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High internal phase Pickering emulsions (HIPEs) constitute a significant research domain within colloid interface chemistry, addressing the demand for robust emulsion systems across various applications. An innovative nanoparticle, synthesized from a cyclodextrin metal-organic framework encapsulated with a composite of resveratrol and soy isolate protein (RCS), was employed to fortify a high internal phase emulsion. The emulsion's three-dimensional printing capabilities, alongside the encapsulated delivery efficacy for β-carotene, were thoroughly examined. Cyclodextrin metal-organic frameworks (CD-MOFs), facilitated by cellulose nanofibrils, were synthesized to yield particles at the nanoscale, maintaining a remarkable 97.67 % cellular viability at an elevated concentration of 1000 μg/ml. The RCS nanoparticles demonstrated thermal stability and antioxidant capacities surpassing those of CD-MOF. The integration of soybean isolate protein augmented both the hydrophobicity (from 21.95 ± 0.64° to 59.15 ± 0.78°) and the interfacial tension (from 14.36 ± 0.46 mN/m to 5.34 ± 0.81 mN/m) of the CD-MOF encapsulated with resveratrol, thereby enhancing the RCS nanoparticles' adsorption at the oil-water interface with greater stability. The durability of the RCS-stabilized high internal phase emulsions was contingent upon the RCS concentration. Emulsions stabilized with 5 wt%-RCS exhibited optimal physical and chemical robustness, demonstrating superior performance in emulsion 3D printing and β-carotene encapsulation delivery. This investigation furnishes a novel perspective on the amalgamation of food customization and precision nutrition., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

D-allulose, a low-calorie rare sugar catalyzed by D-allulose 3-epimerase (DAE), is highly sought after for its potential health benefits. However, poor reusability and stability of DAE limited its popularization in industrial applications. Although metal-organic frameworks (MOFs) offer a promising enzyme platform for enzyme immobilization, developing customized strategies for MOF immobilization of enzymes remains challenging. In this study, we introduce a designable strategy involving the construction of bimetal-organic frameworks (ZnCo-MOF) based on metal ions compatibility. The DAE@MOFs materials were prepared and characterized, and the immobilization of DAE and the enzymatic characteristics of the MOF-immobilized DAE were subsequently evaluated. Remarkably, DAE@ZnCo-MOF exhibited superior recyclability which could maintain 95 % relative activity after 8 consecutive cycles. The storage stability is significantly improved compared to the free form, with a relative activity of 116 % remaining after 30 days. Molecular docking was also employed to investigate the interaction between DAE and the components of MOFs synthesis. The results demonstrate that the DAE@ZnCo-MOF exhibited enhanced catalytic efficiency and increased stability. This study introduces a viable and adaptable MOF-based immobilization strategy for enzymes, which holds the potential to expand the implementation of enzyme biocatalysts in a multitude of disciplines., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Improving electron transfer rate of Co species and inhibiting aggregation of metal-organic frameworks (MOFs) particles are essential prerequisites for activating advanced oxidation process in wastewater treatment field. Here, we exploit Cu species with variable valence states to accelerate electron transfer of Co species and then to boost the unsatisfactory degradation efficiency for refractory pharmaceuticals via in-situ growth of copper and cobalt species on l-lysine functionalized carboxylated cellulose nanofibers. Utilizing the synergistic interplay of Co sites and deliberately exposed Cu 0 /Cu 1+ atoms, the subtly designed catalyst exhibited a surprising degradation efficiency (~100 %) toward tetracycline hydrochloride within 10 min (corresponding to a catalytic capacity of 267.71 mg/g) without adjusting temperature and pH. Meanwhile, the catalyst displays good recyclability, well tolerance for coexisting ions and excellent antibacterial performance derived from the intrinsic antibacterial property of Cu-MOF. This research provided a novel strategy to construct MOFs-cellulose materials toward degrading various stubborn antibiotic pollutants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The development of advanced nanofluidic membranes with better ion selectivity, efficient energy conversion and high output power density remains challenging. Herein, we prepared nanofluidic hybrid membranes based on TEMPO oxidized cellulose nanofibers (T-CNF) and manganese-based metal organic framework (MOF) using a simple in situ synthesis method. Incorporated T-CNF endows the MOF/T-CNF hybrid membrane with a high cation selectivity up to 0.93. Nanoporous MOF in three-dimensional interconnected nanochannels provides massive ion transport pathways. High transmembrane ion flux and low ion permeation