Metal-organic Framework ZIF-8 Research Articles

Submersible voltammetric sensing probe for rapid and extended remote monitoring of opioids in community water systems

The intensifying global opioid crisis, majorly attributed to fentanyl (FT) and its analogs, has necessitated the development of rapid and ultrasensitive remote/on-site FT sensing modalities. However, current approaches for tracking FT exposure through wastewater-based epidemiology (WBE) are unadaptable, time-consuming, and require trained professionals. Toward developing an extended in situ wastewater opioid monitoring system, we have developed a screen-printed electrochemical FT sensor and integrated it with a customized submersible remote sensing probe. The sensor composition and design have been optimized to address the challenges for extended in situ FT monitoring. Specifically, ZIF-8 metal–organic framework (MOF)-derived mesoporous carbon (MPC) nanoparticles (NPs) are incorporated in the screen-printed carbon electrode (SPCE) transducer to improve FT accumulation and its electrocatalytic oxidation. A rapid (10 s) and sensitive square wave voltammetric (SWV) FT detection down to 9.9 µgL−1 is thus achieved in aqueous buffer solution. A protective mixed-matrix membrane (MMM) has been optimized as the anti-fouling sensor coating to mitigate electrode passivation by FT oxidation products and enable long-term, intermittent FT monitoring. The unique MMM, comprising an insulating polyvinyl chloride (PVC) matrix and carboxyl-functionalized multi-walled carbon nanotubes (CNT-COOH) as semiconductive fillers, yielded highly stable FT sensor operation (> 95% normalized response) up to 10 h in domestic wastewater, and up to 4 h in untreated river water. This sensing platform enables wireless data acquisition on a smartphone via Bluetooth. Such effective remote operation of submersible opioid sensing probes could enable stricter surveillance of community water systems toward timely alerts, countermeasures, and legal enforcement.Graphical abstract

Biomimetic Metal-Organic Framework Gated Nanoplatform for Sonodynamic Therapy against Extensively Drug Resistant Bacterial Lung Infection.

Novel antimicrobial strategies are urgently needed to treat extensively drug-resistant (XDR) bacterial infections due to the high mortality rate and lack of effective therapeutic agents. Herein, nanoengineered human umbilical cord mesenchymal stem cells (hUC-MSCs), named PMZMU, are designed as a sonosensitizer for synergistic sonodynamic-nano-antimicrobial therapy against gram-negative XDR bacteria. PMZMU is composed of a bacterial targeting peptide (UBI29-41) modified hUC-MSCs membrane (MSCm), a sonosensitizer meso-tetra(4-car-boxyphenyl) porphine doped mesoporous organo-silica nanoparticle and an acidity-responsive metal-organic framework ZIF-8. This innovative formulation enables efficient loading of polymyxin B, reduces off-target drug release, increases circulation and targeting efficacy, and generates reactive oxygen species upon ultrasound irradiation. PMZMU exhibits remarkable in vitro inhibitory activity against four XDR bacteria: Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa (PA), and Escherichia coli. Taking advantage of the bacterial targeting ability of UBI29-41 and the inflammatory chemotaxis of hUC-MSC, PMZMU can be precisely delivered to lung infection sites thereby augmenting polymyxin B concentration. PMZMU-mediated sonodynamic therapy significantly reduces bacterial burden, relieves inflammatory damage by promoting the polarization of macrophages toward M2 phenotype, and improves survival rates without introducing adverse events. Overall, this study offers promising strategies for treating deep-tissue XDR bacterial infections, and guides the design and optimization of biomimetic nanomedicine.

