Silver Nanoparticle-Loaded Titanium-Based Metal-Organic Framework for Promoting Antibacterial Performance by Synergistic Chemical-Photodynamic Therapy.

The abuse of antibiotics leads to an increasing emergence of drug-resistant bacteria, which not only causes a waste of medical resources but also seriously endangers people's health and life safety. Therefore, it is highly desirable to develop an efficient antibacterial strategy to reduce the reliance on traditional antibiotics. Antibacterial photodynamic therapy (aPDT) is regarded as an intriguing antimicrobial method that is less likely to generate drug resistance, but its efficiency still needs to be further improved. Herein, a robust titanium-based metal-organic framework ACM-1 was adopted to support Ag nanoparticles (NPs) to obtain Ag NPs@ACM-1 for boosting antibacterial efficiency via synergistic chemical-photodynamic therapy. Apart from the intrinsic antibacterial nature, Ag NPs largely boost ROS production and thus improve aPDT efficacy. As a consequence, Ag NPs@ACM-1 shows excellent antibacterial activity under visible light illumination, and its minimum bactericidal concentrations (MBCs) against E. coli, S. aureus, and MRSA are as low as 39.1, 39.1, and 62.5 µg mL-1, respectively. Moreover, to expand the practicability of Ag NPs@ACM-1, two (a dense and a loose) Ag NPs@ACM-1 films were readily fabricated by simply dispersing Ag NPs@ACM-1 into heated aqueous solutions of edible agar and sequentially cooling through heating or freeze-drying, respectively. Notably, these two films are mechanically flexible and exhibit excellent antibacterial activities, and their antimicrobial performances can be well retained in their recyclable and remade films. As agar is nontoxic, degradable, inexpensive, and ecosustainable, the dense and loose Ag NPs@ACM-1 films are potent to serve as recyclable and degradable antibacterial plastics and antibacterial dressings, respectively.

Association of age at first sexual intercourse and lifetime number of sexual partners with cardiovascular diseases: a bi-directional Mendelian randomization study.

Background: Limited studies have explored the association between sexual factors [age at first sexual intercourse (AFS) and lifetime number of sexual partners (LNSP)] and cardiovascular diseases (CVDs), leaving the causality inconclusive. Methods: We performed a bi-directional Mendelian randomization (MR) study to investigate the causality between sexual factors and CVDs, including coronary artery disease, myocardial infarction, atrial fibrillation (AF), heart failure (HF), and ischemic stroke (IS). Single-nucleotide polymorphisms (SNPs) for sexual factors were extracted from the UK Biobank. Statistics for each CVD were derived from two different databases. MR estimates were calculated per outcome database and were combined through meta-analysis. Several complementary sensitivity analyses were also performed. Results: The primary analysis suggested that AFS was causally associated with the risk of CVDs; the odds ratios (ORs) ranged from 0.686 [95% confidence interval (CI), 0.611-0.770] for HF to 0.798 (95% CI, 0.719-0.886) for AF. However, the association between AFS and IS (OR, 0.844; 95% CI, 0.632-1.126) was not consistent in the meta-analysis after excluding SNPs related to confounders. Moreover, non-significant associations were found between LNSP and CVDs. Reverse direction MR analysis showed that CVDs were not associated with sexual factors. Conclusions: Genetic evidence suggested that AFS was causally associated with the risk of CVDs except for IS, whereas non-significant association of LNSP with CVDs was detected. Further investigation into AFS could be warranted in preventing the progression of CVDs.

Boosting Antibacterial Photodynamic Therapy in a Nanosized Zr MOF by the Combination of Ag NP Encapsulation and Porphyrin Doping.