energy barrier are correlated with a superior energy conversion efficiency (36 %) in MOF/T-CNF hybrid membrane. When operating under 50-fold salinity gradient by mixing simulated seawater and river water, the MOF/T-CNF hybrid membrane achieves a maximum power density value of 1.87 W m -2 . About 5-fold increase in output power density was achieved compared to pure T-CNF membrane. The integration of natural nanofibers with high charge density and nanoporous MOF materials is demonstrated an effective and novel strategy for the enhancement of output power density of nanofluidic membranes, showing the great potential of MOF/T-CNF hybrid membranes as efficient nanofluidic osmotic energy generators., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The solubility of cyclodextrin metal-organic frameworks (CD-MOFs) in aqueous media making it not suitable as sustained-release drug carrier. Here, curcumin-loaded CD-MOFs (CD-MOFs-Cur) was embedded in chitosan-graft-poly(lactic acid) (CS-LA) via a solid-in-oil-in-oil (s/o/o) emulsifying solvent evaporation method forming the sustained-release composite microspheres. At CS-LA concentration of 20 mg/mL, the composite microspheres showed good sphericity. The average particle size of CS-LA/CD-MOFs-Cur (2:1), CS-LA/CD-MOFs-Cur (4:1) and CS-LA/CD-MOFs-Cur (6:1) composite microspheres was about 9.3, 12.3 and 13.5 μm, respectively. The above composite microspheres exhibited various degradation rates and curcumin release rates. Treating in HCl solution (pH 1.2) for 120 min, the average particle size of above microspheres reduced 28.19 %, 24.34 % and 6.19 %, and curcumin released 86.23 %, 78.37 % and 52.57 %, respectively. Treating in PBS (pH 7.4) for 12 h, the average particle size of above microspheres reduced 30.56 %, 26.56 % and 10.66 %, and curcumin released 68.54 %, 54.32 % and 31.25 %, respectively. Moreover, the composite microspheres had a favorable cytocompatibility, with cell viability of higher than 90 %. These composite microspheres open novel opportunity for sustained drug release of CD-MOFs., Competing Interests: Declaration of competing interest We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influences our work. There is no professional or other personal interest of any nature or kind in any product., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The present study describes the trace analysis of 23 fluorinated aromatic carboxylic acids based on the dispersive solid-phase extraction (dSPE) technique using UiO-66-NH 2 MOF as efficient, recyclable sorbent, and GC-MS negative ionization mass spectrometry (NICI MS) as determination technique. All 23 fluorobenzoic acids (FBAs) were enriched, separated, and eluted in a shorter retention time; the derivatization was done by pentafluorobenzyl bromide (1% in acetone), in which the use of inorganic base K 2 CO 3 was improved by triethylamine to increase the lifespan of the GC column. The performance of UiO-66-NH 2 was evaluated by dSPE in Milli-Q water, artificial seawater, and tap water samples, and the impact of various parameters on the extraction efficiency was investigated by GC-NICI MS. The method was found to be precise, reproducible, and applicable to the seawater samples. In the linearity range, the regression value was found to be >0.98; LOD and LOQ were found to be in the range of 0.33-1.17 ng/mL and 1.23-3.33 ng/mL, respectively; and the value of the extraction efficiency was found to range between 98.45 and 104.39% for Milli-Q water samples, 69.13-105.48% for salt-rich seawater samples, and 92.56-103.50% for tap water samples with a maximum RSD value of 6.87% that confirms the applicability of the method to different water matrices., (© 2023. Springer-Verlag GmbH Germany, part of Springer Nature.)

Excessive phosphorus causes eutrophication problems. The adsorptive removal of phosphate is prevalent and practical in large-scale applications, such as column adsorption. A metal organic framework (MOF)-enhanced layered double hydroxide (LDH) adsorbent material was developed and studied for batch adsorption and then combined with polyacrylonitrile (PAN) to form MOF/LDH/PAN composite beads working as a functional material for columns. Scanning electron microscopy (SEM) images showed the well-dispersed adsorbent powder in porous composite beads. The Fowler-Guggenheim isotherm model described the phosphate adsorption behavior of the MOF/LDH powder with a maximum capacity of 74.96 mg P/g. Mass transfer in the composite beads was successfully described with the Fickian diffusion model. The composite-packed fixed bed treated 37.95 BVs of the influent (55.51 mg P/L phosphate solution) and achieved an uptake of 18.92 mg P/g, with a removal efficiency of 96.42%, before the breakthrough point in the column study. The phosphate-loaded composite bed was regenerated with 0.1 M NaOH to 70% efficiency within 30 BVs. The polymer composite can be considered a practical solution for adsorption-based water treatment applications in tank and column processes where powder adsorbents cannot be applied.

