Preparation and application of achiral UiO-66-NH2 MOFs for enantioselective fluorescent detection of lysine enantiomers.

Lysine (Lys) is an essential nutrient that plays a crucial role in the growth and development of living organisms. Chiral analysis of Lys holds significant importance for ensuring the safety of food, pharmaceuticals, and health products. In this work, an achiral Zr-based metal organic frameworks (MOFs), UiO-66-NH2, was proposed as a fluorescent probe to achieve rapid response to l-lysine (L-Lys) in solution. Additionally, Zr4+ in the skeleton of UiO-66-NH2 framework exhibited different binding capacities towards Lys enantiomers, leading to distinct fluorescence responses for L-Lys and d-lysine (D-Lys). Leveraging these properties, the UiO-66-NH2 probe enabled accurate determination of L-Lys concentrations in solution, as well as the enantiomeric excess (ee) values of Lys solutions. Notably, in the detection of Lys enantiomers, the achiral UiO-66-NH2 acted as both a chiral selector and a fluorescent indicator, greatly improving the efficiency and stability of the detection system. The probable mechanism was further elucidated by pH titration experiments and density functional theory calculations. Additionally, the general applicability of this mechanism was validated by similar amino MOFs. The application of the UiO-66-NH2 fluorescent probe in analysis of infant formula milk powders and liquid milk samples confirmed the reliability of the method. Moreover, the construction of fluorescence test paper by immobilizing UiO-66-NH2 onto filler papers enabled the rapid identification of Lys enantiomers. Compared to previous fluorescent analyses of chiral amino acids assisted by additional metal ions, this study presented a novel approach and methodology that offers high efficiency, stability, reproducibility and reusability for the identification and detection of Lys enantiomers, highlighting the potential of the UiO-66-NH2 fluorescent probe in advancing analytical techniques.

MOF@MXene nanocomposite as a novel modifier to extend the application of PES mixed-matrix nanofiltration membranes for water treatment.

MXene-based membranes, as a type of modified membrane, have unique structures that attract attention for water treatment but suffer from low water flux. To address this, MXene was manipulated with UiO-66-NH2 nanoparticles to create UiO-66-NH2@MXene 2D-nanocomposites for the modification of the PES membrane. Herein, we synthesized a novel modified MXene-based PES membrane. The MXene, UiO-66-NH2, and UiO-66-NH2@MXene were assessed using the Fourier transform infrared, X-ray diffraction pattern, X-ray photoelectron spectroscopy, and zeta potential analysis. Field emission scanning electron microscopy was used to evaluate the MXene-based materials and prepared membranes, and the surface topography of the fabricated membranes was studied using atomic force microscopy. The membrane modified by 0.25 wt% of modifier was able to not only remove 72% and 81% of methylene blue and crystal violet cationic dyes, but also recorded more than 91% rejections for methyl blue, methyl orange, acid fusion, and Congo red anionic dyes. Using the same membrane, salt rejections of 91%, 87%, 79%, and 62% were achieved for Na2SO4, MgSO4, MgCl2, and NaCl, respectively. Water flux was also increased by more than 4 times in the membrane modified with 0.25 wt% of the novel nanocomposite modifier, and the water contact angle of the membrane with 0.5 wt% decreased from 65° to 38° compared to the pristine PES membrane. Besides, the anti-fouling properties were exceptionally improved in the membranes modified by the introduced UiO-66-NH2@MXene nanocomposite modifier.

Sonocatalytic degradation of tetracycline hydrochloride using SnO2 hollow-nanofiber decorated with UiO-66-NH2.