Antibacterial photodynamic therapy (aPDT) is regarded as one of the most promising antibacterial therapies due to its nonresistance, noninvasion, and rapid sterilization. However, the development of antibacterial materials with high aPDT efficacy is still a long-standing challenge. Herein, we develop an effective antibacterial photodynamic composite UiO-66-(SH)2@TCPP@AgNPs by Ag encapsulation and 4,4',4″,4‴-(porphine-5,10,15,20-tetrayl)tetrakis(benzoic acid) (TCPP) dopant. Through a mix-and-match strategy in the self-assembly process, 2,5-dimercaptoterephthalic acid containing -SH groups and TCPP were uniformly decorated into the UiO-66-type framework to form UiO-66-(SH)2@TCPP. After Ag(I) impregnation and in situ UV light reduction, Ag NPs were formed and encapsulated into UiO-66-(SH)2@TCPP to get UiO-66-(SH)2@TCPP@AgNPs. In the resulting composite, both Ag NPs and TCPP can effectively enhance the visible light absorption, largely boosting the generation efficiency of reactive oxygen species. Notably, the nanoscale size enables it to effectively contact and be endocytosed into bacteria. Consequently, UiO-66-(SH)2@TCPP@AgNPs show a very high aPDT efficacy against Gram-negative and Gram-positive bacteria as well as drug-resistant bacteria (MRSA). Furthermore, the Ag NPs were firmly anchored at the framework by the high density of -SH moieties, avoiding the cytotoxicity caused by the leakage of Ag NPs. By in vitro experiments, UiO-66-(SH)2@TCPP@AgNPs show a very high antibacterial activity and good biocompatibility as well as the potentiality to promote cell proliferation.

Assessment of causal associations between handgrip strength and cardiovascular diseases: A two sample mendelian randomization study.

Background: Several observational studies have identified that handgrip strength was inversely associated with cardiovascular diseases (CVDs). Nevertheless, causality remains controversial. We conducted Mendelian randomization (MR) analysis to examine whether handgrip strength and risk of CVDs are causally associated. Methods: We identified 160 independent single nucleotide polymorphisms (SNPs) for right-hand grip strength and 136 independent SNPs for left-hand grip strength at the genome-wide significant threshold (P < 5 × 10-8) from UK Biobank participants and evaluated these in relation to risk of CVDs. MR estimates was calculated using the inverse-variance weighted (IVW) method and multiple sensitivity analysis was further conducted. Results: Genetical liability to handgrip strength was significantly associated with coronary artery disease (CAD) and myocardial infarction (MI), but not stroke, hypertension, or heart failure. Additionally, there was significant association between right-hand grip strength and atrial fibrillation (OR, 0.967; 95% CI, 0.950-0.984; p = 0.000222), however, suggestive significance was found between left-hand grip strength and atrial fibrillation (OR, 0.977; 95% CI, 0.957-0.998; p = 0.033). Results were similar in several sensitivity analysis. Conclusion: Our study provides support at the genetic level that handgrip strength is negatively associated with the risk of CAD, MI, and atrial fibrillation. Specific handgrip strength interventions on CVDs warrant exploration as potential CVDs prevention measures.

Robust Mesoporous Functional Hydrogen-Bonded Organic Framework for Hypochlorite Detection.

Although tremendous progress has been achieved in the field of hydrogen-bonded organic frameworks (HOFs), the low stability, small/none pores, and difficult functionality severely obstruct their development. Herein, a novel robust mesoporous HOF (HOF-FAFU-1) decorated with a high density of free hydroxy moieties has been designed and readily synthesized in the de novo synthesis. In HOF-FAFU-1, the planar building blocks are connected to each other by typical intermolecular carboxylate dimers to form two-dimensional (2D) layers with sql topology, which are further connected to their adjacent layers by face-to-face π-π interactions to obtain a three-dimensional (3D) open mesoporous framework. Owing to the high density of intermolecular hydrogen bonding and strong π-π interactions, HOF-FAFU-1 is very stable, allowing it to retain its structure in aqueous solutions with a pH range of 1-9. Benefiting from the decorated hydroxy moieties, HOF-FAFU-1 was exploited as a fluorescent sensor for hypochlorite detection in water media by a turn-off mode, which cannot be realized by its nonhydroxy groups anchoring counterpart (HOF-TCBP). The proposed sensing system is highly efficient, validated by a very broad linear range (0-0.45 mM), fast response (15 s), and small limit of detection (LOD) (1.32 µM). The fluorescent quenching of HOF-FAFU-1 toward hypochlorite was also investigated, mainly being ascribed to the transformation of building blocks from the fluorescent reduced state to the nonfluorescent oxidative state. This work not only demonstrates that HOFs integrated with high stability and large pores as well as high density of functional groups can be simultaneously realized by judicious design of building blocks but also conceptually elucidates that such HOFs can effectively extend the application fields of HOFs.

Multifunctional Porous Hydrogen-Bonded Organic Frameworks: Current Status and Future Perspectives.

