Zeolitic Imidazolate Framework Research Articles

Strategic Fabrication of Au4Cu2 NC/ZIF‐8 Composite Via In Situ Integration Technique for Enhanced Energy Storage Applications

AbstractMetal–organic frameworks (MOFs), known for their extensive porosity and versatile crystallinity, play a crucial role in the development of advanced energy storage materials. However, their application is limited by stability and conductivity issues. This study addresses these challenges by integrating ultrasmall metal nanoclusters, specifically Au4Cu2 NC, synthesized using a mixed ligand strategy combining 2, 4‐Dimethyl benzene thiol (2,4‐DMBTH) and 1,2‐bis(diphenylphosphino)ethane (dppe). The bimetallic Au4Cu2 NC, characterized by Single Crystal X‐Ray Diffraction (SCXRD), is applied to zeolitic imidazolate framework‐8 (ZIF‐8) using both in situ and ex situ methods to explore their electrochemical and physicochemical properties in energy storage. The in situ Au4Cu2 NC/ZIF‐8 composite demonstrated a specific capacitance that is almost two times higher than its ex situ counterpart, attributed to homogeneous dispersion and hence enhanced conductivity. This in situ integration of atomically precise bimetallic nanoclusters on MOFs significantly boosts supercapacitor performance, offering a more effective and reliable solution for energy storage. Further, in practical applications, this device demonstrated an energy density of 87.2 Wh kg−1 at a power density of 1474 W kg−1, highlighting its robustness and potential for high‐performance energy storage applications. This approach effectively combats the issue of nanocluster aggregation on substrates, marking a significant progression in supercapacitor technology.

Magnetic and pH dual responsive injectable magnetic zeolitic imidazole framework based colloidal gel for interventional treatment on hepatocellular carcinoma

Thermal ablation is frequently combined with systemic chemotherapy for treating hepatocellular carcinoma (HCC). However, the side effects of systemic chemotherapy on normal tissues limit its clinical application. Herein, we report a magnetic and pH dual-responsive colloidal gel assembled by doxorubicin (DOX)-loaded magnetic ZIF-8 and gelatin nanoparticles for HCC. The magnetic colloidal gel shows improved injectability and high functional particle loading, which could be injected through a 27G needle with an injection force as low as 8.8 N at 150 mg/mL solid content. Meanwhile, this colloidal gel could be magnetically heated and accelerated release DOX under tumor microenvironment, which presents a synergistic therapeutic effect by combining magnetic hyperthermia and localized chemotherapy. Furthermore, this colloidal gel could be manually injected interventional under ultrasound-guidance, exhibiting effective deep tumor treatment effect. Due to the high solid content, suitable injectability, and mechanical properties, the colloidal gel is also a promising embolic agent for transarterial embolization in HCC treatment.

Determination of Glucose by an Optical Biosensor Composed of a Molecularly Imprinted Polymer, Glucose Oxidase, and Bromothymol Blue

An optical biosensor was developed as a novel adsorbent to isolate glucose from saliva. A straightforward procedure was used to create the glucose-imprinted polymer coating on the surface of zeolitic imidazolate framework (ZIF-8) nanoparticles which served as the adsorbent. Glucose oxidase was immobilized. Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) analysis were used to characterize the novel adsorbent. The ZIF-8 nanoparticles were synthesized and coated with the MIP via precipitation polymerization on the surface of ZIF-8 nanoparticles with glucose acting as a template. To determine glucose, glucose oxidase catalyzed the conversion of adsorbed analyte on the polymer surface to gluconic acid. The resulting color change due to bromothymol blue was characterized using a colorimetric-based smartphone using the RGB profile. Key parameters such as pH, adsorbent mass, adsorption time, and indicator concentration were optimized and under these conditions this biosensor showed few interferences and good sensitivity with a 20 s response time. A linear range from 300 to 500 mg dL−1 was demonstrated by an exponentially growing calibration curve when saliva with pixel slopes (R + G + B) were used for calibration. This biosensor provides a low-cost and fast approach for glucose determination in biological samples.

