be easily combined with various types of inorganic nanoparticles, including metals, metal oxides, semiconducting nanoparticles, quantum dots, organic polymers and biomolecules, to create a diverse range of graphene-based nanocomposites with enhanced sensitivity for biosensor applications. This review summarizes the advances in two-dimensional (2D) and three-dimensional (3D) graphene-based nanocomposites as emerging electrochemical and fluorescent biosensing platforms for the detection of a wide range of biomolecules with enhanced sensitivity, selectivity and a low limit of detection. The biofunctionalization and nanocomposite formation processes of graphene-based materials and their unique properties, surface functionalization, enzyme immobilization strategies, covalent immobilization, physical adsorption, biointeractions and direct electron transfer (DET) processes are discussed in connection with the design and fabrication of biosensors. The enzymatic and nonenzymatic reactions on graphene-based nanocomposite surfaces for glucose- and cholesterol-related electrochemical biosensors are analyzed. This review covers a very broad range of graphene-based electrochemical and fluorescent biosensors for the detection of glucose, cholesterol, hydrogen peroxide (H₂O₂), nucleic acids (DNA/RNA), genes, enzymes, cofactors nicotinamide adenine dinucleotide (NADH) and adenosine triphosphate (ATP), dopamine (DA), ascorbic acid (AA), uric acid (UA), cancer biomarkers, pathogenic microorganisms, food toxins, toxic heavy metal ions, mycotoxins, and pesticides. The sensitivity and selectivity of graphene-based electrochemical and fluorescent biosensors are also examined with respect to interfering analytes present in biological systems. Finally, the future outlook for the development of graphene based biosensing technology is outlined.

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The first bioinspired microporous metal-organic framework (MOF) synthesized using ellagic acid, a common natural antioxidant and polyphenol building unit, is presented. Bi₂O(H₂O)₂(C₁₄H₂O₈)·<i>n</i>H₂O (SU-101) was inspired by bismuth phenolate metallodrugs, and could be synthesized entirely from nonhazardous or edible reagents under ambient aqueous conditions, enabling simple scale-up. Reagent-grade and affordable dietary supplement-grade ellagic acid was sourced from tree bark and pomegranate hulls, respectively. Biocompatibility and colloidal stability were confirmed by in vitro assays. The material exhibits remarkable chemical stability for a bioinspired MOF (pH = 2-14, hydrothermal conditions, heated organic solvents, biological media, SO₂ and H₂S), attributed to the strongly chelating phenolates. A total H₂S uptake of 15.95 mmol g^-1 was recorded, representing one of the highest H₂S capacities for a MOF, where polysulfides are formed inside the pores of the material. Phenolic phytochemicals remain largely unexplored as linkers for MOF synthesis, opening new avenues to design stable, eco-friendly, scalable, and low-cost MOFs for diverse applications, including drug delivery.

Abstract The inert nature of most commercial polymers and nanomaterials results in limitations of applications in various industrial fields. This can be solved by surface modifications to improve physicochemical and biological properties, such as adhesion, printability, wetting and biocompatibility. Polymer functionalization allows to graft specific moieties and conjugate molecules that improve material performances. In the last decades, several approaches have been designed in the industry and academia to graft functional groups on surfaces. Here, we review surface decoration of polymers and nanomaterials, with focus on major industrial applications in the medical field, textile industry, water treatment and food packaging. We discuss the advantages and challenges of polymer functionalization. More knowledge is needed on the biology behind cell–polymer interactions, nanosafety and manufacturing at the industrial scale.

Food packaging has a crucial function in the modern food industry. New food packaging technologies seek to meet consumers and industrial's demands. Changes related to food production, sale practices and consumers' lifestyles, along with environmental awareness and the advance in new areas of knowledge (such as nanotechnology or biotechnology), act as driving forces to develop smart packages that can extend food shelf-life, keeping and supervising their innocuousness and quality and also taking care of the environment. This review describes the main concepts and types of active and intelligent food packaging, focusing on recent progress and new trends using biodegradable and biobased polymers. Numerous studies show the great possibilities of these materials. Future research needs to focus on some important aspects such as possibilities to scale-up, costs, regulatory aspects, and consumers' acceptance, to make these systems commercially viable.

Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.

Covalent organic frameworks (COFs) have been designed and successfully synthesized by condensation reactions of phenyl diboronic acid {C6H4[B(OH)2]2} and hexahydroxytriphenylene [C18H6(OH)6]. Powder x-ray diffraction studies of the highly crystalline products (C3H2BO)6.(C9H12)1 (COF-1) and C9H4BO2 (COF-5) revealed expanded porous graphitic layers that are either staggered (COF-1, P6(3)/mmc) or eclipsed (COF-5, P6/mmm). Their crystal structures are entirely held by strong bonds between B, C, and O atoms to form rigid porous architectures with pore sizes ranging from 7 to 27 angstroms. COF-1 and COF-5 exhibit high thermal stability (to temperatures up to 500 degrees to 600 degrees C), permanent porosity, and high surface areas (711 and 1590 square meters per gram, respectively).