Hydrogen-bonded organic frameworks (HOFs), self-assembled from organic or metalated organic building blocks (also termed as tectons) by hydrogen bonding, π-π stacking, and other intermolecular interactions, have become an emerging class of multifunctional porous materials. So far, a library of HOFs with high porosity has been synthesized based on versatile tectons and supramolecular synthons. Benefiting from the flexibility and reversibility of H-bonds, HOFs feature high structural flexibility, mild synthetic reaction, excellent solution processability, facile healing, easy regeneration, and good recyclability. However, the flexible and reversible nature of H-bonds makes most HOFs suffer from poor structural designability and low framework stability. In this Outlook, we first describe the development and structural features of HOFs and summarize the design principles of HOFs and strategies to enhance their stability. Second, we highlight the state-of-the-art development of HOFs for diverse applications, including gas storage and separation, heterogeneous catalysis, biological applications, sensing, proton conduction, and other applications. Finally, current challenges and future perspectives are discussed.

Dual-emissive metal-organic framework: a novel turn-on and ratiometric fluorescent sensor for highly efficient and specific detection of hypochlorite.

Hypochlorite (ClO-) is widely used as a disinfectant, whose residue content in water should be strictly controlled due to the potential threat to human health in an inappropriate concentration. Herein, dual-emissive metal-organic frameworks with a UiO-66 prototype structure, PDA/Eu/PDA-UiO-66-NH2(x), were elegantly designed and prepared by a mixed ligand assembly and sequential post-synthesis strategy. Since blue emission is sensitive to ClO-, PDA/Eu/PDA-UiO-66-NH2(40) was selected as a model nanosensor for ratiometric and turn-on sensing of ClO- while red emission acts as a reference signal. Remarkably, PDA/Eu/PDA-UiO-66-NH2(40) shows high efficiency and specificity toward ClO- detection, as verified by a very short response time of 15 s, a wide linear range of 0.1-60 µM, a low detection limit of 0.10 µM, and excellent selectivity toward common competing ions. The recovery experiments show that the recoveries of spiking ClO- in tap water range from 96 to 103%. The rigidification of the coordinated H2N-BDC2- ligands should be responsible for the turn-on fluorescence of PDA/Eu/PDA-UiO-66-NH2(40). This work not only shows a highly efficient and specific fluorescent nanosensor for ClO- detection but also presents the first MOF-based fluorescent probe for turn-on and ratiometric sensing of ClO-.

Microporous Hydrogen-Bonded Organic Framework for Highly Efficient Turn-Up Fluorescent Sensing of Aniline.

A microporous three-dimensional (3D) hydrogen-bonded organic framework (HOF-20) has been constructed from an aromatic-rich tetratopic carboxylic acid, 5-(2,6-bis(4-carboxyphenyl)pyridin-4-yl)isophthalic acid (H4BCPIA). The activated HOF-20a has a moderately high Brunauer-Emmett-Teller (BET) surface area of 1323 m2 g-1 and excellent stability in water and HCl aqueous solution. HOF-20 exhibits highly efficient turn-up fluorescent sensing of aniline in water with a detection limit of 2.24 µM and is selective toward aniline in the presence of aromatic interferents, owing to the hydrogen bonding and edge-to-face π-π stacking interactions between the HOF-20 host and the guest aniline molecules, as demonstrated in the single-crystal X-ray structure of HOF-20⊃aniline. Density functional theory (DFT) calculations further demonstrate that the recognition of aniline molecules by HOF-20 could restrict the rotation of the aromatic rings in H4BCPIA linkers, reducing the nonradiative decay pathways upon photoexcitation and subsequently enhancing the fluorescence intensity.

Dual-Emissive Metal-Organic Framework as a Fluorescent "Switch" for Ratiometric Sensing of Hypochlorite and Ascorbic Acid.

The detection of hypochlorite (ClO-) content in tap water is extremely important because excess amounts of hypochlorite can convert into highly toxic species and inadequate amounts of hypochlorite cannot fully kill bacteria and viruses. Although several metal-organic frameworks (MOFs) have been successfully employed as fluorescent sensors for hypochlorite detection, all these sensors are based on single emission that responds to the dose of hypochlorite. Ratiometric sensors are highly desirable, which can improve the sensitivity, accuracy, and reliability via self-calibration. Herein, a nanoscale dual-emission multivariate 5-5-Eu/BPyDC@MOF-253-NH2 was synthesized by sequential mixed-ligand self-assembly and postsynthesis method. Among the two emission bands of 5-5-Eu/BPyDC@MOF-253-NH2, the strong blue emitting derived from ligands is sensitive to hypochlorite, while the red emitting derived from Eu(III) almost keeps invariable. Therefore, 5-5-Eu/BPyDC@MOF-253-NH2 was exploited as a fluorescent ratiometric nanosensor for "on-off" sensing of hypochlorite. Notably, the proposed sensing system showed an excellent performance including fast response (within 15 s), relative high specificity, wide linear range (0.1-30 µM), and low detection limit (0.094 µM). Besides, the suppressed blue emitting was recovered after the addition of ascorbic acid (AA) that consumes ClO- via the redox reaction. Therefore, 5-5-Eu/BPyDC@MOF-253-NH2 was further employed as a fluorescent ratiometric nanosensor for the "on-off-on" sensing of AA. This work represents the first MOF-based fluorescent "switch" for the ratiometric sensing of hypochlorite and the second for ratiometric sensing of AA.