In this study, a porous hollow nanofiber SnO2 was decorated with UiO-66-NH2 nanoparticles with straightforward solvothermal method and utilized for sonocatalytic degradation of tetracycline (TC) by ultrasonic irradiation (USI). The prepared materials were characterized using different techniques such as SEM, EDS, FTIR, XRD, BET, XPS, UV-DRS, EIS, and zeta potential. SnO2 PHNF/UiO-66-NH2 nanocomposite offered the highest apparent rate constant of 0.0397 min-1 which was 6.3 and 3.1 times higher than those obtained for SnO2 PHNF and UiO-66-NH2, respectively. The integration of nanocomposite components revealed the synergy factor of 1.58, which can be due to the created heterojunctions resulted in efficiently charge carriers separation and retaining high redox ability. The effects of different affecting parameters such as TC initial concentration, pH of the solution, catalyst dosage, trapping agents, and coexisting anions on the catalytic performance were examined. The inhibitory effects of anions were confirmed to be decreased in the sequence of Cl- > NO3- > SO42-, while the sonocatalytic efficiency of the nanocomposite improved considerably in the presence of humic acid and bicarbonate. Also, the excellent performance of the catalyst was preserved during six successive cycles, suggesting the high stability of the prepared catalyst. In addition, based on the scavenger analysis, the created O2·-, OH·, and holes were contributed to the TC degradation. In conclusion, the creation heterojunction is an impressive methodology for improving the sonocatalytic activity of a catalyst, and SnO2 PHNF/UiO-66-NH2 nanocomposite was introduced as a satisfactory catalyst in sonocatalytic degradation of organic contaminants.

Highly Mesoporous Zr-Based MOF-Fabric Composites: A Benign Approach for Expeditious Degradation of Chemical Warfare Agents and Simulants.

Recent research has demonstrated the degradation of organophosphonates through hydrolysis using microporous UiO-66-NH2-fabric composites. Yet, challenges remain due to the limitations of organophosphonates accessing active sites in large, engineered granules. To address this, an innovative approach to integrate mesoporous UiO-66-NH2 onto various fabrics is provided, thereby overcoming previous mass transfer limitations. Mesoporosity in the UiO-66-NH2-fabric is attributed to the amphoteric cocamidopropylbetaine (CAPB) surfactant which templates the mesochannel construction. Unexpectedly, because the synthesis is aqueous, benign, low temperature (60°C), and avoids strong acids and toxic solvents, it is compatible with fragile supports such as untreated cotton. The UiO-66-NH2-fabric composite formed using treated polypropylene (PP) attains a BET specific surface area of 360 m2 g-1 comp. Remarkably, the mesoporous UiO-66-NH2-composites exhibit a pore volume as large as 0.2 cm3 g-1 comp, 33% in the mesoporous range, which is higher than other previous reports. Practically, the mesoporous UiO-66-NH2-treated PP composite enhances the rate of methyl paraoxon (DMNP) degradation, showing a t1/2 value that is 15 times faster than microporous UiO-66-NH2 composites measured under the same conditions. Similar trends are observed in the degradation of actual nerve agents. These composites hold significant potential across diverse applications, including filtration, protection, and catalysis.

Synthesis of UiO-66-Pyca-CuO by a Simple and Novel Method: MOF-based Metal Thin Film as Heterogeneous Catalysts for the Synthesis of α-Aminonitriles.

Metal-organic frameworks (MOFs), particularly UiO-66-NH2, are employed as catalysts in many industrial catalyst applications. As converting catalysts into thin film significantly increases their catalytic properties, we report a general approach to synthesizing MOF thin films (UiO-66-Pyca-CuO). First, functionalization of UiO-66-NH2 was done with 3-pyridine carboxaldehyde by the postsynthesis method, and then, UiO-66-Pyca was entangled on the surface of copper oxide nanoparticles with a modern strategy (MOF thin film). The morphology and structure of the synthesized UiO-66-Pyca-CuO were determined by using X-ray diffraction, Fourier transform infrared, field-emission scanning electron microscopy, energy-dispersive analysis of X-ray, inductively coupled plasma-mass spectrometry, elemental analyses of CHNOS, temperature-programmed desorption of ammonia, Brunauer-Emmett-Teller, and X-ray photoelectron spectroscopy. We studied the catalytic action of the UiO-66-Pyca-CuO thin film in the synthesis of α-aminonitriles via Strecker reaction. Our studies show that this catalysis can be a suitable catalyst in the synthesis of α-aminonitriles because of having advantages such as using the solvent being environmentally friendly, easy separation of the catalyst (only by picking up the MOF thin film from inside the solution), the reaction at room temperature, high yield, and reusability.