Simultaneous determination of lead and cadmium in water by metal oxide framework complex-modified glassy carbon electrodes

Lead (Pb) and cadmium (Cd) are pervasive environmental pollutants known for their significant biological toxicity. The traditional methods for detecting these ions often necessitate large-scale instruments and complex procedures. In contrast, electrochemical detection methods offer advantages such as rapidity, portability, and sensitivity, making them suitable for the simultaneous detection of heavy metals. Metal-organic frameworks (MOFs), characterized by their exceptional adsorption and enrichment capabilities for heavy metal ions, have shown promise in this regard. Nevertheless, the poor conductivity of most MOFs has limited their electrochemical applications. In this study, glassy carbon electrodes (GCEs) were modified using the MOF ZIF-8, in combination with a bismuth complex and carboxylated multi-walled carbon nanotubes, resulting in the fabrication of Bi@ZIF-8/CMWCNTs/GCE electrochemical sensors. Leveraging the porous nature and large specific surface area of ZIF-8, the lead and cadmium ion adsorption by bismuth akin to mercury, and the conductivity of carboxylated multi-walled carbon nanotubes, the sensor developed in this study exhibits excellent capability for simultaneous detection of lead and cadmium ions in water. Under optimized conditions, Pb2+ and Cd2+ showed good linear relationships with the peak current in the concentration range of 2.0–50.0 μg/L. In the concentration range studied, the regression equations for Pb2+ and Cd2+ were determined as follows: y = 0.2982x + 0.4553 (r = 0.9962) for Pb2+ and y = 0.3631x + 0.1242 (r = 0.9949) for Cd2+. The detection limits for Pb2+ and Cd2+ were 0.76 μg/L and 0.87 μg/L, respectively. The relative standard deviations (RSDs) for 50 μg/L mixed standard solution of Pb and Cd were 1.89 % and 1.23 %, respectively. Furthermore, the RSDs for the same modified electrode tested with 50 μg/L Pb2+ and Cd2+ mixed standard solution over seven consecutive days were 2.27 % and 1.42 %, respectively, under identical conditions. In practice, the lead and cadmium concentrations of a lake were found to range from 4.42 μg/L to 5.60 μg/L, while the lead and cadmium concentrations of effluent from a wastewater plant ranged from 11.83 μg/L to 14.49 μg/L. This research not only describes a new electrochemical platform for the simultaneous determination of lead and cadmium in water but also provides a new method for the simultaneous determination of lead and cadmium in water. This research is valuable for promoting the application of MOFs in the field of electrochemistry.

ZIF-8@Hydroxyapatite Composite as a High Potential Material for Prolonged Delivery of Agrochemicals.

Although agrochemical practices can enhance agricultural productivity, their intensive application has resulted in the deterioration of ecosystems. Therefore, it is necessary to develop more efficient and less toxic methods against pests and infections while improving crop productivity. Moving toward sustainable development, in this work, we originally described the preparation of a composite (ZIF-8@HA) consisting of the coating of zeolitic-like metal-organic framework (MOF) ZIF-8 (based on Zn, an essential micronutrient in plants with antibacterial, antifungal, and antifouling properties) with hydroxyapatite (HA) nanoparticles (i.e., nanofertilizer). The interaction between the HA and ZIF-8 has been characterized through a combination of techniques, such as microscopic techniques, where the presence of a HA coating is demonstrated; or by analysis of the surface charge with a dramatic change in the Z-potential (from +18.7 ± 0.8 to -27.6 ± 0.7 mV for ZIF-8 and ZIF-8@HA, respectively). Interestingly, the interaction of HA with ZIF-8 delays the MOF degradation (from 4 h for pristine ZIF-8 to 168 h for HA-coated material), providing a slower and gradual release of zinc. After a comprehensive characterization, the potential combined fertilizer and bactericidal effect of ZIF-8@HA was investigated in wheat (Triticum aestivum) seeds and Pseudomonas syringae (Ps). ZIF-8@HA (7.3 ppm) demonstrated a great fertilizer effect, increasing shoot (9.4 %) and root length (27.1 %) of wheat seeds after 11 days at 25 °C under dark conditions, improving the results obtained with HA, ZIF-8, or ZnSO4 or even physically mixed constituents (HA + ZIF-8). It was also effective in the growth inhibition (>80 % of growth inhibition) of Ps, a vegetal pathogen causing considerable crop decline. Therefore, this work demonstrates the potential of MOF@HA composites and paves the way as a promising agrochemical with improved fertilizer and antibacterial properties.