The capture of radioactive iodine is an inevitable requirement in nuclear industry for environmental protection. Metal-organic frameworks (MOFs) are a new generation of sorbents that have wide applications for iodine adsorption and recovery. Although the loading of MOFs on wood can avoid the drawbacks of the powder form of MOFs in implementation, the dense structure of wood results in the lower loading, even after delignification, which limits the adsorption capacity. Herein, a hierarchically porous UiO-66-NH 2 @WCA composite was fabricated by in-situ synthesis of UiO-66-NH 2 in wood-derived cellulose aerogel (WCA) that was further removed hemicellulose from delignified wood. UiO-66-NH 2 @WCA exhibited a high loading (36 wt%) of UiO-66-NH 2 crystals and a high adsorption capacity of 704 mg/g for iodine vapor and 248 mg/g for iodine aqueous solution. The adsorption behavior in iodine aqueous solution was well predicted by the Freundlich isotherm and pseudo-second-order kinetic model. The adsorption capacity of UiO-66-NH 2 @WCA was highest in solution when the pH was 6, while the ionic strength had little effect. The hydroxyl groups on the WCA matrix had a charge transfer effect with iodine, providing additional sites for iodine capture. Furthermore, a packed column system was applied to demonstrate the excellent recyclability and potential for practical application., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Due to the poor enzyme thermal stability, the efficient conversion of high crystallinity cellulose into glucose in aqueous phase over 50 °C is challenging. Herein, an enzyme-induced MOFs encapsulation of β-glucosidase (β-G) strategy was proposed for the first time. By using various methods, including SEM, XRD, XPS, NMR, FTIR and BET, the successful preparation of a porous channel-type flower-like enzyme complex (β-G@MOFs) was confirmed. The prepared enzyme complex (β-G@MOFs) materials showed improved thermal stability (from 50 °C to 100 °C in the aqueous phase) and excellent resistance to ionic liquids (the reaction temperature was as high as 110 °C) compared to the free enzyme (β-G). Not only the catalytic hydrolysis of cellulose by single enzyme (β-G) in ionic liquid was realized, but also the high-temperature continuous reaction performance of the enzyme was significantly improved. Benefiting from the significantly improved heat resistance, the β-G@MOFs exhibited 32.1 times and 34.2 times higher enzymatic hydrolysis rate compared to β-G for cellobiose and cellulose substrates, respectively. Besides, the catalytic activity of β-G@MOFs was retained up to 86 % after five cycles at 110 °C. This was remarkable because the fixation of the enzyme by the MOFs ensured that the folded structure of the enzyme would not expand at high temperatures, allowing the native conformation of the encapsulated protein well-maintained. Furthermore, we believe that this structural stability was caused by the confinement of flower-like porous MOFs., (© 2022 Wiley-VCH GmbH.)

Developing new and efficient technologies for environmental remediation is becoming significant due to the increase in global concerns such as climate change, severe epidemics, and energy crises. Air pollution, primarily due to increased levels of H 2 S, SO x , NH 3 , NO x , CO, volatile organic compounds (VOC), and particulate matter (PM) in the atmosphere, has a significant impact on public health, and exhaust gases harm the natural sulfur, nitrogen, and carbon cycles. Similarly, wastewater discharged to the environment with metal ions, herbicides, pharmaceuticals, personal care products, dyes, and aromatics/organic compounds is a risk for health since it may lead to an outbreak of waterborne pathogens and increase the exposure to endocrine-disrupting agents. Therefore, developing new and efficient air and water quality management systems is critical. Metal-organic frameworks (MOFs) are novel materials for which the main application areas include gas storage and separation, water harvesting from the atmosphere, chemical sensing, power storage, drug delivery, and food preservation. Due to their versatile structural motifs that can be modified during synthesis, MOFs also have a great promise for green applications including air and water pollution remediation. The motivation to use MOFs for environmental applications prompted the modification of their structures via the addition of metal and functional groups, as well as the creation of heterostructures by mixing MOFs with other nanomaterials, to effectively remove hazardous contaminants from wastewater and the atmosphere. In this review, we focus on the state-of-the-art environmental applications of MOFs, particularly for water treatment and air pollution, by highlighting the groundbreaking studies in which MOFs have been used as adsorbents, membranes, and photocatalysts for the abatement of air and water pollution. We finally address the opportunities and challenges for the environmental applications of MOFs., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Perfluorooctanoic