Zr-Based Metal-Organic Frameworks with Intrinsic Peroxidase-Like Activity for Ultradeep Oxidative Desulfurization: Mechanism of H2O2 Decomposition.

The restriction of sulfur content in fuels has become increasingly stringent as a result of the growing environmental concerns. Although several MOF-derived materials like POM@MOF composites have shown the ability to catalyze oxidative desulfurization (ODS), their catalytic activities inevitably obstructed by the encapsulated catalytic sites like POM due to the blockage of cavities. Therefore, MOFs with intrinsic and accessible catalytic sites are highly desirable for their applications in ultradeep ODS. Herein, four representative Zr-based MOFs (Zr-MOFs), namely, UiO-66, UiO-67, NU-1000, and MOF-808, were assessed for catalytic ODS. These MOFs were confirmed that they have peroxidase-like activity and can catalyze ODS with H2O2 as oxidant. Among them, MOF-808 showed the highest catalytic activity and it can fully desulfurize dibenzothiophene (DBT) in a model gasoline with a S concentration of 1000 ppm under 40 °C within 5 min. An extremely low apparent Arrhenius activation energy (22.0 KJ·mol-1) and an extraordinarily high TOF value (42.7 h-1) were obtained, ranking MOF-808 among the best catalysts for the catalytic DBT oxidation. Further studies confirmed that the excellent catalytic activity is mainly responsible for the high concentration of the accessible Zr-OH(H2O) catalytic sites decorated in MOF-808. The superoxide radicals (•O2-) and hydroxyl radicals (•OH) were identified and were proved to involve in the DBT oxidation. Besides, the effects of Brönsted and lewis acidity to the catalytic efficiency were also discussed. Based on the experimental results, a plausible mechanism concerning on Zr-OH(H2O) groups promoting the H2O2 decomposion in to both •O2- and •OH was first proposed. Moreover, MOF-808 can be facilely reused for at least eight runs without significant loss of its catalytic activity. By the integration of facile synthesis, high catalytic efficiency, and good stability, MOF-808 thus represents a new benchmark catalyst for catalytic oxidative desulfurization.

Hydrothermal synthesis of nitrogen and copper co-doped carbon dots with intrinsic peroxidase-like activity for colorimetric discrimination of phenylenediamine isomers.

Carbon dots doped with nitrogen and copper have been synthesized via a hydrothermal method. They possess favorable peroxidase-like catalytic activity over a wide range of pH values and temperatures. Specifically, they were used to catalyze the oxidation of ortho- and para-phenylenediamine (OPD and PPD) by H2O2. The resulting products possess different colors (yellow for OPD and brown for PPD), which can be visually discriminated. The corresponding typical absorption peaks of oxidized products for OPD and PPD are at 413 nm and 500 nm, respectively. The method displays excellent discrimination ability and selectivity over potential interferents. The detection limits are 1.1 µM for OPD and 1.9 µM for PPD. The respective linear ranges are from 5 to 200 µM for OPD and from 2.5 to 700 µM for PPD. The method was applied to the quantification of OPD and PPD in spiked natural waters. Graphical abstract Schematic presentation of the synthesis of nitrogen and copper co-doped carbon dots (N,Cu-CDs) and their application as an enzyme mimic for colorimetric discrimination of ortho-, meta- and para-phenylenediamine (OPD, MPD and PPD).

Encapsulation of Phosphotungstic Acid into Metal-Organic Frameworks with Tunable Window Sizes: Screening of PTA@MOF Catalysts for Efficient Oxidative Desulfurization.

