The active sites of inexpensive transition metal electrocatalysts are sparse and singular, thus high-entropy alloys composed of non-precious metals have attracted considerable attention due to their multi-component synergistic effects. However, the facile synthesis of high-entropy alloy composites remains a challenge. Herein, we report a \"one-stone, two-birds\" method utilizing zinc (Zn)-rich metal-organic frameworks as precursors, by virtue of the low boiling point of Zn (907 °C) and its high volatility in alloys, high-entropy alloy carbon nanocomposite with a layered pore structure was ultimately synthesized. The experimental results demonstrate that the volatilization of zinc can prevent metal agglomeration and contribute to the formation of uniformly dispersed high-entropy alloy nanoparticles at slower pyrolysis and cooling rates. Simultaneously, the volatilization of Zn plays a crucial role in creating the hierarchical porous structure. Compared to the zinc-free HEA/NC-1, the HEA/NC-5 derived from the precursor containing 0.8 Zn exhibit massive micropores and mesopores. The resulting nanocomposites represent a synergistic effect between highly dispersed metal catalytic centers and hierarchical adsorption sites, thus achieving excellent electrocatalytic oxygen reduction performance with low catalyst loading compared to commercial Pt/C. This convenient zinc-rich precursor method can be extended to the production of more high-entropy alloys and various application fields.

Microwave thermotherapy (MWTT), as a treatment for tumors, lacks specificity and requires sensitizers. Most reported microwave sensitizers are single metal-organic frameworks (MOFs), which must be loaded with ionic liquids to enhance the performance in MWTT. Meanwhile, MWTT is rarely combined with other treatment modalities. Here, we synthesized a novel Fe-Cu bimetallic organic framework FeCuMOF (FCM) by applying a hydrothermal method and further modified it with methyl polyethylene glycol (mPEG). The obtained FCM@PEG (FCMP) showed remarkable heating performance under low-power microwave irradiation; it also acted as a novel nanospheres enzyme to catalyze H2O2 decomposition, producing abundant reactive oxygen species (ROS) to deplete glutathione (GSH) and prevent ROS clearance from tumor cells during chemodynamic treatment. The FCMP was biodegradable and demonstrated excellent biocompatibility, allowing it to be readily metabolized without causing toxic effects. Finally, it was shown to act as a suitable agent for T2 magnetic resonance imaging (MRI) in vitro and in vivo. This new bimetallic nanostructure could successfully realize two tumor treatment modalities (MWTT and chemodynamic therapy) and dual imaging modes (T2 MRI and microwave thermal imaging). Our findings represent a breakthrough for integrating the diagnosis and treatment of tumors and provides a reference for developing new microwave sensitizers.

Microplastics (MPs) and other organic matters in textile wastewater have posed a formidable challenge for treatment processes, particularly in the primary stages such as ultrafiltration (UF). UF plays a crucial role in preventing the entry of pollutants into subsequent treatment steps. However, the performance efficiency of UF membranes is compromised by the potential fouling of membrane pores by MPs, dyes and other organic pollutants such as bovine serum albumin (BSA). This study focuses on enhancing UF membrane performance, specifically its antifouling properties, through the development of high-performance membranes using MIL-53(Fe) metal-organic framework (MOF) particles (noted as MIL-53 here). Various concentrations of the MIL-53 (0.05, 0.1, 0.2, and 0.5 wt%) were integrated into the membrane structure through phase inversion process. Streaming zeta potential results confirmed the negatively charged surface of the membranes and their high hydrophilicity was validated through contact angle analysis. FTIR, SEM, EDS, and XRD confirmed the presence of MIL-53 particles on the surface of membranes. The developed membranes were tested for 24 h to assess their antifouling properties, with a subsequent 30-min hydraulic flush to measure their flux recovery ratios. Methylene Blue (MB) dye was used as a cationic dye present in textile wastewater to evaluate the efficiency of the developed membranes in dye removal and the synergistic effects of dye rejection in the presence of organic matters (i.e., MPs and BSA). Since previous studies have not fully addressed the combination of dyes and organic matter, this study thoroughly investigated the effect of particle-type foulants (MPs) and their interactions with dye (MB), as well as water soluble protein-type foulants (BSA) and their interaction with MB. The results indicated that the developed membranes exhibited higher MB rejection when the dye was present with either MP or BSA, along with improved antifouling properties. The optimised UF membrane integrated with 0.1 wt% MIL-53 demonstrated nearly 96% BSA rejection and around 86% MB rejection in the mixed foulant case (BSA-MB). The modified membrane exhibited a substantial increase in water flux from 176 L m-2.h-1 to 327 L m-2.h-1. The findings of this research show the potential of iron-based MOFs in improving the performance of UF membranes and provide a platform for future studies on significant areas such as long-term stability studies and testing with other pollutants found in textile wastewater.