Highly Defective Zirconium-Based Metal-Organic Frameworks for the Efficient Adsorption and Detection of Sugar Phosphates in the Biological Sample.

Enrichment and quantification of sugar phosphates (SPx) in biological samples were of great significance in biological medicine. In this work, a series of zirconium-based metal-organic frameworks (MOFs) with different degrees of defects, namely, HP-UiO-66-NH2-X, were synthesized using acetic acid as a modulator and were utilized as high-capacity adsorbents for the adsorption of SPx in biological samples. The results indicated that the addition of acetic acid altered the morphology of HP-UiO-66-NH2-X, with corresponding changes in pore size (3.99-9.28 nm) and specific surface area (894.44-1142.50 m2·g-1). HP-UiO-66-NH2-10 showed the outstanding performance by achieving complete adsorption of all four SPx using only 80 µg of the adsorbent. The excellent adsorption efficiency of HP-UiO-66-NH2-10 was also obtained with a wide pH range and short adsorption time (10 min). Adsorption experiments demonstrated that the adsorption process involved chemical adsorption and multilayer adsorption. By utilizing X-ray photoelectron spectroscopy and density functional theory to explain the adsorption mechanism, it was found that various interactions (including coordination, hydrogen bonding, and electrostatic interactions) collectively contributed to the exceptional adsorption capability of HP-UiO-66-NH2-10. Those results indicated that the defect strategy not only increased the specific surface area and pore size, providing additional adsorption sites, but also reduced the adsorption energy between HP-UiO-66-NH2-10 and SPx. Moreover, HP-UiO-66-NH2-10 showed a low limit of detection (0.001-0.01 ng·mL-1), high precision (<13.77%), and accuracy (80.10-111.83%) in serum, liver, and cells, good stability, high selectivity (SPx/glucose, 1:100 molar ratio), and high adsorption capacity (292 mg·g-1 for SPx). The practical detection of SPx from human serum was also verified, prefiguring the great potentials of defective zirconium-based MOFs for the enrichment and detection of SPx in the biological medicine.

Sodium Alginate/UiO-66-NH2 Nanocomposite for Phosphate Removal.

Environmental pollution of phosphorus is becoming increasingly concerning, and phosphate removal from water has become an important issue for controlling eutrophication. Modified metal-organic framework (MOF) materials, such as UiO-66-NH2, are promising adsorbents for phosphate removal in aquatic environments due to their high specific surface area, high porosity, and open active metal sites. In this study, a millimeter-sized alginate/UiO-66-NH2 composite hydrogel modified by polyethyleneimine (UiO-66-NH2/SA@PEI) was prepared. The entrapping of UiO-66-NH2 in the alginate microspheres and its modification with PEI facilitate easy separation in addition to enhanced adsorption properties. The materials were characterized by SEM, FTIR, XRD, and BET. Static, dynamic, and cyclic adsorption experiments were conducted under different pH, temperature, adsorbent dosage, and initial concentration conditions to assess the phosphate adsorption ability of UiO-66-NH2/SA@PEI. Under optimal conditions of 65 °C and pH = 2, 0.05 g UiO-66-NH2/SA@PEI adsorbed 68.75 mg/g, and the adsorption rate remained at 99% after five cycles of UiO-66-NH2/SA@PEI. These results suggest that UiO-66-NH2/SA@PEI composite materials can be used as an effective adsorbent for phosphate removal from wastewater.

A novel robust hydrogel-assisted paper-based sensor based on fluorescence UiO-66-NH2@ZIF-8 for the dual-channel detection of captopril.