Ammonia-Responsive Colorimetric Film of Phytochemical Formulation (Alizarin) Grafted onto ZIF-8 Carrier with Poly(vinyl alcohol) and Sodium Alginate for Beef Freshness Monitoring.

In this study, we devised a photothermally stable phytochemical dye by leveraging alizarin in conjunction with the metal-organic framework ZIF-8 (AL@ZIF-8). The approach involved grafting alizarin into the microporous structure of ZIF-8 through physical adsorption and hydrogen-bonding interactions. AL@ZIF-8 significantly enhanced the photostability and thermostability of alizarin. The nanoparticles demonstrate substantial color changes in various pH environments, showcasing their potential for meat freshness monitoring. Furthermore, we introduced an intelligent film utilizing poly(vinyl alcohol)-sodium alginate-AL@ZIF-8 (PA-SA-ZA) for detecting beef freshness. The sensor exhibited a superior water contact angle (52.34°) compared to the alizarin indicator. The color stability of the film was significantly enhanced under visible and UV light (ΔE < 5). During beef storage, the film displayed significant color fluctuations correlating with TVB-N (R2=0.9067), providing precise early warning signals for assessing beef freshness.

Cryo-EM combined with image deconvolution to determine ZIF-8 crystal structure

Abstract Metal-organic frameworks (MOFs) are crystalline porous materials with tunable properties, exhibiting great potential in gas adsorption, separation and catalysis.[1, 2] It is challenging to visualize MOFs with transmission electron microscopy (TEM) due to their inherent instability under electron beam irradiation. Here, we employ cryo-electron microscopy (cryo-EM) to capture images of MOF ZIF-8, revealing inverted-space structural information at a resolution of up to about 1.7 Å and enhancing its critical electron dose to around 20 e-/Å2. In addition, it is confirmed by electron-beam irradiation experiments that the high voltage could effectively mitigate the radiolysis, and the structure of ZIF-8 is more stable along the [100] direction under electron beam irradiation. Meanwhile, since the high-resolution electron microscope images is modulated by contrast transfer function (CTF) and it is difficult to determine the positions corresponding to the atomic columns directly from the images. We employ image deconvolution to eliminate the impact of CTF and obtain the structural images of ZIF-8. As a result, the heavy atom Zn and the organic imidazole ring within the organic framework can be distinguished from structural images.

Removal of Humic Acid from Water by Adsorption Using Chitosan and Metal Organic Framework ZIF 8 Loaded Chitosan Adsorbents

Water is the most necessary need for life on the earth. There are a lot of organic pollutants in water. One of the organic pollutants is natural organic substances. Humic acid, a natural organic substance, turns into very harmful substances along with other pollutants. In this study, the humic acid removal from aqueous solution by adsorption using chitosan and chitosan/ZIF 8 composite spheres was examined. Chitosan spheres cross-linked with epichlorohydrin (ECH) and composite spheres consisting of metal organic framework ZIF8 and chitosan were prepared as adsorbents. Equilibrium, kinetic, and thermodynamic studies were investigated for humic acid adsorption by pristine chitosan-ECH and composite chitosan/ZIF 8 adsorbents. Chemical adsorption was found to be compatible with the Freundlich isotherm model and the pseudo-first-order kinetic model for pure chitosan adsorbents. Studies were carried out using chitosan/ZIF8 composite adsorbent, and the most suitable models for chemical adsorption were determined as Langmuir isotherm and pseudo-second order kinetic model. The response surface method was applied with the design expert program to determine the optimum experimental conditions. The adsorption tests were carried out using chitosan-ECH, ZIF 8 and chitosan/ZIF 8 adsorbents for specified optimum conditions, and the humic acid removal was determined as 95.1%, 98.3%, and 97.3%, respectively. In addition, desorption was performed using chitosan-ECH and chitosan/ZIF 8 spheres, and the desorption efficiency was found to be 20.9% and 82.5%, respectively. It has been observed that the developed adsorbents have potential in removing humic acid from water.