Investigating the effect of ZIF-8@PEI filler and its comparison with ZIF-8 in mixed matrix membranes for CO2/CH4 separation with the help of DFT study

In this study, Zeolitic Imidazolate Framework-8 (ZIF-8) and modified ZIF-8 (ZIF-8@PEI)with polyethyleneimine (PEI) were used as dispersed particles inside the polysulfone (PSF) matrix to separate CO2 and CH4. The distributions of dispersed particles in mixed matrix membranes (MMMs) were analysed with the help of Fourier transfer infrared radiation, Thermal gravimetric analysis, Scanning electronic microscope and X-ray diffraction. The mixed matrix membranes investigated the permeability and selectivity of pure gas (CO2) and mixed gas (CO2/CH4). It was highest at 5 wt% ZIF-8@PEI blended into the PSF matrix. In case of pure gas studies, we investigated the CO2 permeability (18.10 Barrer) and CO2/CH4 selectivity (23.91) as compared to ZIF-8/PSF MMM (10.36 Barrer, 5.81); and in case of mixed gas studies, the CO2 permeability (17.11 Barrer) and CO2/CH4selectivity (21.28) as compared to ZIF-8/PSF MMM (7.86 Barrer, 4.21).Using DFT studies, the interaction energies of the ZIF-8@PEI material with CO2 and CH4 gas molecules werefound to be -74.39 kJ/mol and -23.25 kJ/mol, respectively. It was more toward the ZIF-8@PEI-CO2geometry complex.From the observation, the experimentalgas permeation results and DFT studiesinvestigated that ZIF-8@PEI filler can be a good candidate for applying CO2 capture.

Facile metal-oriented in-situ growth of zeolitic imidazole framework membranes on carbon fiber cloth with superior capacitive performance

Facile metal-oriented in-situ growth of zeolitic imidazole framework membranes on carbon fiber cloth with superior capacitive performance

Synthesis of g-C3N4 decorated with ZIF-8 and CuFe2O4 as a highly efficient and magnetically separable photocatalyst for degradation of tetracycline

In this study, for the first time a magnetically recoverable zeolitic imidazolate framework-8 (ZIF-8) / graphite carbon nitride (g-C3N4)/ cooper ferrite (CuFe2O4) nanocomposite was prepared through a fast and simple wet impregnation procedure. The magnetic behavior of the ZIF-8/g-C3N4/CuFe2O4 heterostructure was used for the easy recovery of the nanocomposite by an external magnet. After studying the structural, crystallinity, magnetic, and photophysical properties of the as-syntesized sample, its application was investigated for the enhanced photodegradation of tetracycline under visible light illumination. The band gap energies for ZIF-8, g-C3N4, and CuFe2O4 were obtained 5.1 eV, 2.8 eV, and 1.3 eV, respectively. After combination of ZIF-8, g-C3N4, and CuFe2O4, the band gap energy was obtained to 2.4 eV, which indicate the improvement of photocatalytic activity of ZIF-8/g-C3N4/CuFe2O4 nanocomposite. Among the as-synthesized photocatalyst samples, the ZIF-8/g-C3N4/CuFe2O4 showed an excellent photocatalytic activity (99.15 %) for degradation of tetracycline within 65 min irradiation of visible light, solution pH of 5 and photocatalyst dosage of 0.75 g/L. The rate constant of the ZIF-8/g-C3N4/CuFe2O4 is almost 13.1, 9.9, and 15.6 times higher than that of ZIF-8, g-C3N4, and CuFe2O4, respectively. The ZIF-8/g-C3N4/CuFe2O4 heterojunction showed the effective degradation activity for four consecutive cycles, which exhibited its excellent reusability and stability. Moreover, the free radical quenching tests confirmed that holes, and hydroxyl radicals were the main reaction species for degradation of tetracycline. Altogether the preparation of novel ZIF-8/g-C3N4/CuFe2O4 provides an promise avenue for the development of high potential magtenticaly photocatalytic systems for sustainable tetracycline production with remarkable efficiencies.

Self-Assembly of a Hierarchical Metal-Organic Framework at the Liquid/Liquid Interface via π-π Stacking Manipulations in Organoplatinum(IV) Complexes for Methanol Fuel Cells.