ADVERTISEMENT RETURN TO ISSUEEditorialNEXTIntroduction to Metal–Organic FrameworksHong-Cai Zhou, Jeffrey R. Long, and Omar M. YaghiView Author Information Texas A&M University University of California, Berkeley University of California, BerkeleyCite this: Chem. Rev. 2012, 112, 2, 673–674Publication Date (Web):January 26, 2012Publication History Published online26 January 2012Published inissue 8 February 2012https://pubs.acs.org/doi/10.1021/cr300014xhttps://doi.org/10.1021/cr300014xeditorialACS PublicationsCopyright © 2012 American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions This publication is free to access through this site. Learn MoreArticle Views212040Altmetric-Citations5979LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail PDF (2 MB) Get e-AlertscloseSUBJECTS:Adsorption,Chemical structure,Crystal structure,Hydrogen,Metal organic frameworks Get e-Alerts

A critical review of the emerging field of MOF-based catalysis is presented. Discussed are examples of: (a) opportunistic catalysis with metal nodes, (b) designed catalysis with framework nodes, (c) catalysis by homogeneous catalysts incorporated as framework struts, (d) catalysis by MOF-encapsulated molecular species, (e) catalysis by metal-free organic struts or cavity modifiers, and (f) catalysis by MOF-encapsulated clusters (66 references).

Adsorptive separation is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties must be found. Metal-organic frameworks (MOFs), constructed by metal-containing nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions observed in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable molecular sieves are emphasized and the underlying working mechanism elucidated. In addition to the experimental aspect, theoretical investigations from adsorption equilibrium to diffusion dynamics via molecular simulations are also briefly reviewed. Furthermore, gas separations in MOFs, including the molecular sieving effect, kinetic separation, the quantum sieving effect for H2/D2 separation, and MOF-based membranes are also summarized (227 references).

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTMetal–Organic Frameworks for SeparationsJian-Rong Li, Julian Sculley, and Hong-Cai Zhou*View Author Information Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012, United States*E-mail: [email protected]Cite this: Chem. Rev. 2012, 112, 2, 869–932Publication Date (Web):October 6, 2011Publication History Received30 May 2011Published online6 October 2011Published inissue 8 February 2012https://pubs.acs.org/doi/10.1021/cr200190shttps://doi.org/10.1021/cr200190sreview-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views61971Altmetric-Citations5547LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information SUBJECTS:Adsorption,Membranes,Metal organic frameworks,Molecules,Selectivity Get e-Alerts

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ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTCarbon Dioxide Capture in Metal–Organic FrameworksKenji Sumida, David L. Rogow, Jarad A. Mason, Thomas M. McDonald, Eric D. Bloch, Zoey R. Herm, Tae-Hyun Bae, and Jeffrey R. Long*View Author Information Department of Chemistry, University of California, Berkeley, California 94720-1460, United States*E-mail: [email protected]Cite this: Chem. Rev. 2012, 112, 2, 724–781Publication Date (Web):December 28, 2011Publication History Received19 August 2011Published online28 December 2011Published inissue 8 February 2012https://pubs.acs.org/doi/10.1021/cr2003272https://doi.org/10.1021/cr2003272review-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views81380Altmetric-Citations5582LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Adsorption,Materials,Membranes,Metal organic frameworks,Selectivity Get e-Alerts

Covalent organic frameworks (COFs) are a class of crystalline porous polymers that allow the atomically precise integration of organic units to create predesigned skeletons and nanopores. They have recently emerged as a new molecular platform for designing promising organic materials for gas storage, catalysis, and optoelectronic applications. The reversibility of dynamic covalent reactions, diversity of building blocks, and geometry retention are three key factors involved in the reticular design and synthesis of COFs. This tutorial review describes the basic design concepts, the recent synthetic advancements and structural studies, and the frontiers of functional exploration.

Just over a century ago, Lewis published his seminal work on what became known as the covalent bond, which has since occupied a central role in the theory of making organic molecules. With the advent of covalent organic frameworks (COFs), the chemistry of the covalent bond was extended to two- and three-dimensional frameworks. Here, organic molecules are linked by covalent bonds to yield crystalline, porous COFs from light elements (boron, carbon, nitrogen, oxygen, and silicon) that are characterized by high architectural and chemical robustness. This discovery paved the way for carrying out chemistry on frameworks without losing their porosity or crystallinity, and in turn achieving designed properties in materials. The recent union of the covalent and the mechanical bond in the COF provides the opportunity for making woven structures that incorporate flexibility and dynamics into frameworks.

Covalent organic frameworks (COFs) represent an exciting new type of porous organic materials, which are ingeniously constructed with organic building units via strong covalent bonds. The well-defined crystalline porous structures together with tailored functionalities have offered the COF materials superior potential in diverse applications, such as gas storage, adsorption, optoelectricity, and catalysis. Since the seminal work of Yaghi and co-workers in 2005, the rapid development in this research area has attracted intensive interest from researchers with diverse expertise. This critical review describes the state-of-the-art development in the design, synthesis, characterisation, and application of the crystalline porous COF materials. Our own opinions on further development of the COF materials are also presented for discussion (155 references).