ZIF-8 functionalized S-tapered fiber-optic sensor for polystyrene nanoplastics detection by electrostatic adsorption

Microplastic (MP) residues in marine have become an increasingly serious environmental pollution issue, and in recent years the detection of MPs in marine started to attract worldwide research interests. Optical-fiber-based environmental sensors have been extensively employed for their several merits such as high sensitivity, pressure resistance, compactness and ease of constructing communication networks. However, fiber-optic refractive index sensors are not specifically developed for distinguishing MPs from other inorganic particles suspended in water. In this paper, an metal-organic framework (MOF) ZIF-8 functionalized S-tapered fiber (STF) sensor is proposed for specific detection of polystyrene nanoplastics (PSNPs) in aqueous environment. ZIF-8 coordination nanoporous polymers with different film thickness were immobilized over the surface of the fabricated STF structure based on self-growth technique and yielding a large surface area over the sensor surface. High sensitivity detection can be achieved by converting the concentration perturbation of PSNPs into evanescent waves over the ZIF-8 functionalized STF surface through the strong electrostatic adsorption effect and π-π stacking, while the fabricated sensor is insensitive to gravels with silica as the primary component in water. It is found that the proposed detector with 18 film layers achieves a sensitivity up to 114.1353nm/%(w/v) for the PSNPs concentration range of 0.01 %(w/v) to 0.08 %(w/v).

Use of a pH-responsive imatinib mesylate sustained-release hydrogel for the treatment of tendon adhesion by inhibiting PDGFRβ/CLDN1 pathway

Adhesion after tendon injury, which can result in limb movement disorders, is a common clinical complication; however, effective treatment methods are lacking. Hyaluronic acid hydrogels are a new biomedical material used to prevent tendon adhesion owing to their good biocompatibility. In addition, potential drugs that inhibit adhesion formation have gradually been discovered. The anti-adhesion effects of a combination of loaded drugs into hydrogels have become an emerging trend. However, current drug delivery systems usually lack specific regulation of drug release, and the effectiveness of drugs for treating tendon adhesions is mostly flawed. In this study, we identified a new drug, imatinib mesylate (IM), that prevents tendon adhesion and explored its related molecular pathways. In addition, we designed a pH-responsive sustained-release hydrogel for delivery. Using the metal-organic framework ZIF-8 as a drug carrier, we achieved controlled drug release to increase the effective drug dose at the peak of adhesion formation to achieve better therapeutic effects. The results showed that IM blocked the formation of peritendon adhesions by inhibiting the PDGFRβ/ERK/STAT3/CLDN1 pathway. Furthermore, the hydrogel with ZIF-8 exhibited better physical properties and drug release curves than the hydrogel loaded only with drugs, showing better prevention and treatment effects on tendon adhesion.

3D-printing of alginate/gelatin scaffold loading tannic acid@ZIF-8 for wound healing: In vitro and in vivo studies