Captopril (CP) is commonly used as an active enzyme inhibitor for the treatment of coronary heart disease, hypertension and angina pectoris. The development of sensitive and efficient method for CP analysis is of great importance in biomedical research. Herein, we fabricated a sensitive and robust hydrogel-assisted paper-based sensor based on fluorescence UiO-66-NH2@ZIF-8 and Co, N-doped carbon nanozymes with oxidase-mimicking activity for accurate monitoring of captopril. The hydrogel-assisted paper-based sensor appeared a visible pink signal due to the catalytic oxidation of colorless N,N-diethyl-p-phenylenediamine (DPD) to oxDPD by Co, N-doped carbon-based nanozymes, and resulted in the fluorescence quenching of UiO-66-NH2@ZIF-8. In the presence of captopril, the oxidation of chromogenic substrate DPD by Co, N-doped nanozymes in the hydrogel-assisted paper-based sensor was hindered and accompanied by a change in the visible color, leading to recovery of the fluorescence of UiO-66-NH2@ZIF-8, and the change in the fluorescence color could also be observed. Therefore, the quantitative detection of captopril is achieved by taking a smartphone photograph and converting the image parameters into data information using ImageJ software. The portable hydrogel-assisted paper sensor provided sensitive detection of captopril in two modes based on visible color change as well as fluorescence color change with limits of detection of 0.45 µM and 0.47 µM, respectively. This hydrogel-assisted paper-based sensor has been successfully applied to the accurate monitoring of captopril in human serum, providing a potential avenue for in situ detection of captopril.

Construction of greenly biodegradable bacterial cellulose/UiO-66-NH2 composite separators for efficient enhancing performance of lithium-ion battery.

The disposal of waste lithium batteries, especially waste separators, has always been a problem, incineration and burial will cause environmental pollution, therefore, the development of degradable and high-performance separators has become an important challenge. Herein, UiO-66-NH2 particles were successfully anchored onto bacterial cellulose (BC) separators by epichlorohydrin (ECH) as a crosslinker, then a BC/UiO-66-NH2 composite separator was prepared by vacuum filtration. The ammonia groups (-NH2) from UiO-66-NH2 can form hydrogen bonds with PF6- in the electrolyte, promoting lithium-ion transference. Additionally, UiO-66-NH2 can store the electrolyte and tune the porosity of the separator. The lithium ion migration number (0.62) of the battery assembled with BC/UiO-66-NH2 composite separator increased by 50 % compared to the battery assembled with commercial PP separator (0.45). The discharge specific capacity of the battery assembled with BC/UIO-66-NH2 composite separator after 50 charge and discharge cycles is 145.4 mAh/g, which is higher than the average discharge specific capacity of 114.3 mAh/g of the battery assembled with PP separator. When the current density is 2C, the minimum discharge capacity of the battery assembled with BC/UiO-66-NH2 composite separator is 85.3 mAh/g. The electrochemical performance of the BC/UiO-66-NH2 composite separator is significantly better than that of the commercial PP separator. In addition, -NH2 can offer a nitrogen source to facilitate degradation of the BC separators, whereby the BC/UiO-66-NH2 composite separator could be completely degraded in 15 days.

Electrochemical Nanosensor for the Simultaneous Determination of Anticancer Drugs Epirubicin and Topotecan Using UiO-66-NH2/GO Nanocomposite Modified Electrode.

In this work, UiO-66-NH2/GO nanocomposite was prepared using a simple solvothermal technique, and its structure and morphology were characterized using field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD). An enhanced electrochemical sensor for the detection of epirubicin (EP) was proposed, which utilized a UiO-66-NH2/GO nanocomposite-modified screen-printed graphite electrode (UiO-66-NH2/GO/SPGE). The prepared UiO-66-NH2/GO nanocomposite improved the electrochemical performance of the SPGE towards the redox reaction of EP. Under optimized experimental conditions, this sensor demonstrates a remarkable limit of detection (LOD) of 0.003 µM and a linear dynamic range from 0.008 to 200.0 µM, providing a highly capable platform for sensing EP. Furthermore, the simultaneous electro-catalytic oxidation of EP and topotecan (TP) was investigated at the UiO-66-NH2/GO/SPGE surface utilizing differential pulse voltammetry (DPV). DPV measurements revealed the presence of two distinct oxidation peaks of EP and TP, with a peak potential separation of 200 mV. Finally, the UiO-66-NH2/GO/SPGE sensor was successfully utilized for the quantitative analysis of EP and TP in pharmaceutical injection, yielding highly satisfactory results.