Covalent organic frameworks (COFs) are a class of crystalline porous organic polymers with permanent porosity and highly ordered structures. Unlike other polymers, a significant feature of COFs is that they are structurally predesignable, synthetically controllable, and functionally manageable. In principle, the topological design diagram offers geometric guidance for the structural tiling of extended porous polygons, and the polycondensation reactions provide synthetic ways to construct the predesigned primary and high-order structures. Progress over the past decade in the chemistry of these two aspects undoubtedly established the base of the COF field. By virtue of the availability of organic units and the diversity of topologies and linkages, COFs have emerged as a new field of organic materials that offer a powerful molecular platform for complex structural design and tailor-made functional development. Here we target a comprehensive review of the COF field, provide a historic overview of the chemistry of the COF field, survey the advances in the topology design and synthetic reactions, illustrate the structural features and diversities, scrutinize the development and potential of various functions through elucidating structure-function correlations based on interactions with photons, electrons, holes, spins, ions, and molecules, discuss the key fundamental and challenging issues that need to be addressed, and predict the future directions from chemistry, physics, and materials perspectives.

Crystalline solids with extended non-interpenetrating three-dimensional crystal structures were synthesized that support well-defined pores with internal diameters of up to 48 angstroms. The Zn4O(CO2)6 unit was joined with either one or two kinds of organic link, 4,4',4''-[benzene-1,3,5-triyl-tris(ethyne-2,1-diyl)]tribenzoate (BTE), 4,4',44''-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate (BBC), 4,4',44''-benzene-1,3,5-triyl-tribenzoate (BTB)/2,6-naphthalenedicarboxylate (NDC), and BTE/biphenyl-4,4'-dicarboxylate (BPDC), to give four metal-organic frameworks (MOFs), MOF-180, -200, -205, and -210, respectively. Members of this series of MOFs show exceptional porosities and gas (hydrogen, methane, and carbon dioxide) uptake capacities. For example, MOF-210 has Brunauer-Emmett-Teller and Langmuir surface areas of 6240 and 10,400 square meters per gram, respectively, and a total carbon dioxide storage capacity of 2870 milligrams per gram. The volume-specific internal surface area of MOF-210 (2060 square meters per cubic centimeter) is equivalent to the outer surface of nanoparticles (3-nanometer cubes) and near the ultimate adsorption limit for solid materials.

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Metal-organic frameworks (MOFs) are a unique class of crystalline solids comprised of metal cations (or metal clusters) and organic ligands that have shown promise for a wide variety of applications. Over the past 15 years, research and development of these materials have become one of the most intensely and extensively pursued areas. A very interesting and well-investigated topic is their optical emission properties and related applications. Several reviews have provided a comprehensive overview covering many aspects of the subject up to 2011. This review intends to provide an update of work published since then and focuses on the photoluminescence (PL) properties of MOFs and their possible utility in chemical and biological sensing and detection. The spectrum of this review includes the origin of luminescence in MOFs, the advantages of luminescent MOF (LMOF) based sensors, general strategies in designing sensory materials, and examples of various applications in sensing and detection.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTEngineering Metal Organic Frameworks for Heterogeneous CatalysisA. Corma*, H. García, and F. X. Llabrés i XamenaView Author Information Instituto de Tecnología Química (UPV-CSIC), Universidad Politécnica de Valencia, Consejo Superior de Investigaciones Científicas, Avenida de los Naranjos s/n, 46022 Valencia, Spain* To whom correspondence should be addressed. E-mail: [email protected]Cite this: Chem. Rev. 2010, 110, 8, 4606–4655Publication Date (Web):April 1, 2010Publication History Received2 December 2009Published online1 April 2010Published inissue 11 August 2010https://pubs.acs.org/doi/10.1021/cr9003924https://doi.org/10.1021/cr9003924review-articleACS PublicationsCopyright © 2010 American Chemical SocietyRequest reuse permissionsArticle Views38208Altmetric-Citations3174LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Catalysts,Ligands,Materials,Metal organic frameworks,Metals Get e-Alerts

Three-dimensional covalent organic frameworks (3D COFs) were synthesized by targeting two nets based on triangular and tetrahedral nodes: ctn and bor. The respective 3D COFs were synthesized as crystalline solids by condensation reactions of tetrahedral tetra(4-dihydroxyborylphenyl) methane or tetra(4-dihydroxyborylphenyl)silane and by co-condensation of triangular 2,3,6,7,10,11-hexahydroxytriphenylene. Because these materials are entirely constructed from strong covalent bonds (C-C, C-O, C-B, and B-O), they have high thermal stabilities (400 degrees to 500 degrees C), and they also have high surface areas (3472 and 4210 square meters per gram for COF-102 and COF-103, respectively) and extremely low densities (0.17 grams per cubic centimeter).