In the present study, ZIF-8 metal-organic framework (MOF) modified with Tannic acid (TA@ZIF-8) was synthesized and impregnated in alginate-gelatin (Alg-Gel) hydrogel. The Alg-Gel scaffolds containing 0, 5, and 10 % of TA@ZIF-8 were fabricated through the 3D printing method specifically denoted as Alg-Gel 0 %, Alg-Gel 5 %, and Alg-Gel 10 %. XRD, FTIR, FESEM, and EDX physically and chemically characterized the synthesized ZIF-8 and TA@ZIF-8 MOFs. Besides, Alg-Gel containing TA@ZIF-8 prepared scaffolds and their biological activity were also evaluated. SEM images verified the nano-size formation of MOFs. Improved swelling and decreased degradation rates after adding TA@ZIF-8 were also reported. Increased compression strength from 0.628 to 1.63 MPa in Alg-Gel 0 % and Alg-Gel 10 %, respectively, and a 2.19 increase in elastic modulus in Alg-Gel 10 % scaffolds were exhibited. Biological activity of scaffolds, including Live-dead and Cell adhesion, antibacterial, in-vivo, and immunohistochemistry assays, demonstrated desirable fibroblast cell proliferation and adhesion, increased bacterial growth inhibition zone, accelerated wound closure and improved expression of anti-inflammatory cytokines in Alg-Gel 10 % scaffolds. The findings of this study confirm that Alg-Gel 10 % scaffolds promote full-thickness wound healing and could be considered a potential candidate for full-thickness wound treatment purposes.

Efficient Removal of Tetracycline by Metal–Organic Framework ZIF-67 and Its Mechanism

The widespread use of tetracycline (TC) poses potential hazards to ecosystems and human health. In this study, ZIF-67 was successfully synthesized using a room-temperature static synthesis method and applied to the efficient removal of TC from water. It was shown that the maximum adsorption of TC by ZIF-67 could reach 1583.128 mg·g−1 at pH = 5.0, an initial TC concentration of 450 mg·g−1, an adsorption time of 720 min, and a temperature of 308K.The pseudo-second-order kinetic model and Langmuir’s isothermal adsorption model could describe the adsorption process better, which proved that the adsorption of ZIF-67 on TC was mainly monolayer adsorption dominated by chemisorption. Mechanistic studies showed that the adsorption process of ZIF-67 on TC was mainly through electrostatic interactions, pore adsorption, π–π interactions, and framework coordination of ZIF-67 surface cations with TC.

Comparison study between as-synthesized ZnO and ZnO derived from ZiF-8 metalorganic framework in removing methylene blue

The nanoporous materials derived from the ZiF-8 metalorganic framework are highly interesting because of their features like good thermal stability, catalytic performance, and electric conductivity. Therefore, ZiF-derived metal oxide was utilized in several applications, for instance, energy storage and environmental remediations. Herin, we compare the as-prepared ZnO, ZiF-8, and ZnO derived from ZiF-8 in terms of structural, thermal, and morphological properties. Thus, the photocatalytic performance of all compositions. The preparation process is an effective parameter in the morphology of the sample surface. The as-synthesized ZnO had nanoparticle morphology with a size of 50–80[Formula: see text]nm. However, the ZiF-8 has cubic morphology with a long rod. The decomposition of ZiF-8 converted the sample to ZnO coated by carbon, indicating a high surface and fit morphology for photocatalysis. These results mean that ZnO derivative from ZiF-8 nanoparticles has the best efficiency for water desalination with 95%. ZnO drives from ZiF-8 demonstrated the smallest charge transfer resistance compared to that of as-prepared ZnO, and ZIF-8, coinciding with the conclusion of the EIS results. The transient photoresponses and electrochemical impedance spectra of the compounds were used further to explore the separation efficiency of the photogenerated charge carriers.

Establishing ZIF-8 as a reference material for hydrogen cryoadsorption: An interlaboratory study.