Clean fuels with extremely low sulfur content are highly desirable due to environmental concerns. Herein, three water-stable and eco-friendly metal-organic frameworks with tunable window diameters, denoted as MOF-808X, have been employed as PTA solid supports. An array of PTA@MOF-808X composites were facilely synthesized via the encapsulation strategy. With tunable window sizes and adjustable PTA loading amounts, the obtained PTA@MOF-808X composites were screened for catalytic oxidative desulfurization (ODS) with H2O2 serving as oxidant. The experiments found that 42%PTA@MOF-808A had the highest catalytic ODS activity and could completely remove dibenzothiophene (DBT) in a model fuel with an initial sulfur content of 1000 ppm within 30 min, which falls far below the acceptable limits for fuel standards (10 ppm). Further investigations revealed that this high catalytic activity could be attributed to the cooperative catalysis of metal clusters in the host framework and the guest PTA molecules. Moreover, 42%PTA@MOF-808A could be facilely recovered and reused for at least five runs without loss of catalytic activity. Having a combination of eco-sustainability, high stability, high catalytic activity, and good recyclability, 42%PTA@MOF-808A therefore represents a new benchmark material for catalytic ODS and provides a new perspective for ultradeep desulfurization.

MOF-808: A Metal-Organic Framework with Intrinsic Peroxidase-Like Catalytic Activity at Neutral pH for Colorimetric Biosensing.

Natural enzyme mimetics with high catalytic activity at nearly neutral pH values are highly desired for their applications in biological systems. Herein for the first time a stable MOF, namely MOF-808, has been shown to possess high intrinsic peroxidase-like catalytic activity under acidic, neutral, and alkaline conditions. As a novel peroxidase mimetic, MOF-808 can effectively catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine when H2O2 serves as oxidant, accompanied by a significant color variation in the solution. The catalytic activity and the color variation were greatly dependent on H2O2 concentration, and thus MOF-808 can be applied to the colorimetric sensing of H2O2. The H2O2 detection limit is 4.5 µM, and the linear range is 10 µM to 15 mM. In view of the significant inhibition effect produced by ascorbic acid, a facile and sensitive approach for colorimetric sensing of ascorbic acid was successfully established. The AA detection limit is 15 µM, and the linear range is 30-1030 µM. Further investigation found that the catalytic activity of MOF-808 could be mainly ascribed to the Zr-OH(OH2) groups. Such active Zr-OH(OH2) groups can be effectively shielded by gluconic acid, and subsequently the catalytic activity of MOF-808 was significantly suppressed. With these findings, a facile and selective colorimetric assay for glucose sensing has been successfully explored via combination of the glucose oxidation with the TMB oxidation. The glucose detection limit is 5.7 µM, and the linear range is 5.7-1700 µM. MOF-808 is one of the best colorimetric biosensors among the peroxidase mimics reported for H2O2, AA, and glucose detection.

Efficient Capture and Effective Sensing of Cr2O72- from Water Using a Zirconium Metal-Organic Framework.

Highly efficient decontamination of heavily toxic Cr2O72- from water remains a serious task for public health and ecosystem protection. An easily regenerative and reused sorbent with suitable porosity may address this task. Herein, a series of water-stable and ecofriendly metal-organic frameworks (MOFs) with large surface areas were assessed for their ability to adsorb and separate Cr2O72- from aqueous solutions. Among these tested MOFs, NU-1000 shows an extraordinary capability to efficiently capture (within 3 min) Cr2O72- with a sorption capacity of up to 76.8 mg/g, which is the largest one for the neutral MOF-based Cr2O72- sorbents. NU-1000 also shows remarkable selectivity for Cr2O72- capture and can effectively reduce the Cr(VI) concentration from 24 ppm to 60 ppb, which is below the acceptable limit for the drinking water standard (100 ppb by the U.S. Environmental Protection Agency). Moreover, this adsorbent can be easily regenerated by Soxhlet extraction with an acidic methanol solution (2.5 M HCl) and can be reused at least three times without a significant loss of it adsorption ability. More intriguingly, NU-1000 can also serve as an efficient photoluminescent probe for the selective detection of Cr2O72- in aqueous media. The Cr2O72- detection limit is as low as 1.8 µM, and the linear range is from 1.8 to 340 µM. Our work shows that NU-1000 is a unique material combining both efficient sorption and exceptional fluorescent sensing of Cr2O72- in aqueous media.

Water-Stable Anionic Metal-Organic Framework for Highly Selective Separation of Methane from Natural Gas and Pyrolysis Gas.