This study focuses on the facile synthesis of the hierarchical architecture of zeolitic imidazolate framework-8 (ZIF-8) films containing an ultrasmall amount of Pt(0) by investigating the synthesis of different organoplatinum complexes and manipulating the π-π stacking effect in these complexes at the liquid/liquid interface. The organometallic Pt(IV) precursors were complexes with a formula of [PtXMe2(R)(bpy)] (bpy = 2,2'-bipyridine; for complex 2, R = CH2CH═CHC6H5 and X = Br; for complex 3, R = CH2CH═CH2 and X = Br; for complex 4, R = Me and X = I) prepared by oxidative addition of cinnamyl bromide, allyl bromide, or methyl iodide to [PtMe2(bpy)] (complex 1). Different thin films were synthesized starting from three organometallic Pt(IV) precursors (i) by reduction of the Pt complexes at the toluene/water interface (TF2-TF4), (ii) by encapsulation of the Pt precursors in a ZIF-8 (TF5-TF7), and (iii) by reduction of the Pt precursors onto a ZIF-8 (TF8-TF10). The self-assembly of ZIF-8 and different organoplatinum precursors at the interface of two immiscible liquids leads to the preparation of films with well-engineered structures such as rhombic dodecahedra, nanorods, hierarchical architectures, and nanowires, which are very difficult and complicated to synthesize under normal conditions. The ultralow loading of platinum complexes with different degrees of π-π stacking of dangling moieties has a great impact on the structure and morphology (directing agent), which in turn drastically changes the catalytic properties. The obtained films were applied as electrocatalysts for methanol oxidation in fuel cells. The electrocatalytic performance of organoplatinum containing a cinnamyl group in hierarchical architecture TF8 was found to be superior to those of nonhierarchical structures.

Zeolitic Imidazolate Framework-8 enhanced with tungsten carbide for high-performance hybrid supercapacitors and hydrogen evolution

A promising metal-organic framework (MOF) called Zeolitic Imidazolate Framework-8 (ZIF-8) stands out for its electrochemical applications. Its versatility in physicochemical properties makes it a strong candidate for breakthroughs in energy storage and electrochemical water splitting. The electrode nanomaterials lower specific capacity, small charging/discharging rate, and low conductivity limit its supercapacitor and hydrogen evaluation reaction (HER) applications. The ZIF-8 zeolite structure was decorated with tungsten carbide (WC) to overcome these issues. These modifications result in improved porosity, surface area, density, and pore size, shape, and structure. These characteristics contribute significantly to enhanced electrochemical activity. ZIF-8 MOF/WC nanocomposites have excellent dispersion and stability due to their porosity and strong connection between embedded WC nanoclusters and the framework. The prepared electrode showed a 118.11 mV overpotential and 36.45 mV/dec Tafel slope throughout HER activity. ZIF-8 MOF/WC was used for electrochemical studies and to make a hybrid energy storage device using activated carbon (AC). The hybrid supercapacitor had higher energy and power densities (87 W h/kg and 850 W/kg). The theoretical technique (Dunn model) was also employed to analyze experimental results more thoroughly.

Three-dimensional porous structured cobalt- and nitrogen-doped carbon nanotube electrocatalyst derived from cobalt-based zeolitic imidazolate framework nanoleaves for high performance zinc-air battery

The development of efficient and cost-effective electrocatalysts to overcome the intrinsic sluggish kinetics of the oxygen reduction reaction (ORR) in zinc-air batteries is crucial. In this study, we introduce a strategy that integrates a template-assisted synthesis with subsequent thermal treatment to fabricate an active and stable cobalt-based nitrogen-doped carbon electrocatalyst, denoted as Co-N-CNT. The strategy adjusts the disordered architecture of the zeolitic imidazolate framework (ZIF) through the synergistic effect of bimetallic species, restricted the growth of zeolitic imidazolate framework nanoleaves (ZIF-L) using salt templates, and directed the transformation from a two-dimensional blade-like morphology to a three-dimensional multi-tiered composite structure. Notably, the Co-N-CNT-800 sample, synthesized at an optimized pyrolysis temperature of 800 °C, exhibits a half-wave potential of 0.89 V and demonstrates stability with sustained cycling over 21 h, which is comparable to the performance of commercial Pt/C electrocatalysts. Moreover, when employed as the cathode in zinc-air batteries, Co-N-CNT-800 not only surpasses Pt/C in terms of power density but also exhibits long-term charge/discharge stability. This findings offer a viable pathway for the design of active and cost-effective ORR electrocatalysts, holding promise for applications in the electrochemical energy storage and conversion systems.