Hydrogen storage by cryoadsorption on porous materials has the advantages of low material cost, safety, fast kinetics, and high cyclic stability. The further development of this technology requires reliable data on the H2 uptake of the adsorbents, however, even for activated carbons the values between different laboratories show sometimes large discrepancies. So far no reference material for hydrogen cryoadsorption is available. The metal-organic framework ZIF-8 is an ideal material possessing high thermal, chemical, and mechanical stability that reduces degradation during handling and activation. Here, we distributed ZIF-8 pellets synthesized by extrusion to 9 laboratories equipped with 15 different experimental setups including gravimetric and volumetric analyzers. The gravimetric H2 uptake of the pellets was measured at 77 K and up to 100 bar showing a high reproducibility between the different laboratories, with a small relative standard deviation of 3-4 % between pressures of 10-100 bar. The effect of operating variables like the amount of sample or analysis temperature was evaluated, remarking the calibration of devices and other correction procedures as the most significant deviation sources. Overall, the reproducible hydrogen cryoadsorption measurements indicate the robustness of the ZIF-8 pellets, which we want to propose as a reference material.

Stable Mg Single-Atom Solid Base Catalysts Anchored on Metal-Organic Framework-Derived Nitrogen-Doped Carbon.

Solid base catalysts are widely used in the chemical industry owing to their advantages of environmental friendliness and easy separation. However, their application is limited by basic site aggregation and poor stability. In this study, we report the preparation of magnesium (Mg) single-atom catalysts with high activity and stability by a sublimation-trapping strategy. The Mg net was sublimated as Mg vapor at 620 °C, subsequently transported through argon, and finally trapped on the defects of nitrogen-doped carbon derived from metal-organic framework ZIF-8, producing Mg1/NC. Because of the atomically dispersed Mg sites, the obtained Mg1/NC exhibits high catalytic activity and stability for Knoevenagel condensation of benzaldehyde with malononitrile, which is a typical base-catalyzed reaction. The Mg1/NC catalyst achieves a high efficiency with a turnover frequency of 49.6 h-1, which is much better than that of the traditional counterpart MgO/NC (7.7 h-1). In particular, the activity of Mg1/NC shows no decrease after five catalytic cycles, while that of MgO/NC declines due to the instability of basic sites.

Unveiling the mechanisms behind high CO2 adsorption by the selection of suitable ionic liquids incorporated into a ZIF-8 metal organic framework: A computational approach

There is growing focus on the crucial task of effectively capturing carbon dioxide (CO2) from the atmosphere to mitigate environmental consequences. Metal-organic frameworks (MOFs) have been used to replace many conventional materials in gas separation, and the incorporation of ionic liquids (ILs) into porous MOFs has shown promise as a new technique for improving CO2 capture and separation. However, the driving force underlying the electronic modulation of MOF nanostructures and the mechanisms behind their high CO2 adsorption remain unclear. This study reports the effect of encapsulating different imidazolium ILs in porous ZIF-8, to clarify the adsorption mechanism of CO2 using density functional theory (DFT)-based approaches. For this purpose, a range of anions, including bis(trifluoromethylsulfonyl)imide [NTf2], methanesulfonate [MeSO3], and acetate [AC], were combined with the 1-ethyl-3-methylimidazolium [EMIM]+ cation. [EMIM]+-based ILs@ZIF-8 composites were computationally investigated to identify suitable materials for CO2 capture. First, the intermolecular and intramolecular interactions between [EMIM]+ and different anions were examined in detail, and their effects on CO2 adsorption were explored. Subsequently, the integration of these ILs into the ZIF-8 solid structure was studied to reveal how their interactions influenced the CO2 adsorption behavior. Our results demonstrate that the incorporation of ILs strongly affects the adsorption capability of CO2, which is highly dependent on the nature of the ILs inside the ZIF-8 framework. DFT simulations further confirmed that the incorporation of ILs into ZIF-8 led to superior CO2 capture compared to isolated ILs and pristine ZIF-8. This improvement was attributed to the mutual interactions between the ILs and ZIF-8, which effectively fine-tuned CO2 adsorption within the composite structure. This understanding may act as a general guide for gaining more insight into the interfacial interactions between ILs and ZIFs structures and how these molecular-level interactions can help predict the selection of ILs for CO2 adsorption and separation, thereby addressing environmental challenges with greater precision and effectiveness.