Homogeneous electrochemical ratiometric biosensor for MircoRNA detection based on UiO-66-NH2 signal probe and waste-free entropy-driven DNA machine.

The construction of efficient methods for highly sensitive and rapid detection of disease markers is essential for the early diagnosis of serious diseases. In this paper, taking advantage of the UiO-66-NH2 signal molecule in combination with a waste-free entropy-driven DNA machine, a novel homogeneous electrochemical ratiometric platform is developed to detect MircoRNA (miRNA). Metal-organic framework materials (UiO-66-NH2 MOF) and ferrocene were utilized as electrochemical signal tags and reference probes, respectively. The target-initiated waste-free three-dimensional (3D) entropy-driven DNA nanomachine is activated in the presence of miRNA, resulting in DNA-labeled-UiO-66-NH2 falling off from the electrode, leading to a decrease in the signal of UiO-66-NH2 at 0.83V. Our strategy can mitigate false positive responses induced by the DNA probes immobilized on electrodes in traditional distance-dependent signal adjustment ratiometric strategies. The proposed ratiometric platform demonstrates superior sensitivity (a detection limit of 9.8 fM), simplified operation, high selectivity, and high repeatability. The ratiometric biosensor is also applied to detect miRNA content in spiked serum samples.

Smartphone-based dual inverse signal MOFs fluorescence sensing for intelligent on-site visual detection of malachite green.

The development of intelligent, sensitive, and visual methods for the rapid detection of veterinary drug residues is essential to ensure food quality and safety. Here, a smartphone-based dual inverse signal MOFs fluorescence sensing system was proposed for intelligent in-site visual detection of malachite green (MG). A UiO-66-NH2@RhB-dual-emission fluorescent probe was successfully synthesized in one step using a simple one-pot method. The inner filter effect (IFE) quenches the red fluorescence, while hydrogen bonding interaction enhances the blue fluorescence, enabling highly sensitive, accurate, and visual detection of MG dual inverse signals through fluorescence analysis. The probe showed great linearity over a wide range of 0.1-100 µmol/L, with a limit of detection (LOD) of 20 nmol/L. By integrating smartphone photography and RGB (red, green, and blue) analysis, accurate quantitative analysis of MG in water and actual fish samples can be achieved within 5 min. This developed platform holds great promise for the on-site detection of MG in practical applications, with the advantages of simplicity, cost-effectiveness, and rapidity. Consequently, it may open up a new pathway for on-site evaluation of food safety and environmental health.

Sandwich-type electrochemical immunosensing of CA125 by using nanoribbon-like Ti3C2Tx MXenes and toluidine blue/UIO-66-NH2.

CA125 (carbohydrate antigen 125) is an important biomarker of ovarian cancer, so developing effective method for its detection is of great significance. In the present work, a novel sandwich-like electrochemical immunosensor (STEM) of CA125 was constructed by preparing nanoribbon-like Ti3C2Tx MXenes (Ti3C2TxNR) to immobilize primary antibody (PAb) of CA125 and UIO-66-NH2 MOFs structure to immobilize second antibody (SAb) and electroactive toluidine blue (Tb) probe. In this designed STEM assay, the as-prepared Ti3C2TxNR nanohybrid offers the advantages in large surface area and conductivity as carrier, and UIO-66-NH2 provided an ideal platform to accommodate SAb and a large number of Tb molecules as signal amplifier. In the presence of CA125, the peak currents of Tb from the formed STEM structure increase with the increase of CA125 level. After optimizing the related control conditions, a wide linear range (0.2-150.0 U mL-1) and a very low detection limit (0.05 U mL-1) of CA125 were achieved. It's thus expected the developed STEM strategy has important applications for the detection of CA125.

Scaling-Up Microwave-Assisted Synthesis of Highly Defective Pd@UiO-66-NH2 Catalysts for Selective Olefin Hydrogenation under Ambient Conditions.