Investigation on the Drug Release Efficacy of the Ibuprofen-Loaded ZIF-8/Fe3O4 NPs Nanocarrier.

In this work, a one-pot multicomponent synthesis of the ibuprofen-loaded Fe3O4 nanoparticles-supported zeolitic imidazolate framework-8 (Ibu-ZIF-8/Fe3O4 NPs) nanohybrid was carried out. The ZIF-8/Fe3O4 NPs nanohybrid was used as a drug carrier for the in vitro release of ibuprofen in a PBS solution. The structure and morphology of the synthesized materials were investigated by powder X-ray diffraction (PXRD) analysis, transmission electron microscopy (TEM) analysis, UV-visible absorption studies, FTIR spectroscopy, and thermogravimetric analysis (TGA). The ibuprofen release kinetics was studied by UV-visible spectroscopy. The mechanism of drug delivery was thoroughly investigated and the Higuchi model was found as the best-fitted model for the ibuprofen release study. The 20 wt % Fe3O4 NPs-supported ZIF-8 nanohybrid exhibited more than 95% ibuprofen release efficiency in phosphate buffer saline of pH 7.4 within 2 h. The separation ability of the nanohybrid was very good, and it was easily separated by a simple commercial magnet. In order to investigate the cell viability, the cytotoxicity of ZIF-8, Fe3O4 NPs, and ZIF-8/20 wt % Fe3O4 NPs was investigated using MTT assays against Leishmania donovani promastigotes. The ZIF-8/20 wt % Fe3O4 NPs nanohybrid carrier exhibited a cell growth inhibition effect with a high correlation coefficient and low probability (p) values. The high release of drug molecules may be due to the more open site of the ZIF-8/Fe3O4 NPs nanohybrid. The drug release profile suggests that the nanohybrid can be potentially used as a drug carrier for targeted drug delivery systems.

Evolution of the Structure and Morphology of Dual-Linker ZIF-301-eIm.

Few studies have reported on the continuous evolution of dual-linker zeolitic imidazolate frameworks' (ZIFs) structure and morphology during the crystal growth process. Herein, we report the synthesis of a novel ZIF material with CHA topology (ZIF-301-eIm) via the combination of a small-sized 2-ethylimidazole (eIm) with the large-sized 5-chlorobenzimidazole ligand. A series of derivative materials with distinct structures and morphologies were obtained via two pathways: (1) insufficient amount of eIm with prolonged crystallization time (pathway A) and (2) sufficient amount of eIm with prolonged crystallization time (pathway B). Various characterization techniques revealed the continuous evolution of structure and morphology during the crystal growth process. Insufficient amount of eIm and crystallization time (crystallization pathway A) led to ZIF-301-eIm derivatives with defective and open structures alongside an aggregated morphology of nanoparticles. Prolonging the crystallization time allowed small-sized eIm ligands to gradually fill into the framework, resulting in the formation of ZIF-301-eIm-A5 characterized by complete but dense structures with a perfect polyhedral morphology. Remarkably, a sufficient amount of eIm during synthesis (crystallization pathway B) formed ZIF-301-eIm-B1 with a similar structure and morphology to ZIF-301-eIm-A5 in just 1 day. ZIF-301-eIm-B3, with intact, dense structures, exhibits superior acetone/butanol separation performance compared to ZIF-301-eIm-A3 due to small pore windows and large cages facilitating selective adsorption of acetone through exclusion separation.

MOF-derived high-density carbon nanotubes “tentacle” with boosting electrocatalytic activity for detecting ascorbic acid

Accurate detection of ascorbic acid (AA) plays a significant role in food and human physiological processes. Herein, a three-dimensional flexible leaf-like nitrogen-doped hierarchical carbon nanoarrays with high-density carbon nanotube “tentacle” architecture (NC/CNT-Co), which possesses high specific surface area, plenty of active defect sites, and various pore size distributions, was synthesized by the pyrolysis of zeolitic imidazolate framework (ZIF(Co)), while g-C3N4 acted as carbon source and heteroatom doping agent. Benefiting from its unique structure and surface properties, a selective and highly sensitive AA sensor was developed using this material. Compared to powder materials, NC/CNT-Co modified CF (CF@NC/CNT-Co) which don't be extra decorated, exhibits lower detection limit (1 μM), a wider linear range (20–1400 μM), and better stability, showing higher performance in electrocatalysis and detection of AA. Furthermore, CF@NC/CNT-Co also demonstrates high resistance to interference and fouling in AA detection. Particularly, the prepared CF@NC/CNT-Co electrode could determine AA in beverage samples with a recovery rate of 96.3–103.5 %. Therefore, the three-dimensional NC/CNT-Co hierarchical structure can be provided as an original electrode nanomaterial suitable for the selective and sensitive detection of AA, with a wide range of practical applications from food analysis to the pharmaceutical industry.