Biocompatible metal-organic frameworks as promising platforms to eradicate HIV reservoirs ex vivo in people living with HIV.

The HIV attacks the immune system provoking an infection that is considered a global health challenge. Despite antiretroviral treatments being effective in reducing the plasma viral load in the blood to undetectable levels in people living with HIV (PLWH), the disease is not cured and has become chronic. This happens because of the existence of anatomical and cellular viral reservoirs, mainly located in the lymph nodes and gastrointestinal tract, which are composed of infected CD4+ T cells with a resting memory phenotype and inaccessible to antiretroviral therapy. Herein, a new therapeutic strategy based on nanotechnology is presented. Different combinations of antiretroviral drugs (bictegravir/tenofovir/emtricitabine and nevirapine/tenofovir/emtricitabine) and toll-like receptor agonists were encapsulated into metal-organic frameworks (MOFs) PCN-224 and ZIF-8. The encapsulation efficiencies of all the drugs, as well as their release rate from the carriers, were measured. In vitro studies about the cell viability, the hemocompatibility, and the platelet aggregation of the MOFs were carried out. Epifluorescence microscopy assays confirmed the ability of ZIF-8 to target a carboxyfluorescein probe inside HeLa cell lines and PBMCs. These results pave the way for the use of these structures to eliminate latent HIV reservoirs from anatomical compartments through the activation of innate immune cells, and a higher efficacy of the triplet combinations of antiretroviral drugs.

Nanoscale solvent organization in metal-organic framework ZIF-8 probed by EPR of flexible β-phosphorylated nitroxides.

Metal-organic frameworks (MOFs) draw increasing attention as nanoenvironments for chemical reactions, especially in the field of catalysis. Knowing the specifics of MOF cavities is decisive in many of these cases; yet, obtaining them in situ remains very challenging. We report the first direct assessment of the apparent polarity and solvent organization inside MOF cavities using a dedicated structurally flexible spin probe. A stable β-phosphorylated nitroxide radical was incorporated into the cavities of a prospective MOF ZIF-8 in trace amounts. The spectroscopic properties of this probe depend on local polarity, structuredness, stiffness and cohesive pressure and can be precisely monitored by Electron Paramagnetic Resonance (EPR) spectroscopy. Using this approach, we have demonstrated experimentally that the cavities of bare ZIF-8 are sensed by guest molecules as highly non-polar inside. When various alcohols fill the cavities, remarkable self-organization of solvent molecules is observed leading to a higher apparent polarity in MOFs compared to the corresponding bulk alcohols. Accounting for such nanoorganization phenomena can be crucial for optimization of chemical reactions in MOFs, and the proposed methodology provides unique routes to study MOF cavities inside in situ, thus aiding in their various applications.

Improving thermostability, solvent tolerance, and reusability of methyl parathion hydrolase through immobilization into the metal-organic framework ZIF-8

The metal-organic framework (MOF) ZIF-8 has found extensive application in the medicinal and agricultural fields. This study aimed to immobilize the methyl parathion hydrolase (MPH) enzyme from Azohydromonas australica (Azau-MPH) within ZIF-8 using an in-situ synthesis method. Interestingly, the immobilized Azau-MPH (abbreviated as Azau-MPH@ZIF-8) exhibited enhanced thermostability and tolerability towards organic solvents compared to the free enzyme. Moreover, Azau-MPH@ZIF-8 retained more than 50% of its initial activity after six cycles, demonstrating its desirable reusability. To further improve the recyclability and catalytic activity of the immobilized enzyme, we introduced magnetic Fe3O4 nanoparticles into the immobilization carrier. Notably, the resulting Azau-MPH@(Fe3O4@ZIF-8) biocomposite displayed superior catalytic activity and stability when compared to Azau-MPH@ZIF-8. In practical applications, we employed Azau-MPH@ZIF-8 for cyclic degradation of methyl parathion (20 mg/L) in cherries, and it exhibited exceptional degradation ability. Hence, both Azau-MPH@ZIF-8 and Azau-MPH@(Fe3O4@ZIF-8) hold great promise as valuable biodegradation tools against MP contamination.