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTSynthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and CompositesNorbert Stock* and Shyam BiswasView Author Information Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Str. 2, 24118 Kiel, Germany*E-mail: [email protected]Cite this: Chem. Rev. 2012, 112, 2, 933–969Publication Date (Web):November 18, 2011Publication History Received4 August 2011Published online18 November 2011Published inissue 8 February 2012https://pubs.acs.org/doi/10.1021/cr200304ehttps://doi.org/10.1021/cr200304ereview-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views131503Altmetric-Citations3929LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Chemical synthesis,Crystallization,Crystals,Metal organic frameworks,Solvents Get e-Alerts

This tutorial review presents recent developments of homochiral metal-organic frameworks (MOFs) in enantioselective catalysis. Following a brief introduction of the basic concepts and potential virtues of MOFs in catalysis, we summarize three distinct strategies that have been utilized to synthesize homochiral MOFs. Framework stability and accessibility of the open channels to reagents are then addressed. We finally survey recent successful examples of catalytically active homochiral MOFs based on three approaches, namely, homochiral MOFs with achiral catalytic sites, incorporation of asymmetric catalysts directly into the framework, and post-synthetic modification of homochiral MOFs. Although still in their infancy, homochiral MOFs have clearly demonstrated their utility in heterogeneous asymmetric catalysis, and a bright future is foreseen for the development of practically useful homochiral MOFs in the production of optically pure organic molecules.

The purpose of this critical review is to give a representative and comprehensive overview of the arising developments in the field of magnetic metal-organic frameworks, in particular those containing cobalt(II). We examine the diversity of magnetic exchange interactions between nearest-neighbour moment carriers, covering from dimers to oligomers and discuss their implications in infinite chains, layers and networks, having a variety of topologies. We progress to the different forms of short-range magnetic ordering, giving rise to single-molecule-magnets and single-chain-magnets, to long-range ordering of two- and three-dimensional networks (323 references).

Linking organic molecules by covalent bonds into extended solids typically generates amorphous, disordered materials. The ability to develop strategies for obtaining crystals of such solids is of interest because it opens the way for precise control of the geometry and functionality of the extended structure, and the stereochemical orientation of its constituents. Covalent organic frameworks (COFs) are a new class of porous covalent organic structures whose backbone is composed entirely of light elements (B, C, N, O, Si) that represent a successful demonstration of how crystalline materials of covalent solids can be achieved. COFs are made by combination of organic building units covalently linked into extended structures to make crystalline materials. The attainment of crystals is done by several techniques in which a balance is struck between the thermodynamic reversibility of the linking reactions and their kinetics. This success has led to the expansion of COF materials to include organic units linked by these strong covalent bonds: B-O, C-N, B-N, and B-O-Si. Since the organic constituents of COFs, when linked, do not undergo significant change in their overall geometry, it has been possible to predict the structures of the resulting COFs, and this advantage has facilitated their characterization using powder X-ray diffraction (PXRD) techniques. It has also allowed for the synthesis of COF structures by design and for their formation with the desired composition, pore size, and aperture. In practice, the modeled PXRD pattern for a given expected COF is compared with the experimental one, and depending on the quality of the match, this is used as a starting point for solving and then refining the crystal structure of the target COF. These characteristics make COFs an attractive class of new porous materials. Accordingly, they have been used as gas storage materials for energy applications, solid supports for catalysis, and optoelectronic devices. A large and growing library of linkers amenable to the synthesis of COFs is now available, and new COFs and topologies made by reticular synthesis are being reported. Much research is also directed toward the development of new methods of linking organic building units to generate other crystalline COFs. These efforts promise not only new COF chemistry and materials, but also the chance to extend the precision of molecular covalent chemistry to extended solids.

Advances in flexible and functional metal-organic frameworks (MOFs), also called soft porous crystals, are reviewed by covering the literature of the five years period 2009-2013 with reference to the early pertinent work since the late 1990s. Flexible MOFs combine the crystalline order of the underlying coordination network with cooperative structural transformability. These materials can respond to physical and chemical stimuli of various kinds in a tunable fashion by molecular design, which does not exist for other known solid-state materials. Among the fascinating properties are so-called breathing and swelling phenomena as a function of host-guest interactions. Phase transitions are triggered by guest adsorption/desorption, photochemical, thermal, and mechanical stimuli. Other important flexible properties of MOFs, such as linker rotation and sub-net sliding, which are not necessarily accompanied by crystallographic phase transitions, are briefly mentioned as well. Emphasis is given on reviewing the recent progress in application of in situ characterization techniques and the results of theoretical approaches to characterize and understand the breathing mechanisms and phase transitions. The flexible MOF systems, which are discussed, are categorized by the type of metal-nodes involved and how their coordination chemistry with the linker molecules controls the framework dynamics. Aspects of tailoring the flexible and responsive properties by the mixed component solid-solution concept are included, and as well examples of possible applications of flexible metal-organic frameworks for separation, catalysis, sensing, and biomedicine.

Metal-organic frameworks (MOFs), also known as porous coordination polymers (PCPs), synthesized by assembling metal ions with organic ligands have recently emerged as a new class of crystalline porous materials. The amenability to design as well as fine-tunable and uniform pore structures makes them promising materials for a variety of applications. Controllable integration of MOFs and functional materials is leading to the creation of new multifunctional composites/hybrids, which exhibit new properties that are superior to those of the individual components through the collective behavior of the functional units. This is a rapidly developing interdisciplinary research area. This review provides an overview of the significant advances in the development of diverse MOF composites reported till now with special emphases on the synergistic effects and applications of the composites. The most widely used and successful strategies for composite synthesis are also presented.