The need to develop green and cost-effective industrial catalytic processes has led to growing interest in preparing more robust, efficient, and selective heterogeneous catalysts at a large scale. In this regard, microwave-assisted synthesis is a fast method for fabricating heterogeneous catalysts (including metal oxides, zeolites, metal-organic frameworks, and supported metal nanoparticles) with enhanced catalytic properties, enabling synthesis scale-up. Herein, the synthesis of nanosized UiO-66-NH2 was optimized via a microwave-assisted hydrothermal method to obtain defective matrices essential for the stabilization of metal nanoparticles, promoting catalytically active sites for hydrogenation reactions (760 kg·m-3·day-1 space time yield, STY). Then, this protocol was scaled up in a multimodal microwave reactor, reaching 86% yield (ca. 1 g, 1450 kg·m-3·day-1 STY) in only 30 min. Afterward, Pd nanoparticles were formed in situ decorating the nanoMOF by an effective and fast microwave-assisted hydrothermal method, resulting in the formation of Pd@UiO-66-NH2 composites. Both the localization and oxidation states of Pd nanoparticles (NPs) in the MOF were achieved using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray photoelectron spectroscopy (XPS), respectively. The optimal composite, loaded with 1.7 wt % Pd, exhibited an extraordinary catalytic activity (>95% yield, 100% selectivity) under mild conditions (1 bar H2, 25 °C, 1 h reaction time), not only in the selective hydrogenation of a variety of single alkenes (1-hexene, 1-octene, 1-tridecene, cyclohexene, and tetraphenyl ethylene) but also in the conversion of a complex mixture of alkenes (i.e., 1-hexene, 1-tridecene, and anethole). The results showed a powerful interaction and synergy between the active phase (Pd NPs) and the catalytic porous scaffold (UiO-66-NH2), which are essential for the selectivity and recyclability.

Mechanochemical Encapsulation of Caffeine in UiO-66 and UiO-66-NH2 to Obtain Polymeric Composites by Extrusion with Recycled Polyamide 6 or Polylactic Acid Biopolymer.

The development of capsules with additives that can be added to polymers during extrusion processing can lead to advances in the manufacturing of textile fabrics with improved and durable properties. In this work, caffeine (CAF), which has anti-cellulite properties, has been encapsulated by liquid-assisted milling in zirconium-based metal-organic frameworks (MOFs) with different textural properties and chemical functionalization: commercial UiO-66, UiO-66 synthesized without solvents, and UiO-66-NH2 synthesized in ethanol. The CAF@MOF capsules obtained through the grinding procedure have been added during the extrusion process to recycled polyamide 6 (PA6) and to a biopolymer based on polylactic acid (PLA) to obtain a load of approximately 2.5 wt% of caffeine. The materials have been characterized by various techniques (XRD, NMR, TGA, FTIR, nitrogen sorption, UV-vis, SEM, and TEM) that confirm the caffeine encapsulation, the preservation of caffeine during the extrusion process, and the good contact between the polymer and the MOF. Studies of the capsules and PA6 polymer+capsules composites have shown that release is slower when caffeine is encapsulated than when it is free, and the textural properties of UiO-66 influence the release more prominently than the NH2 group. However, an interaction is established between the biopolymer PLA and caffeine that delays the release of the additive.

Novel Metal-Organic Framework Nanoparticle for Letrozole Delivery: A New Advancement in Breast Cancer Treatment.