Smart Bandage Based on a ZIF-8 Triboelectric Nanogenerator for In Situ Real-Time Monitoring of Drug Concentration.

For chronic wounds, frequent replacement of bandages not only increases the likelihood of secondary damage and the risk of cross infection but also wastes medication. Therefore, in situ real-time monitoring of the concentrations of residual drugs in bandages is crucial. Here, we propose a novel strategy that combines a triboelectric nanogenerator (TENG) with medical bandages to develop a smart bandage based on zeolite imidazolate framework TENG. During the process of wound healing, the electrical output of TENG changes with the continuous release of drugs. Based on the correlation between the electrical signal of TENG and drug concentration, the concentration of residual drugs in the bandage can be monitored in real-time in situ, guiding medical staff to replace the bandage at the most appropriate time. The smart bandage based on TENG provides a new strategy for in situ real-time monitoring of drug concentration and also provides an ideal and feasible solution for the field of biomedical drug sensing.

Pore-Specific Anisotropic Etching of Zeolitic Imidazolate Frameworks by Carboxylic Acid Vapors.

Anisotropic etching is a powerful way to customize metal-organic frameworks with advanced nanostructures, but it is still in its infancy. Herein, we proposed an unprecedented etching strategy that created anisotropic hollow structures in various zeolitic imidazolate framework (ZIF) nano/single crystals via pore-specific carving. The etching occurred through a newly discovered gas-solid reaction where carboxylic acid vapors bind with ligands in ZIFs at room temperature to form ionic liquid (IL). A series of experiments were conducted to decode the origin of anisotropy and the "hollowing out" effect. We found that large pore openings on {111} facets provide access for the entry of carboxylic acid vapors and the outflow of the IL, resulting in pore-dependent anisotropy features. The unique "etching after adsorption" mechanism and the adsorption capacity of the IL enable acid vapors to hollow out nanocrystals and even single crystals. By altering carboxylic acids and ligands in ZIFs, the etching process can be precisely tuned from the inside out or the outside in. This new method demonstrates broad universality and brings unprecedented morphologies and complexities. It may offer great opportunities for achieving purposeful modification of ZIFs and the rational construction of intricate architectures.

Insights into Amorphous Metal‐Organic Framework as Carbonic Anhydrase Mimic

AbstractCarbonic anhydrase (CA) is an important enzyme which breaks the C−O bond and catalyzes the hydration of CO2 and developing artificial enzyme to mimic the function of CA is important for the related applications. Zeolitic imidazolate frameworks (ZIFs) with typical tetrahedral Zn−N coordination units which were similar to the catalytically active site of natural CA have been reported to displayed CA‐like activities. However, the activity of crystalline ZIFs remains unsatisfactory. Herein, amorphous zeolitic imidazolate framework (aZIF) was fabricated through a facile self‐assembly process and exhibited 2.2‐fold higher CA‐like hydrolytic activity than the corresponding crystalline ZIF‐8.This phenomenon can be ascribed to the unsaturated Zn−N coordination structure and mesopores inside aZIF. This work affords a new avenue for the rational design of nanozymes.

Suitable Pore Confinement with Multiple Interactions in a Low-Cost Zeolitic Imidazolate Framework for Efficient Xe Capture and Separation