Design Principles Guiding Solvent Size Selection in ZIF-Based Type 3 Porous Liquids for Permanent Porosity.

Porous liquids (PLs), which are solvent-based systems that contain permanent porosity due to the incorporation of a solid porous host, are of significant interest for the capture of greenhouse gases, including CO2. Type 3 PLs formed by using metal-organic frameworks (MOFs) as the nanoporous host provide a high degree of chemical turnability for gas capture. However, pore aperture fluctuation, such as gate-opening in zeolitic imidazole framework (ZIF) MOFs, complicates the ability to keep the MOF pores available for gas adsorption. Therefore, an understanding of the solvent molecular size required to ensure exclusion from MOFs in ZIF-based Type 3 PLs is needed. Through a combined computational and experimental approach, the solvent-pore accessibility of exemplar MOF ZIF-8 was examined. Density functional theory (DFT) calculations identified that the lowest-energy solvent-ZIF interaction occurred at the pore aperture. Experimental density measurements of ZIF-8 dispersed in various-sized solvents showed that ZIF-8 adsorbed solvent molecules up to 2 Å larger than the crystallographic pore aperture. Density analysis of ZIF dispersions was further applied to a series of possible ZIF-based PLs, including ZIF-67, -69, -71(RHO), and -71(SOD), to examine the structure-property relationships governing solvent exclusion, which identified eight new ZIF-based Type 3 PL compositions. Solvent exclusion was driven by pore aperture expansion across all ZIFs, and the degree of expansion, as well as water exclusion, was influenced by ligand functionalization. Using these results, a design principle was formulated to guide the formation of future ZIF-based Type 3 PLs that ensures solvent-free pores and availability for gas adsorption.

Recombinant streptococcal protein G-modified metal-organic framework ZIF-8 for the highly selective purification of immunoglobulin G from human serum

A novel solid phase extractant His-rSPG@ZIF-8 was prepared by covalently coupling recombinant streptococcal protein G (His-rSPG) with ZIF-8. The His-rSPG@ZIF-8 composite was characterized by Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy (Raman), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Due to the specific binding between the immunoglobulin binding region of His-rSPG and the Fc region of immunoglobulin G (IgG), the His-rSPG@ZIF-8 composite demonstrated exceptional selectivity in adsorbing IgG. In Britton-Robinson buffer (BR buffer) with a salt concentration of 500 mmol L−1 (0.04 mol L−1, pH 8.0), the His-rSPG@ZIF-8 composite exhibited a remarkable adsorption efficiency of 99.8 % for 0.05 mg of the composite on 200 μL of IgG solution (100 μg mL−1). The adsorption behavior of the His-rSPG@ZIF-8 composite aligns with the Langmuir adsorption model, and the theoretical maximum adsorption capacity is 1428.6 mg g−1. The adsorbed IgG molecules were successfully eluted using a SDS solution (0.5 %, m/m), resulting in a recovery rate of 91.2 %. Indeed, the His-rSPG@ZIF-8 composite was successfully utilized for the isolation and purification of IgG from human serum samples. The obtained IgG exhibited high purity, as confirmed by SDS-PAGE analysis. Additionally, LC-MS/MS analysis was employed to identify the human serum proteins following the adsorption and elution process using the His-rSPG@ZIF-8 composite material. The results revealed that the recovered solution contained an impressive content of immunoglobulin, accounting for 62.4 % of the total protein content. Furthermore, this process also led to the significant enrichment of low abundance proteins such as Serpin B4 and Cofilin-1. Consequently, the His-rSPG@ZIF-8 composite holds great promise for applications such as IgG purification and immunoassays. At the same time, it expands the application of metal-organic frameworks in the field of proteomics.