Water-stable metal-organic frameworks based on UIO-66@NH2 were synthesized to transport Letrozole into breast cancer cells. The UIO-66@NH2 nanoparticles had a spherical shape and triangular base pyramid morphology, with a size range of 100-200 nm. Fourier transform infrared spectroscopy confirmed the efficient adsorption of Letrozole on UIO-66@NH2. The drug release profile showed a gradual, pH-dependent release of Letrozole from the nanoparticles, with a significant increase in acidic environments, indicating the adaptable release potential of UIO-66@NH2@Let in the breast cancer microenvironment. The size and entrapment efficiency were more stable at 4 °C than at 25 °C. To evaluate the cytotoxic effects of UIO-66@NH2@Let, MTT assay, gene expression analysis, flow cytometry, reactive oxygen species generation, migration assay, and DAPI staining were performed. Moreover, according to IC50 results, the incorporation of Letrozole into UIO-66@NH2 significantly improved its anticancer activity. The results also showed that the developed formulations induced apoptosis through both intrinsic and extrinsic pathways and inhibited cancer progression. The efficacy of the formulations in inducing apoptosis was validated by DAPI staining microscopy and flow cytometry analysis. Therefore, the Letrozole-loaded UIO-66@NH2 MOFs developed in this study can be considered as a unique and sophisticated anticancer delivery nanosystem with promising in vitro anticancer properties.

Design and Machine Learning Prediction of In Situ Grown PDA-Stabilized MOF (UiO-66-NH2) Membrane for Low-Pressure Separation of Emulsified Oily Wastewater.

Significant progress has been made in designing advanced membranes; however, persistent challenges remain due to their reduced permeation rates and a propensity for substantial fouling. These factors continue to pose significant barriers to the effective utilization of membranes in the separation of oil-in-water emulsions. Metal-organic frameworks (MOFs) are considered promising materials for such applications; however, they encounter three key challenges when applied to the separation of oil from water: (a) lack of water stability; (b) difficulty in producing defect-free membranes; and (c) unresolved issue of stabilizing the MOF separating layer on the ceramic membrane (CM) support. In this study, a defect-free hydrolytically stable zirconium-based MOF separating layer was formed through a two-step method: first, by in situ growth of UiO-66-NH2 MOF into the voids of polydopamine (PDA)-functionalized CM during the solvothermal process, and then by facilitating the self-assembly of UiO-66-NH2 with PDA using a pressurized dead-end assembly. A stable MOF separating layer was attained by enriching the ceramic support with amines and hydroxyl groups using PDA, which assisted in the assembly and stabilization of UiO-66-NH2. The PDA-s-UiO-66-NH2-CM membrane displayed air superhydrophilicity and underwater superoleophobicity, demonstrating its oil resistance and high antifouling behavior. The PDA-s-UiO-66-NH2-CM membrane has shown exceptionally high permeability and separation capacity for challenging oil-in-water emulsions. This is attributed to numerous nanochannels from the membrane and its high resistance to oil adhesion. The membranes showed excellent stability over 15 continuous test cycles, which indicates that the developed MOFs separating layers have a low tendency to be clogged by oil droplets during separation. Machine learning-based Gaussian process regression (GPR) models as nonparametric kernel-based probabilistic models were employed to predict the performance efficiency of the PDA-s-UiO-66-NH2-CM membrane in oil-in-water separation. The outcomes were compared with the support vector machine (SVM) and decision tree (DT) algorithm. This efficiency includes various metrics related to its separation accuracy, and the models were developed through feature engineering to identify and utilize the most significant factors affecting the membrane's performance. The results proved the reliability of GPR optimization with the highest prediction accuracy in the validation phase. The average percentage increase of the GPR model compared to the SVM and DT model was 6.11 and 42.94%, respectively.

Biomimetic delivery of emodin via macrophage membrane-coated UiO-66-NH2 nanoparticles for acute pancreatitis treatment.

Acute pancreatitis (AP) is a severe inflammatory condition with a rising incidence and high mortality rates, especially in severe cases. Emodin (ED), known for its potent anti-inflammatory properties, holds promise in addressing AP. However, its clinical application is hindered by limitations such as low bioavailability and insufficient target specificity. Herein, we developed a novel drug delivery system using macrophage membrane-coated UiO-66-NH2 nanoparticles loaded with ED (MVs-UiO-ED). UiO-66-NH2 was successfully synthesized and characterized, revealing an octahedral structure with a suitable size distribution. The successful loading of ED onto UiO-66-NH2 was confirmed by ultraviolet and infrared spectroscopy. Subsequently, MVs-UiO-ED was prepared by coating macrophage membrane-derived vesicles onto UiO-ED, resulting in a biomimetic delivery system. In vitro release studies demonstrated that MVs-UiO-ED exhibited a sustained-release profile, indicating its potential for prolonged drug circulation. An AP mouse model was established to evaluate the therapeutic efficacy of MVs-UiO-ED. Compared with the model group, MVs-UiO-ED significantly reduced serum levels of α-amylase and lipase, two indicators of pancreatitis severity. Furthermore, histopathological examinations revealed that MVs-UiO-ED ameliorated pancreatic tissue damage. This study underscores the potential of MVs-UiO-ED as an effective therapeutic approach for AP.