The increasing industrial demand for the noble gases xenon (Xe) and krypton (Kr), along with growing environmental concerns on their radionuclides, has made the efficient separation and purification of Xe and Kr a critical issue. Leveraging advanced porous materials to achieve highly efficient adsorptive Xe/Kr separation has been recognized as an energy-saving and economical alternative to the widely used cryogenic distillation technology. Herein, we present a stable, low-cost, and easily scalable zeolitic imidazolate framework (ZIF) material, ZIF-4, for effective xenon adsorption and separation. ZIF-4 possesses uniformly distributed pore cavities with ideally matched pore size (4.3 Å) with that of Xe atom (4.047 Å), providing appropriate pore confinement for Xe binding. Sorption isotherms of ZIF-4 demonstrate the remarkably high Xe uptake (1.64 mmol/g at 0.2 bar and 298 K) and excellent Xe/Kr separation selectivity (16.2 for IAST selectivity of 20/80 Xe/Kr gas mixtures). Breakthrough experiments further validate the efficient separation performance of ZIF-4 in both binary Xe/Kr (20/80) gas mixtures and under dilute conditions. Single-crystal X-ray diffraction studies of activated and Xe-loaded ZIF-4 crystals reveal that the flexible pore cavities of ZIF-4 can self-adaptively adsorb and accommodate Xe atoms through the rotation of imidazolate rings, forming multiple Xe···H and Xe···π interactions to create strong binding sites for Xe capture and discrimination. The stability, economic feasibility, and scalability of ZIF-4 underscore its significant potential for industrial Xe/Kr separation.

Ratiometric fluorescent determination of sulfadimethoxine in foods based on a dual-emission metal-organic framework.

Ratiometric fluorescence detection is endowed with higher accuracy than single fluorescence signal assay. In this work, we construct a ratiometric fluorescence probe for the facile quantification of sulfadimethoxine (SDM) in foods. By wrapping N-doped carbon dots (N-CDs) and gold nanoclusters (AuNCs) into zeolitic imidazolate framework-8 (ZIF-8), the nanocomposite of N-CDs/AuNCs@ZIF-8 is facilely prepared and emits two fluorescence including 475nm from N-CDs and 650nm from AuNCs. Since bovine serum albumin (BSA) is the stabilizer of AuNCs, SDM can form a complex with BSA, resulting in the fluorescence quenching of AuNCs at 650nm by a static quenching mechanism. In contrast, SDM has a rare influence on the fluorescence of N-CDs (475nm). As a result, the use of the probe of N-CDs/AuNCs@ZIF-8 for SDM detection enables simultaneous measurement of response signal and reference signal. Under the optimal condition, the SDM assay based on the probe has a good linear relationship within 10 to 2 × 106ng/mL and the limit of detection (LOD) is low to 1.064ng/mL. In addition, the fluorescent probe shows good reliability for the detection of SDM in practical food samples.

Rational Construction of a 3D Self-Supported Electrode Based on ZIF-67 and Amorphous NiCoP for an Enhanced Oxygen Evolution Reaction.

The development of efficient and Earth-abundant electrocatalysts for the oxygen evolution reaction (OER) is an urgent requirement in the field of electrochemical water splitting. The electrocatalytic performance of the OER can be greatly enhanced by the synergistic combination of zeolite imidazolate frameworks (ZIFs) and transition-metal phosphides, both of which individually exhibit promising capabilities in this regard. In this study, a novel amorphous NiCoP deposited on ZIF-67 sheets supported on Ni foam (labeled as NiCoP/ZIF-67/NF) as an OER electrocatalytic material was successfully synthesized using a simple, secure, and time-efficient two-step strategy. The experimental results demonstrate that NiCoP/ZIF-67/NF possesses a large active surface area with abundant active sites. Also, the synergistic effect and interaction between NiCoP and ZIF-67, as well as between Ni and Co within NiCoP, effectively enhance its electrochemical performance under alkaline conditions. Consequently, NiCoP/ZIF-67/NF exhibits outstanding catalytic activity for OER with an overpotential (η) of 175 mV at a current density of 10 mA cm-2 and a long-term stability over 40 h at 20 mA cm-2 in a 1.0 M KOH electrolyte. The corresponding analyses suggest that the real active sites responsible for the OER are identified as NiOOH and CoOOH species within the structure of NiCoP/ZIF-67/NF. Additionally, the catalytic function and stability of ZIF-67 toward the OER under alkaline conditions were also briefly discussed. This work provides a novel catalytic material for the OER along with a facile strategy to fabricate superior, efficient, and noble metal-free catalysts suitable for energy-related applications.