Metal-organic frameworks (MOFs) are a fascinating family of crystalline porous materials made up of metal clusters and organic linkers. In comparison with other porous materials, MOFs have unique characteristics including high surface area, homogeneous open cavities, and permanent high porosity with variable shapes and sizes. For these reasons, MOFs have recently been explored as sorbents in sample preparation by solid-phase extraction (SPE). However, SPE requires large amounts of sorbents and suffers from limited contact surfaces with analytes, which compromises extraction recovery and efficiency. Dispersive SPE (D-SPE) overcomes these limitations by dispersing the sorbents into the sample, which in turn increases contact with the analytes. Miniaturization of the microextraction procedure, particularly the amount of sorbent reduces the amount consumed of the organic solvent and shorten the time required to attain the equilibrium state. This may explain the reported high efficiency and applicability of MOFs in dispersive micro SPE (D-µ-SPE). This method retains all the advantages of solid phase extraction while also being simpler, faster, cheaper, and, in some cases, more effective in comparison with D-SPE. Besides, D-µ-SPE requires smaller amounts of the sorbents which reduces the overall cost, and the amount of waste generated from the analytical process. In this review, we discuss the applications of MOFs in D-µ-SPE of various analytes including pharmaceuticals, pesticides, organic dyes from miscellaneous matrices including water samples, biological samples and food samples.

In this study, a boronic acid incorporated metal organic frameworks (inBA-MIL-100) were prepared via metal-ligand-fragment co-assembly strategy. The prepared frameworks can be served either as enrichment sorbent or SALDI-MS matrix for cis-diol containing molecules. Thus, a dual-modal analysis of cis-diols in traditional Chinese medicine has been established. Several significant advantages of the proposed strategy have been experimentally demonstrated, including high selectivity, high binding capacity (70 mg/g), good generality (5-250 μg/mL for HPLC based sample preparation, 10-500 ng/mL for SALDI-MS), high sensitivity (LOD: 180 ng/mL for HPLC based sample preparation, 5 ng/mL for SALDI-MS) and reliable quantification (RSD<3 % for HPLC based sample preparation, RSD<12 % for SALDI-MS) performance. Finally, the successful analysis of various cis-diols (active component and mycotoxin) in various Chinese traditional medicine was also achieved.

Biomimetic functionalized metal-organic frameworks (Fn-MOFs) represent a cutting-edge approach in the realm of cancer vaccines. These multifunctional agents, inspired by biological systems, offer unprecedented opportunities for the development of next-generation cancer vaccines. The vast surface area, tunable pore size, and diverse chemistry of MOFs provide a versatile scaffold for the encapsulation and protection of antigenic components, crucial for vaccine stability and delivery. This work delves into the innovative design and application of Fn-MOFs, highlighting their role as carriers for immune enhancement and their potential to revolutionize vaccine delivery. By mimicking natural processes, Fn-MOFs, with their ability to be functionalized with a myriad of chemical and biological entities, exhibit superior biocompatibility and stimuli-responsive behavior and facilitate targeted delivery to tumor sites. This review encapsulates the latest advancements in Fn-MOF technology, from their synthesis and surface modification to their integration into stimuli-responsive and combination therapies. It underscores the significance of biomimetic approaches in overcoming current challenges in cancer vaccine development, such as antigen stability and immune evasion. By leveraging the biomimetic nature of Fn-MOFs, this work paves the way for innovative strategies in cancer vaccines, aiming to induce potent and long-lasting immune responses against malignancies.

Metal-organic framework (MOF) modified with iron oxide, Fe3O4-MOF, is a perspective drug delivery agent, enabling magnetic control and production of active hydroxyl radicals, •OH, via the Fenton reaction. This paper studies cytotoxic and radical activities of Fe-containing nanoparticles (NPs): Fe3O4-MOF and its components - bare Fe3O4 and MOF (MIL-88B). Luminous marine bacteria Photobacteriumphosphoreum were used as a model cellular system to monitor bioeffects of the NPs. Neither the NPs of Fe3O4-MOF nor MOF showed cytotoxic effects in a wide range of concentrations (<10 mg/L); while Fe3O4 was toxic at >3·10-3 mg/L. The NPs of Fe3O4 did not affect the bacterial bioluminescence enzymatic system; their toxic effect was attributed to cellular membrane processes. The integral content of reactive oxygen species (ROS) was determined using a chemiluminescence luminol assay. Bacteria mitigated excess of ROS in water suspensions of Fe3O4-MOF and MOF, maintaining bioluminescence intensity closer to the control; this resulted in low toxicity of these NPs. We estimated the activity of •OH radicals in the NPs samples with physical and chemical methods - spin capture technology (using electron paramagnetic resonance spectroscopy) and methylene blue degradation. Physico-chemical interpretation of cellular responses is provided in terms of iron content, iron ions release and •OH radical production.