A 3D water-stable anionic metal-organic framework [Zn4(hpdia)2]·[NH2(CH3)2]·3DMF·4H2O (FJI-C4) was constructed based on an elaborate phosphorus-containing ligand 5,5'-(hydroxyphosphoryl)diisophthalic acid (H5hpdia). FJI-C4 with narrow one-dimensional (1D) pore channels exhibits high selectivity of C3H8/CH4 and C2H2/CH4. It is the first time for the MOF which contains phosphorus for selective separation of methane from natural gas and pyrolysis gas.

Patterned growth of luminescent metal-organic framework films: a versatile electrochemically-assisted microwave deposition method.

Electrochemically-assisted microwave deposition technology, a facile method for the fabrication of luminescent metal-organic framework (LMOF) films, is presented herein. This method was further developed into a versatile method for preparing patterned LMOF films. The strategy based on this method can spatially locate microcrystals of MOFs on a surface, which provides great promise in anti-counterfeiting barcode applications.

An Anion Metal-Organic Framework with Lewis Basic Sites-Rich toward Charge-Exclusive Cationic Dyes Separation and Size-Selective Catalytic Reaction.

Organic dye pollutants become a big headache due to their toxic nature to the environment, and it should be one of the best solutions if we can separate and reuse them. Here, we report the synthesis and characterization of a microporous anion metal-organic framework (MOF) with Lewis basic sites-rich based on TDPAT (2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine) ligand, FJI-C2, which shows high adsorption and separation of cationic dye based on the charge-exclusive effect. Compared to other MOF materials, FJI-C2 shows the largest adsorption amount of methylene blue (1323 mg/g) at room temperature due to the nature of the anion frameworks and high surface area/pore volume. Furthermore, motivated by the adsorption properties of large guest molecules, we proceeded to investigate the catalytic behaviors of FJI-C2, not only because the large pore facilitates the mass transfer of guest molecules but also because the high density of Lewis basic sites can act as effective catalytic sites. As expected, FJI-C2 exhibits excellent catalytic performance for size-selective Knoevenagel condensation under mild conditions and can be reused several times without a significant decrease of the activity.

Porous anionic indium-organic framework with enhanced gas and vapor adsorption and separation ability.

A three-dimensional microporous anionic metal-organic framework (MOF) (Et4N)3[In3(TATB)4] (FJI-C1, H3TATB=4,4',4''-s-triazine-2,4,6-triyltribenzoic acid) with large unit cell volume has been synthesized. Assisted by the organic cation group Et4N in the pores of the compound, FJI-C1 not only shows high adsorption uptakes of C2 and C3 hydrocarbons, but also exhibits highly selective separation of propane, acetylene, ethane, and ethylene from methane at room temperature. Furthermore, it also exhibits high separation selectivity for propane over C2 hydrocarbons and acetylene can be readily separated from their C2 hydrocarbons mixtures at low pressure due to the high selectivity for C2H2 in comparison to C2H4 and C2H6. In addition, FJI-C1 with hydrophilic internal pores surfaces shows highly efficient adsorption separation of polar molecules from nonpolar molecules. Notably, it exhibits high separation selectivity for benzene over cyclohexane due to the π-π interactions between benzene molecules and s-triazine rings of the porous MOF.

Phosphotungstic acid encapsulated in the mesocages of amine-functionalized metal-organic frameworks for catalytic oxidative desulfurization.

Highly dispersed Keggin-type phosphotungstic acid (H3PW12O40, PTA) encapsulated in the mesocages of amine-functionalized metal-organic frameworks MIL-101(Cr)-NH2 has been prepared by an anion-exchange method. PTA anions (PW12O40(3-)) are stabilized in the mesocages via the electrostatic interaction with amino groups of the MIL-101(Cr)-NH2. The obtained catalyst (denoted PTA@MIL-101(Cr)-NH2) exhibits high catalytic activity in the extractive and catalytic oxidative desulfurization (ECODS) system under mild conditions. Moreover, it can be easily recovered and recycled several times without leaching and loss of activity.

Enantioselective inclusion of alcohols by solvent-controlled assembled flexible metal-organic frameworks.

Through judicious choice of the ligands and patient regulation of the solvent conditions, three unique chiral coordination polymeric isomers have been synthesized. Their structures, gas adsorption, and structural interconversion have been studied. One of the isomers displays dynamic behavior, and its use in the enantioselective separation of chiral alcohols has also been reported.