A novel metal‐organic framework encapsulated iridium oxide nanozyme enhanced antisense oligonucleotide combo for osteoarthritis synergistic therapy

AbstractOsteoarthritis (OA) is associated with metabolic imbalance of articular cartilage and an increase of intracellular reactive oxygen species (ROS). Synergistic therapy based on the codelivery of ROS scavengers and antisense oligonucleotides (ASO) into chondrocytes has the potential to effectively treat OA. Here, we developed a novel biocompatible metal‐organic framework (MOF)‐encapsulated nanozyme/ASO delivery platform (miR/IrO2@ZIF‐8) for OA treatment. IrO2 nanoparticles with the catalytic activities of superoxide dismutase/catalase were synthesized using a hydrothermal method, resulting in excellent ROS scavenging performance. IrO2 was further loaded into zeolitic imidazolate framework‐8 (ZIF‐8) to maintain its catalytic efficacy and regulate its size, surface charge, and biocompatibility to enhance the therapeutic effect of the platform. As an effective ASO delivery carrier, the synthesized IrO2@ZIF‐8 exhibited high antagomiR‐181a loading and lysosomal escape capacity, enabling it to rebalance cartilage metabolism. In vitro experiments showed that miR/IrO2@ZIF‐8 could restore ROS levels, mitochondrial membrane potential, and lipid peroxidation in chondrocytes. At the same time, the expression levels of proinflammatory markers (IL‐1β, IL‐6, and COX‐2) as well as the extracellular matrix degrading enzymes (ADAMTS‐5 and MMP13) were downregulated, indicating effective antioxidant, anti‐inflammatory, and anticartilage degradation effects. Notably, miR/IrO2@ZIF‐8 was able to deliver IrO2 nanoparticles and antagomiR‐181a to the cartilage tissue at a depth of up to 1.5 mm, thus solving the problems of poor permeability and difficult retention of drugs in cartilage tissue. This further improves the synergistic therapeutic effect on OA by inhibiting cartilage degradation. The combination of MOF‐encapsulated IrO2 nanozymes with antagomiR‐181a has an excellent therapeutic effect on OA, offering a promising translational medicine paradigm.

Aggregation and Sedimentation Stability of Nanoscale Zeolitic Imidazolate Framework (ZIF‐8) Nanocomposites for Antimicrobial Agent Delivery Applications

ABSTRACTThe applications of nanoscale zeolitic imidazolate frameworks (ZIF‐8) for antimicrobial drug delivery depend on the aqueous suspension stability of the ZIF‐8 which is influenced by their crystallinity, size, shape, aggregation, and surface chemistry. This study evaluated the stability of ZIF‐8 nanoparticles in terms of their aggregation and sedimentation characteristics. ZIF‐8 nanocomposites were synthesized with methanol via sonication at 30°C for 1 h. The effect of drying methods (oven drying at 80°C, and vacuum drying at 35°C), number of washing steps (0 = no wash, 1, 2, 3), and washing medium (washing with water and ethanol instead of methanol, and redispersion in water and ethanol) on the suspension stability was evaluated. The impact of added xanthan gum (XG) and poly‐L‐lysine (PL) as suspension media was also evaluated. ZIF‐8 nanoparticles were also synthesized using ethanol and suspended in PL. % transmittance and zeta potential were measured for freshly prepared ZIF‐8 suspensions in PL and after freeze‐drying and resuspending in water. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and x‐ray diffraction (XRD) analysis were utilized for the assessment of the crystallinity, structure, and morphology of the samples. Antibacterial activity was evaluated by disc diffusion test against Escherichia coli. Dried methanol‐synthesized ZIF‐8 nanoparticles did not suspend in water; only the ZIF‐8 nanoparticles synthesized with reduced washing times and no drying treatment were resuspended in the water, XG and PL solutions. Instead, the ethanol‐synthesized ZIF‐8 nanoparticles were resuspended in water even after being washed three times and dried in a vacuum oven. SEM and TEM images and XRD patterns showed that alcohol can form well‐defined ZIF‐8 nanoparticles. FTIR spectra showed that ZIF‐8 had typical peaks of ZIF‐8 reported by others. Although particle size increased, the PL coating provided a 32.22% increase in zeta potential of ZIF‐8 nanoparticles from 36.25 to 47.93 mV (p < 0.05) and prevented aggregation and sedimentation of the nanoparticles without changing their morphology. All the tested ZIF‐8 nanoparticles showed antibacterial activity with the PL‐coated ZIF‐8 having the highest effect followed by the ZIF‐8 nanoparticles synthesized in ethanol.