Fluorosis disease can be prevented by the defluoridated water. Hence, the present work focused on the fabrication of hybrid materials using graphene oxide (GO) and Ce-based metal organic frameworks namely cerium fumarate (Ce-Fu) which gives GO/Ce-Fu for defluoridation of water. Further, the powdered GO/Ce-Fu was dispersed with alginate (Alg) and chitosan (CS) biopolymeric matrixes to give GO/Ce-Fu/Alg-CS biopolymeric hybrid beads for defluoridation investigations. The developed GO/Ce-Fu and GO/Ce-Fu/Alg-CS beads have defluoridation capacities (DCs) of 4.410 and 4.753 mg/g within 30 min. The fabricated GO/Ce-Fu and GO/Ce-Fu/Alg-CS beads were analyzed by XRD, FTIR, TGA, BET, SEM and EDAX studies. The performance of fluoride adsorption influencing parameters such as dosage, contact time, solution pH, interfering anions and temperature studies were optimized with batch scale. Thermodynamic, adsorption isotherms and kinetic studies were carried out using hybrid materials to find the nature and order of fluoride adsorption. The fluoride adsorption mechanism of GO/Ce-Fu and GO/Ce-Fu/Alg-CS beads was investigated. The performance of recyclability of the hybrid materials was examined. In addition, the field studies of hybrid materials were also explored to identify their field suitability nature.

It is desirable but challenging to develop highly-efficient catalysts for the direct synthesis of dimethyl carbonate (DMC) from methanol and CO2. The vacancy-mediated incorporation of heteroatom into surface reconstruction is an efficient method of defect engineering for enhancing the catalytic properties. In this work, manganese-doped cerium oxide porous nanoribbons (Mn/CeO2-BTC) were prepared derived from a Ce-BTC by a sacrificial template approach. It is found that the catalytic activity of Mn/CeO2-BTC catalysts can be readily controlled by varying the amount of Mn dopants and the as-synthesized 0.1-Mn/CeO2-BTC exhibited an outstanding activity for the synthesis of DMC from CO2 and methanol, which reached a high DMC yield (6.53 mmolDMC/gcat.) without any dehydrating agents. Based on characterization results, the enhanced performance may be attributed to the defective structures caused by Mn doping and the porous nanoribbons of the CeO2 crystals, which provide more surface oxygen vacancies and acidic-basic sites, favoring adsorption and activation of CO2 and methanol.

ABSTRACTMetal-organic frameworks (MOFs) with photocatalytic activity have garnered significant attentions in environmental remediation. Herein, copper-doped zeolitic imidazolate framework-7 (Cu-doped ZIF-7) was synthesized rapidly and easily using a microwave-assisted technique. Various analytical and spectroscopic methods were employed to access the framework, morphology, light absorption, photo-electrochemical and photocatalytic performance of the synthesized materials. Compared to ZIF-7, Cu/ZIF-7 (molar ratio of Cu2+ to Zn2+ is 1:1) demonstrates superior visible light absorption ability, narrower band gap, enhanced charge separation capability, and reduced electron-hole recombination performance. Under visible light irradiation, Cu/ZIF-7 serves as a Fenton-like catalyst and demonstrates exceptional activity for contaminant degradation, while virgin ZIF-7 remains inactive. With the addition of 9.8 mmol H2O2 and exposure to visible light for 30 min, 10 mg of Cu/ZIF-7 can completely decompose RhB solution (10 mg/L, 50 mL). The synergistic effect of the Cu/ZIF-7/H2O2/visible light system is attributed to visible light photocatalysis and Fenton-like reactions. Cu/ZIF-7 demonstrates excellent catalytic performance stability, with only a slight decrease in degradation efficiency from an initial 97.0% to 95.4% over four cycles. Additionally, spin-trapping ESR measurements and active species trapping experiments revealed that h+ and ·OH occupied a significant position for Rhodamine B (RhB) degradation. Degradation intermediate products of Rhodamine B have been identified using UPLC-MS, and the degradation pathways have been proposed and discussed. This work offers a facile and efficient technique for developing MOF-based visible light photocatalysts for water purification.