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Hydrogen-bonded organic frameworks (HOFs) represent an interesting type of polymeric porous materials that can be self-assembled through H-bonding between organic linkers. To realize permanent porosity in HOFs, stable and robust open frameworks can be constructed by judicious selection of rigid molecular building blocks and hydrogen-bonded units with strong H-bonding interactions, in which the framework stability might be further enhanced through framework interpenetration and other types of weak intermolecular interactions such as ππ interactions. Owing to the reversible and flexible nature of H-bonding connections, HOFs show high crystallinity, solution processability, easy healing and purification. These unique advantages enable HOFs to be used as a highly versatile platform for exploring multifunctional porous materials. Here, the bright potential of HOF materials as multifunctional materials is highlighted in some of the most important applications for gas storage and separation, molecular recognition, electric and optical materials, chemical sensing, catalysis, and biomedicine.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTHomochiral Metal–Organic Frameworks for Asymmetric Heterogeneous CatalysisMinyoung Yoon, Renganathan Srirambalaji, and Kimoon Kim*View Author Information Center for Smart Supramolecules, Department of Chemistry, and Division of Advanced Materials Science (WCU project), Pohang University of Science and Technology, San 31 Hyojadong, Pohang 790-784, Republic of Korea*E-mail: [email protected]Cite this: Chem. Rev. 2012, 112, 2, 1196–1231Publication Date (Web):November 15, 2011Publication History Received10 August 2011Published online15 November 2011Published inissue 8 February 2012https://pubs.acs.org/doi/10.1021/cr2003147https://doi.org/10.1021/cr2003147review-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views30667Altmetric-Citations2671LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Catalysts,Ions,Ligands,Metal organic frameworks,Metals Get e-Alerts

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.

New materials are prerequisite for major breakthrough applications influencing our daily life, and therefore are pivotal for the chemical industry. Metal-organic frameworks (MOFs) constitute an emerging class of materials useful in gas storage, gas purification and separation applications as well as heterogeneous catalysis. They not only offer higher surface areas and the potential for enhanced activity than currently used materials like base metal oxides, but also provide shape/size selectivity which is important both for separations and catalysis. In this critical review an overview of the potential applications of MOFs in the chemical industry is presented. Furthermore, the synthesis and characterization of the materials are briefly discussed from the industrial perspective (88 references).

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTWater Stability and Adsorption in Metal–Organic FrameworksNicholas C. Burtch, Himanshu Jasuja, and Krista S. Walton*View Author Information School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW, Atlanta, Georgia 30332, United States*E-mail: [email protected]Cite this: Chem. Rev. 2014, 114, 20, 10575–10612Publication Date (Web):September 29, 2014Publication History Received14 May 2014Published online29 September 2014Published inissue 22 October 2014https://pubs.acs.org/doi/10.1021/cr5002589https://doi.org/10.1021/cr5002589review-articleACS PublicationsCopyright © 2014 American Chemical SocietyRequest reuse permissionsArticle Views40942Altmetric-Citations1980LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information SUBJECTS:Adsorption,Chemical structure,Isotherms,Metal organic frameworks,Stability Get e-Alerts

The generation of metal–organic framework (MOF) coordination polymers enables the tailoring of novel solids with regular porosity from the micro to nanopore scale. Since the discovery of this new family of nanoporous materials and the concept of so called ‘reticular design’, nowadays several hundred different types of MOF are known. The self assembly of metal ions, which act as coordination centres, linked together with a variety of polyatomic organic bridging ligands, results in tailorable nanoporous host materials as robust solids with high thermal and mechanical stability.

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Abstract Covalent organic frameworks (COFs) are crystalline porous polymers formed by a bottom‐up approach from molecular building units having a predesigned geometry that are connected through covalent bonds. They offer positional control over their building blocks in two and three dimensions. This control enables the synthesis of rigid porous structures with a high regularity and the ability to fine‐tune the chemical and physical properties of the network. This Feature Article provides a comprehensive overview over the structures realized to date in the fast growing field of covalent organic framework development. Different synthesis strategies to meet diverse demands, such as high crystallinity, straightforward processability, or the formation of thin films are discussed. Furthermore, insights into the growing fields of COF applications, including gas storage and separations, sensing, electrochemical energy storage, and optoelectronics are provided.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTPostsynthetic Methods for the Functionalization of Metal–Organic FrameworksSeth M. Cohen*View Author Information Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093-0358, United States*E-mail: [email protected]Cite this: Chem. Rev. 2012, 112, 2, 970–1000Publication Date (Web):September 14, 2011Publication History Received20 May 2011Published online14 September 2011Published inissue 8 February 2012https://pubs.acs.org/doi/10.1021/cr200179uhttps://doi.org/10.1021/cr200179ureview-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views37643Altmetric-Citations1983LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Ligands,Materials,Metal organic frameworks,Modification,Physical and chemical processes Get e-Alerts

Covalent organic frameworks (COFs) represent a new field of rapidly growing chemical research that takes direct inspiration from diverse covalent bonds existing between atoms. The success of linking atoms in two and three dimensions to construct extended framework structures moved the chemistry of COFs beyond the structures to methodologies, highlighting the possibility of prospective applications. Although structure to property relation in COFs has led to fascinating properties, chemical stability, processability and scalability were some of the important challenges that needed to be overcome for their successful implementation. In this Perspective, we take a closer look at the growth of COFs from mere supramolecular structures to potential industrializable materials.