acid (PFOA) has demonstrated potential toxicity to human health and has been detected in different environmental matrices due to its stable physical and chemical properties. To degrade PFOA under solar light irradiation, we fabricated a lignin/polyvinyl alcohol (PVA)/Co/Fe metal-organic frameworks (lignin/PVA/bi-MOFs) composite membrane via a typical electrospinning and in-situ solvothermal method for the catalytic degradation of PFOA. In the peroxymonosulfate (PMS)/membranes/solar light system, Electron paramagnetic resonance analysis (EPR) demonstrated the sulfate radicals (SO 4 - ) and hydroxyl radicals (OH) were generated by activating PMS with transition metal and solar light irradiation. Lignin/PVA/bi-MOFs showed outstanding performance in that 89.6% of PFOA was degraded within 3 h under optimal conditions. Compared with that in solar light, only 59.6% PFOA was degraded in the dark, and the rate constant of PFOA degradation decreased from 0.0150 min -1 to 0.0046 min -1 . Moreover, lignin/PVA/bi-MOFs were reused after simply rinsing with ultra-pure water and the degradation capacity of lignin/PVA/bi-MOFs remained at 77% after 4 cycles. The results might provide a new concept for the design of bimetallic MOFs for applications in organic pollutant removal., Competing Interests: Declaration of competing interest We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influence our work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the position presented in, or the review of, the manuscript entitled, “Efficient degradation of perfluorooctanoic acid by electrospun lignin-based bimetallic MOFs nanofibers composite membranes with peroxymonosulfate under solar light irradiation”., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Nanozyme-based chemodynamic therapy (CDT) has emerged as an effective cancer treatment because of its low side effects and without the requirement of exogenous energy. The therapeutic effect of CDT highlights the pivotal importance of active sites, H 2 O 2 supplement and the glutathione (GSH) depletion of a nanozyme. The construction of a single kind of catalyst with multiple functions for the enhanced CDT is still a big challenge. In this work, seven types of bimetallic nanoparticles are synthesized using a metal-organic framework (MOF) as a stable host instead of a Fenton or Fenton-like ions supplier. Among them, Cu-Pd@MIL-101 with an alloy loading of 9.5 wt% modified by PEG (9.5% CPMP) is found to exhibit the highest peroxidase (POD) like activity combined with a superoxide dismutase (SOD) mimic activity and the function of GSH depletion. The in vivo results suggest that the stable and ultrafine nanoparticles possess favorable CDT effect for tumor and good biosafety as well as biocompatibility. This work has provided a credible strategy to construct nanozymes with an excellent activity and may pave a new way for the design of enhanced tumor CDT treatment., (© 2021 Wiley-VCH GmbH.)

In this study, a sulfate radical-advanced oxidation process (SR-AOP) was proposed by utilizing a bimetallic Co/Fe metal-organic frameworks/cellulose nanofiber membrane (Co/Fe bi-MOFs/CNF) as a catalyst for TBBPA degradation. Sulfate radicals (SO 4 -) and hydroxyl radicals (OH·) were generated through the activation of peroxymonosulfate (PMS) by Co/Fe bi-MOFs/CNF. Co/Fe bi-MOFs/CNF was prepared by a facile solvothermal method and vacuum filtration. CNF acted as a natural substrates material to relieve the agglomeration of loaded MOFs. Additionally the composite membranes was easily separated from the reaction solution. The properties of the composite materials and the main factors that influenced TBBPA degradation were elucidated in detail, along with the TBBPA degradation intermediates, recyclability, and TBBPA degradation pathway. Almost 100 % of TBBPA was degraded within 30 min under optimal conditions, and the rate constant was determined to be 0.764 min -1 . Furthermore, the degradation rate of the composite membrane was 60 % after 4 cycles., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Biomass is increasingly used as a source of fuels and chemicals as a renewable alternative to fossil feedstocks. Cellulose, hemicellulose and lignin are converted into platform chemicals from which a large range of compounds are derived with different structures. These biomass transformation processes require the use of efficient and durable catalysts that should drive the selectivity of the process. This review focuses on the use of metal-organic frameworks (MOFs) and derivatives as catalysts for biomass conversion. After an introduction setting up the importance of the field and the MOF features that justify their prevalence as heterogeneous catalysts for liquid phase reactions, the two main parts of the review are the description of MOF synthesis and adaptation and coverage of the catalytic reactions involving biomass substrates organized according to the type of MOF. The last section summarizes the current state of the art and our outlook for the future development of the field.