Silver Nanoparticle-Functionalized Postsynthetically Modified Thiol MOF UiO-66-NH-SH for Efficient CO2 Fixation.

Thiols are essential functional groups imparting unique properties, such as reactivity and selectivity, to many vital enzymes and biomolecules. The integration of electronically soft thiol groups within metal-organic frameworks (MOFs) yields elevated reactivity and a pronounced affinity for soft metal ions. However, the scarcity of thiol-based ligands and synthetic challenges hinder the advancement of thiol-based MOFs. To bypass the difficulties of synthesizing thiol MOFs by a direct reaction between thiol-based ligands and corresponding metal salts, postsynthetic modification (PSM) of MOFs is an efficient strategy to introduce thiol functionality. Herein, we have introduced Ag nanoparticles in postsynthetically modified thiol MOFs UiO-66-NH-SH (1) (synthesized by reaction between UiO-66-NH2 and thioglycolic acid) and UiO-66-NH-SH (2) (synthesized by reaction between UiO-66-NH2 and 3-mercaptopropionic acid) to synthesize a series of heterogeneous catalysts for CO2 fixation. Catalysts Cat 1-2 and Cat 3 - 4 were synthesized from UiO-66-NH-SH (1) and UiO-66-NH-SH (2), respectively, by using varying concentrations of silver (AgNO3). Catalyst Ag@UiO-66-NH-SH (1) (Ag = 3.45%; namely Cat 2) shows the highest efficiency for the catalytic conversion of propargylic alcohol and terminal epoxide to the corresponding cyclic carbonates. Finally, a rationalized reaction mechanism is proposed by correlating our results with the current literature. This work presents a viable strategy to utilize the thiol functionality of MOFs (avoiding the complexities associated with synthesizing thiol MOFs directly from thiol ligands) as a platform for introducing catalytically active metal centers and applying them as a heterogeneous catalyst for CO2 fixation reactions.

A sandwich electrochemiluminescence immunoassay based on 1T-MoS2@dual MOFs for detecting CA153.

A "signal-on" electrochemiluminescence (ECL) immunosensor has been proposed for detecting carbohydrate antigen 153 (CA153) based on the dual MOFs sandwich strategy. The conductive and porous substrate consisting of 1T-MoS2 and two-dimensional conductive metal-organic framework (MOF, Ni-HAB) was anchored onto the glassy carbon electrode (GCE) to label the capture antibody (Ab1), and the luminescence-functionalized MOF (Ru(bpy)32+@UiO-66-NH2) was utilized to immobilize the detection second antibody (Ab2) to construct a "signal-on" responsive sandwich-type electrochemiluminescence immunoassay. Meanwhile, tripropylamine (TPA) acts as the co-reactant and provides a luminescence system for Ru(bpy)32+@UiO-66-NH2. The luminescence-functionalized MOFs showed excellent ECL activity owing to the tunable structure of MOFs. The remarkable enhancement in ECL intensity was obtained by the immunoreaction of antigen and antibody. Under the optimized conditions, the biosensor exhibited a detection limit of 0.0001 U mL-1 (S/N = 3) with a wide range from 0.001 to 50 U mL-1. The proposed ECL immunosensor was applicable for detecting human serum samples with a recovery of 99.83 ∼ 101 % (RSD < 5 %). This work demonstrates that the advantage of multifunctional MOFs could be applied to construct highly selective ECL immunosensor, and it may facilitate the diagnosis of breast cancer in clinics.