Covalent organic frameworks (COFs) are an emerging class of crystalline porous polymers with highly tuneable structures and functionalities. COFs have been proposed as ideal materials for applications in the energy-intensive field of molecular separation due to their notable intrinsic features such as low density, exceptional stability, high surface area, and readily adjustable pore size and chemical environment. This review attempts to highlight the key advancements made in the synthesis of COFs for diverse separation applications such as water treatment or the separation of gas mixtures and organic molecules, including chiral and isomeric compounds. Methods proposed for the fabrication of COF-based columns and continuous membranes for practical applications are also discussed in detail. Finally, a perspective regarding the remaining challenges and future directions for COF research in the field of separation has also been presented.

Conversion of carbon dioxide (CO2) to carbon monoxide (CO) and other value-added carbon products is an important challenge for clean energy research. Here we report modular optimization of covalent organic frameworks (COFs), in which the building units are cobalt porphyrin catalysts linked by organic struts through imine bonds, to prepare a catalytic material for aqueous electrochemical reduction of CO2 to CO. The catalysts exhibit high Faradaic efficiency (90%) and turnover numbers (up to 290,000, with initial turnover frequency of 9400 hour(-1)) at pH 7 with an overpotential of -0.55 volts, equivalent to a 26-fold improvement in activity compared with the molecular cobalt complex, with no degradation over 24 hours. X-ray absorption data reveal the influence of the COF environment on the electronic structure of the catalytic cobalt centers.

A new crystalline porous three-dimensional covalent organic framework, termed COF-300, has been synthesized and structurally characterized. Tetrahedral tetra-(4-anilyl)-methane and linear terephthaldehyde building blocks were condensed to form imine linkages in a material whose X-ray crystal structure shows five independent diamond frameworks. Despite the interpenetration, the structure has pores of 7.2 A diameter. Thus, COF-300 shows thermal stability up to 490 degrees C and permanent porosity with a surface area of 1360 m(2) g(-1).

Covalent organic frameworks (COFs), which are constructed from organic linkers, are a new class of crystalline porous materials comprising periodically extended and covalently bound network structures. The intrinsic structures and the tailorable organic linkers endow COFs with a low density, large surface area, tunable pore size and structure, and facilely-tailored functionality, attracting increasing interests in different fields including membrane separations. Exciting research activities ranging from fabrication strategies to separation applications of COF-based membranes have appeared. This review analyzes the synthesis and applications of diverse continuous/discontinuous COF membranes, such as COF-based mixed matrix membranes (MMMs), COF-based thin film nanocomposite (TFN) membranes, and free-standing COF films. Special attention was given to pore size, stability, hydrophilicity/hydrophobicity and surface charge of COFs in view of determining proper COFs for membrane fabrication, along with the approaches to fabricate COF-based membranes, such as blending, in situ growth, layer-by-layer stacking and interfacial polymerization (IP). Moreover, applications of COF-based membranes in gas separation, water treatment (deaslination and dye removal), organic solvent nanofiltration (OSN), pervaporation and fuel cell are disscussed. Finally, we illustrate the advantages and disadvantages of COF-based membranes through a comparison with MOF-based membranes, and the remaining challenges and future opportunities in this field.

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In the light of increasing energy demand and environmental pollution, it is urgently required to find a clean and renewable energy source. In these years, photocatalysis that uses solar energy for either fuel production, such as hydrogen evolution and hydrocarbon production, or environmental pollutant degradation, has shown great potential to achieve this goal. Among the various photocatalysts, covalent organic frameworks (COFs) are very attractive due to their excellent structural regularity, robust framework, inherent porosity and good activity. Thus, many studies have been carried out to investigate the photocatalytic performance of COFs and COF-based photocatalysts. In this critical review, the recent progress and advances of COF photocatalysts are thoroughly presented. Furthermore, diverse linkers between COF building blocks such as boron-containing connections and nitrogen-containing connections are summarised and compared. The morphologies of COFs and several commonly used strategies pertaining to photocatalytic activity are also discussed. Following this, the applications of COF-based photocatalysts are detailed including photocatalytic hydrogen evolution, CO₂ conversion and degradation of environmental contaminants. Finally, a summary and perspective on the opportunities and challenges for the future development of COF and COF-based photocatalysts are given.

As a novel class of porous crystalline materials, hydrogen-bonded organic frameworks (HOFs), self-assembled from organic or metal-organic building blocks through intermolecular hydrogen-bonding interactions, have attracted more and more attention. Over the past decade, a number of porous HOFs have been constructed through judicious selection of H-bonding motifs, which are further enforced by other weak intermolecular interactions such as π-π stacking and van der Waals forces and framework interpenetration. Since the H-bonds are weaker than coordinate and covalent bonds used for the construction of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), HOFs have some unique features such as mild synthesis condition, solution processability, easy healing, and regeneration. These features enable HOFs to be a tunable platform for the construction of functional materials. Here, we review the H-bonding motifs used for constructing porous HOFs and highlight some of their applications, including gas separation and storage, chiral separation and structure determination, fluorescent sensing, heterogeneous catalysis, biological applications, proton conduction, photoluminescent materials, and membrane-based applications.