In this work, biodegradable cellulose-based biosorbents (MOFs/OCBs) with dual function of dye removal and microbial inactivation were fabricated by in situ anchoring metal-organic frameworks (MOFs) on the TEMPO oxidized corncobs (OCBs). Results showed that delignification and oxidation can develop the OCBs with more cellulose content, carboxyl groups and specific surface area, thus facilitating the deposition of MOFs. The porous and carbohydrate-rich OCBs can serve as supports and stabilizers for MOFs, allowing for enhanced stability and recyclability of MOFs powders. The MOFs, namely HKUST-1 and ZIF-8, can endow the OCBs multiple functions of good adsorption capacity to methyl orange (from 8% of OCBs to 55% of HKUST-1/OCBs and 84% of ZIF-8/OCBs) and excellent antibacterial activity (from 0 of OCBs to 90.2% of HKUST-1/OCBs and 44.8% of ZIF-8/OCBs). Such a concept may offer a new pathway for preparing economical and efficient biosorbents for environmental remedy purposes., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

It is found that strong electronegative groups can selectively adsorb cellulose by hydrogen bonds. Grafting strong negatively charged groups onto catalysts to achieve the functionalization of the catalyst can give it the ability to selectively adsorb cellulose without affecting its catalysis, which is of great significance for the hydrolysis of cellulose. In this study, PTA@MIL-101-X (X = -Br, -NH 2 , -Cl, -NO 2 ) materials were synthesized to investigate the effect of grafting different electronegative groups on carriers to the directional hydrolysis of cellulose. The synthesized catalysts used phosphotungstic acid as the catalytic center while treated MIL-101 structure as the carrier. The grafting of different electronegative groups changed the crystal structure of the metal organic framework without affecting its stability during the reaction. The strong negative functional groups can selectively adsorb cellulose by forming hydrogen bonds with cellulose hydroxyl groups and weaken the hydrogen bonds within cellulose molecules. This hydrogen bond can reduce the side reaction of glucose, lighten the difficulty of cellulose hydrolysis, and improve the efficiency of cellulose conversion at the same time. The hydrolysis rate of cellulose increased with the electronegativity enhancement of the grafted functional groups, and the grafted -NO 2 catalyst PTA@MIL-101-NO 2 obtained the highest glucose yield of 16.2% in the cellulose-directed hydrolysis. The -NH 2 can form a chemical linkage with PTA through electrostatic interaction to get the highest immobilization stability and exhibit excellent stability in the recycling of catalysts. Graphical abstract.

A novel cellulose-based antibacterial material, namely silver nanoparticles@ metal-organic frameworks@ carboxymethylated fibers composites (Ag NPs@ HKUST-1@ CFs), was synthesized. The results showed that the metal-organic frameworks (HKUST-1) were uniformly anchored on the fiber's surfaces by virtue of complexation between copper ions in HKUST-1 and carboxyl groups on the carboxymethylated fibers (CFs). The silver nanoparticles (Ag NPs) were immobilized and well-dispersed into the pores and/or onto the surfaces of HKUST-1 via in situ microwave reduction, resulting in the formation of novel Ag NPs@ HKUST-1@ CFs composites. The antibacterial assays showed that the as-prepared composites exhibited a much higher antibacterial activity than Ag NPs@ CFs or HKUST-1@ CFs samples., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Purpose: Metal-organic frameworks (MOFs) have shown great potentials as drug delivery carriers, but the conventional methods for MOFs synthesis limited their use in biomedicine. The aim of this study was engineered tumor-targeted zinc nanoscale MOFs encapsulating chemotherapy drug., Methods: We employed post-synthetic modification to construct tumor cell-targeted nanoscale zinc MOFs (nanoMOFs) functionalized with folate as the targeting ligand that binds specifically to folate receptors on tumor cells. The cytoctoxicity of drug-loaded nanoMOFs was measured by MTT assay. The cell target was tested by cell compete assay., Results: The successful synthesis of folate-targeted nanoMOFs was confirmed by FTIR, 1 H-NMR and ESI-MS analysis. In the drug loading test, the zinc nanoMOFs functionalized with folate quickly adsorbed up to 24 wt % 5-fluorouracil (5-FU) without causing obvious changes in the supramolecular crystalline organization of the material. The in vitro drug release profile of this nanoMOFs in phosphate buffered saline exhibited a biphasic pattern. The drug sustained release is the effect mainly of diffusion of 5-FU molecules, while the degradation of the carrier itself plays a minor role in this process. The drug-loaded nanoMOFs showed a stronger cytotoxicity than free 5-FU against three cancer cell lines in vitro with a distinct selectivity between folate receptors positive and negative cells., Conclusions: These results encourage further in vivo studies of this nanoMOFs as candidates for tumor-targeted, sustained-release delivery of chemotherapeutic agents.