Designing organic components that can be used to construct porous materials enables the preparation of tailored functionalized materials. Research into porous materials has seen a resurgence in the past decade as a result of finding of self-standing porous molecular crystals (PMCs). Particularly, a number of crystalline systems with permanent porosity that are formed by self-assembly through hydrogen bonding (H-bonding) have been developed. Such systems are called hydrogen-bonded organic frameworks (HOFs). Herein we systematically describe H-bonding patterns (supramolecular synthons) and molecular structures (tectons) that have been used to achieve thermal and chemical durability, a large surface area, and functions, such as selective gas sorption and separation, which can provide design principles for constructing HOFs with permanent porosity.

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The crystallization problem is an outstanding challenge in the chemistry of porous covalent organic frameworks (COFs). Their structural characterization has been limited to modeling and solutions based on powder x-ray or electron diffraction data. Single crystals of COFs amenable to x-ray diffraction characterization have not been reported. Here, we developed a general procedure to grow large single crystals of three-dimensional imine-based COFs (COF-300, hydrated form of COF-300, COF-303, LZU-79, and LZU-111). The high quality of the crystals allowed collection of single-crystal x-ray diffraction data of up to 0.83-angstrom resolution, leading to unambiguous solution and precise anisotropic refinement. Characteristics such as degree of interpenetration, arrangement of water guests, the reversed imine connectivity, linker disorder, and uncommon topology were deciphered with atomic precision-aspects impossible to determine without single crystals.

Two new chemically stable [acid and base] 2D crystalline covalent organic frameworks (COFs) (TpPa-1 and TpPa-2) were synthesized using combined reversible and irreversible organic reactions. Syntheses of these COFs were done by the Schiff base reactions of 1,3,5-triformylphloroglucinol (Tp) with p-phenylenediamine (Pa-1) and 2,5-dimethyl-p-phenylenediamine (Pa-2), respectively, in 1:1 mesitylene/dioxane. The expected enol-imine (OH) form underwent irreversible proton tautomerism, and only the keto-enamine form was observed. Because of the irreversible nature of the total reaction and the absence of an imine bond in the system, TpPa-1 and TpPa-2 showed strong resistance toward acid (9 N HCl) and boiling water. Moreover, TpPa-2 showed exceptional stability in base (9 N NaOH) as well.

Covalent organic-frameworks (COFs) are an emerging class of porous and ordered materials formed by condensation reactions of organic molecules. Recently, the Schiff-base chemistry or dynamic imine-chemistry has been widely explored for the synthesis of COFs. The main reason for this new tendency is based on their high chemical stability, porosity and crystallinity in comparison to previously reported COFs. This critical review article summarizes the current state-of-the-art on the design principles and synthetic strategies toward COFs based on Schiff-base chemistry, collects and rationalizes their physicochemical properties, as well as aims to provide perspectives of potential applications which are at the forefront of research in materials science.

As an emerging class of porous crystalline materials, covalent organic frameworks (COFs) are excellent candidates for various applications. In particular, they can serve as ideal platforms for capturing CO2 to mitigate the dilemma caused by the greenhouse effect. Recent research achievements using COFs for CO2 capture are highlighted. A background overview is provided, consisting of a brief statement on the current CO2 issue, a summary of representative materials utilized for CO2 capture, and an introduction to COFs. Research progresses on: i) experimental CO2 capture using different COFs synthesized based on different covalent bond formations, and ii) computational simulation results of such porous materials on CO2 capture are summarized. Based on these experimental and theoretical studies, careful analyses and discussions in terms of the COF stability, low- and high-pressure CO2 uptake, CO2 selectivity, breakthrough performance, and CO2 capture conditions are provided. Finally, a perspective and conclusion section of COFs for CO2 capture is presented. Recent advancements in the field are highlighted and the strategies and principals involved are discussed.

Two-dimensional covalent organic frameworks (2D COFs) are candidate materials for charge storage devices because of their micro- or mesoporosity, high surface area, and ability to predictably organize redox-active groups. The limited chemical and oxidative stability of established COF linkages, such as boroxines and boronate esters, precludes these applications, and no 2D COF has demonstrated reversible redox behavior. Here we describe a β-ketoenamine-linked 2D COF that exhibits reversible electrochemical processes of its anthraquinone subunits, excellent chemical stability to a strongly acidic electrolyte, and one of the highest surface areas of the imine- or enamine-linked 2D COFs. Electrodes modified with the redox-active COF show higher capacitance than those modified with a similar non-redox-active COF, even after 5000 charge-discharge cycles. These findings demonstrate the promise of using 2D COFs for capacitive storage.

Covalent organic frameworks (COFs), in which molecular building blocks form robust microporous networks, are usually synthesized as insoluble and unprocessable powders. We have grown two-dimensional (2D) COF films on single-layer graphene (SLG) under operationally simple solvothermal conditions. The layered films stack normal to the SLG surface and show improved crystallinity compared with COF powders. We used SLG surfaces supported on copper, silicon carbide, and transparent fused silica (SiO(2)) substrates, enabling optical spectroscopy of COFs in transmission mode. Three chemically distinct COF films grown on SLG exhibit similar vertical alignment and long-range order, and two of these are of interest for organic electronic devices for which thin-film formation is a prerequisite for characterizing their optoelectronic properties.

We synthesized a two-dimensional (2D) crystalline covalent organic framework (sp²c-COF) that was designed to be fully π-conjugated and constructed from all sp² carbons by C=C condensation reactions of tetrakis(4-formylphenyl)pyrene and 1,4-phenylenediacetonitrile. The C=C linkages topologically connect pyrene knots at regular intervals into a 2D lattice with π conjugations extended along both <i>x</i> and <i>y</i> directions and develop an eclipsed layer framework rather than the more conventionally obtained disordered structures. The sp²c-COF is a semiconductor with a discrete band gap of 1.9 electron volts and can be chemically oxidized to enhance conductivity by 12 orders of magnitude. The generated radicals are confined on the pyrene knots, enabling the formation of a paramagnetic carbon structure with high spin density. The sp² carbon framework induces ferromagnetic phase transition to develop spin-spin coherence and align spins unidirectionally across the material.

Three-dimensional porous crystalline polyimide covalent organic frameworks (termed PI-COFs) have been synthesized. These PI-COFs feature non- or interpenetrated structures that can be obtained by choosing tetrahedral building units of different sizes. Both PI-COFs show high thermal stability (>450 °C) and surface area (up to 2403 m(2) g(-1)). They also show high loading and good release control for drug delivery applications.

Covalent organic frameworks (COFs) have been proposed as alternative candidates for molecular sieving membranes due to their chemical stability. However, developing COF membranes with narrowed apertures close to the size of common gas molecules is a crucial task for selective gas separation. Herein, we demonstrate a new type of a two-dimensional layered-stacking COF-COF composite membrane in bilayer geometry synthesized on a porous support by successively regulating the growth of imine-based COF-LZU1 and azine-based ACOF-1 layers via a temperature-swing solvothermal approach. The resultant COF-LZU1-ACOF-1 bilayer membrane has much higher separation selectivity for H₂/CO₂, H₂/N₂, and H₂/CH₄ gas mixtures than the individual COF-LZU1 and ACOF-1 membranes due to the formation of interlaced pore networks, and the overall performance surpasses the Robeson upper bounds. The COF-LZU1-ACOF-1 bilayer membrane also shows high thermal and long-time stabilities.

Covalent organic frameworks (COFs), as an emerging class of crystalline porous polymers connected by dynamic covalent bonds, have been well studied over the past decade. Recently, three dimensional (3D) COFs have attracted extensive interest for the synthesis and applications of novel COFs. The principal reason for this rising trend is based on their unique porous features and excellent performances compared to previously reported two dimensional (2D) frameworks with the layered AA-stacking mode. This critical review describes the current state-of-the-art development of 3D COFs in the design principles, synthetic methods, functionalization strategies, and potential applications. Some major challenges associated with future perspectives are further discussed, inspiring the development of 3D COFs.

Covalent organic frameworks (COFs) are organic porous materials with many potential applications, which very often depend on the presence of chemical functionality at the organic building blocks. Functionality that cannot be introduced into COFs directly via de novo syntheses can be accessed through post-synthetic modification (PSM) strategies. Current strategies for the post-synthetic modification of COFs involve (i) incorporation of a variety of active metal species by using metal complexation through coordination chemistry, (ii) covalent bond formation between existing pendant groups and incoming constituents and (iii) chemical conversion of linkages. (iv) The post-synthetic modification is sometimes assisted by a monomer truncation strategy for the internal functionalization of COFs. (v) Even more intriguing methods that go beyond PSM are herein termed building block exchange (BBE) which encompasses framework-to-framework transformations taking advantage of the fact that reversible bond formation is a characteristic feature of COFs. This strategy allows the use of protoCOF structures (i.e., the utilization of a parent COF as a template) for the evolution of new COF structures with completely new components.

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Hydrogen-bonded organic frameworks (HOFs), self-assembled from strategically pre-designed molecular tectons with complementary hydrogen-bonding patterns, are rapidly evolving into a novel and important class of porous materials. In addition to their common features shared with other functionalized porous materials constructed from modular building blocks, the intrinsically flexible and reversible H-bonding connections endow HOFs with straightforward purification procedures, high crystallinity, solution processability, and recyclability. These unique advantages of HOFs have attracted considerable attention across a broad range of fields, including gas adsorption and separation, catalysis, chemical sensing, and electrical and optical materials. However, the relatively weak H-bonding interactions within HOFs can potentially limit their stability and potential use in further applications. To that end, this Perspective highlights recent advances in the development of chemically and thermally robust HOF materials and systematically discusses relevant design rules and synthesis strategies to access highly stable HOFs.