Metal-organic Frameworks Surface Research Articles

A novel AgNFs/MOF/CFC substrate-based flexible SERS sensor for high-sensitive detection of dye molecules

Metal–organic framework (MOF) materials have been increasingly used owing to their high porosity, chemical stability, and semiconducting properties. With the help of MOF materials, MOF-based SERS substrates can exhibit high sensitivity. Herein, we proposed a flower-like Ag nanoparticles (AgNFs)/metal–organic framework (MOF)/ carbon fiber cloth (CFC) substrate-based surface-enhanced Raman scattering (SERS) sensor for the high-sensitive detection of dye molecules. MOF is used as a signal amplifier to accelerate the approach of dye molecules near AgNFs on the MOF surface and anchor AgNFs on the substrate surface. The detection occurred on the AgNFs/MOF/CFC SERS substrate, providing an enhancement factor (EF) of 5.53 × 107. Benefitting from the signal amplification function of AgNFs/MOF/CFC and the superiority of SERS, this sensor represented high sensitivity performance and a wide detection range. Importantly, the combination of Co elements with silver in the AgNFs/MOF/CFC composite substrate enhances the resistance of Ag to oxidation by atmospheric moisture resulting in excellent stability (the substrate maintained good SERS activity after 45 days of exposure to air) of the SERS substrate. The basic performance of the substrate was evaluated using rhodamine 6 G (R6G). (Detection limit reached 10−12 M) The detection limit of TC was 0.1 ppm. This method provides a potential and cost-effective strategy to develop advanced SERS sensing devices to effectively monitor pollutants in environmental waters.

Bifunctional iron-porphyrin metal-organic frameworks for organic photoelectrochemical transistor gating and biosensing

Iron-porphyrin metal-organic frameworks (MOFs) have emerged as a remarkable class of semiconductors with adjustable photoelectrical properties and peroxidase-mimicking activities, yet their full potential remains largely unexplored. The organic photoelectrochemical transistor (OPECT) has been proven to be a prominent platform for diverse applications. Herein, iron-porphyrin MOFs, as bifunctional photo-gating module and horseradish peroxidase-mimicking nanozyme, is explored for novel OPECT bioanalysis. Exemplified by alpha-fetoprotein (AFP)-dependent sandwich immunorecognition and therein glucose oxidase (GOx)-generated H2O2 to etch CdS quantum dots on the surface of iron-porphyrin MOFs, this OPECT bioanalysis achieved high-performance AFP detection with a low detection limit of 24 fg/mL. This work featured a bifunctional iron-porphyrin MOFs gated OPECT, which is envisioned to inspire more interest in developing the diverse MOFs-nanozymes toward novel optoelectronics and beyond.

A comprehensive study about functionalization and de-functionalization of MOF-808 as a defect-engineered Zr-MOFs for selective catalytic oxidation

In metal–organic frameworks (MOFs), confined space as a chemical nanoreactor is as essential as coordinatively unsaturated metal site catalysis. The properties of MOFs can be adjusted through the incorporation of functional groups and open metal sites in frameworks that can modify the catalytic performance. In this regard, a set of defect-engineered MOFs, Ex-MOF-808(NH2, NO2, H) and Mix-MOF-808(NH2, NO2, H), were synthesized by ultrasonic-assisted linker exchange approach (Ex-MOFs) and solvothermal mixing ligand method (Mix-MOFs), respectively. Further, the relationship between the preparation method, structural properties, and catalytic efficiency of the prepared materials in the selective oxidation of methyl phenyl sulfide (MPS) has been investigated. By analyzing zeta potential, it was found that in the exchange method, the amount of defect and functional groups on the surface of MOFs are more than in the mixing method, which also affects the catalytic activity. In our contribution, mix-MOF-808(NO2) carrying nitro groups at their organic linkers, which has a well-dispersion of nitro groups at the framework exhibits selective conversion of MPS to sulfone (91 %). Furthermore, the performance of stable heterogeneous catalysts was investigated for three cycles, which demonstrated their great potential for advanced catalytic oxidation.

Surface-active agent enhanced FRET effect Cu-doped NH2-MIL-88(Fe) for highly sensitive detection of 3-nitro-L-tyrosine

In this study, Cu-doped NH2-MIL-88(Fe) metal–organic frameworks (MOF) were synthesized via a one-step method. Characterization techniques such as XPS, XRD and FTIR confirmed the successful incorporation of Cu2+ into NH2-MIL-88(Fe), naming this MOF as NH2-MIL-88(Fe)@Cu2+. This MOF was employed to develop a highly sensitive fluorescence sensing platform for detecting 3-nitro-L-tyrosine(3-NT). The potential for fluorescence resonance energy transfer (FRET) was suggested by the spectral overlap between NH2-MIL-88(Fe)@Cu2+'s emission and 3-NT's UV absorption. To augment this effect, cationic surfactant hexadecyltrimethylammonium bromide (CTAB), which self-assembled into nanostructured microspheres above its critical micelle concentration, was utilized. The charged surface of these microspheres, formed by the self-assembly of CTAB, is bound to the MOF surface through electrostatic force and simultaneously attracts 3-NT. Adjusting the solution's pH strengthened the interaction between NH2-MIL-88(Fe)@Cu2+ and 3-NT, thereby enhancing their mutual FRET interaction. Experimental results indicated that CTAB's introduction markedly improved the FRET effects, potentially converting a weak FRET into a strong one and enhancing detection sensitivity and accuracy. Under optimal conditions, NH2-MIL-88(Fe)@Cu2+ detected 3-NT within 0–30 μM range, with a limit of detection (LOD, S/N = 3) of 41.1 nM. Finally, the applicability of the sensor is tested by calibrating measurements in fetal bovine serum samples, achieving good performance in terms of sensitivity, selectivity and reproducibility. This research provides a method for efficient and highly sensitive 3-NT detection and insights into the FRET effect between MOF and target molecules, likely advancing related fields and inspiring future fluorescence sensor designs.

Design of Mixed-Matrix MOF Membranes with Asymmetric Filler Density and Intrinsic MOF/Polymer Compatibility for Enhanced Molecular Sieving.

The separation of high-value-added chemicals from organic solvents is important for many industries. Membrane-based nanofiltration offers a more energy-efficient separation than the conventional thermal processes. Conceivably, mixed-matrix membranes (MMMs), encompassing metal-organic frameworks (MOFs) as fillers, are poised to promote selective separation via molecular sieving, synergistically combining polymers flexibility and fine-tuned porosity of MOFs. Nevertheless, conventional direct mixing of MOFs with polymer solutions results in underutilization of the MOF fillers owing to their uniform cross-sectional distribution. Therefore, in this work, a multizoning technique is proposed to produce MMMs with an asymmetric-filler density, in which the MOF fillers are distributed only on the surface of the membrane, and a seamless interface at the nanoscale. The design strategy demonstrates five times higher MOF surface coverage, which results in a solvent permeance five times higher than that of conventional MMMs while maintaining high selectivity. Practically, MOFs are paired with polymers of similar chemical nature to enhance their adhesion without the need for surface modification. The approach offers permanently accessible MOF porosity, which translates to effective molecular sieving, as exemplified by the polybenzimidazole and Zr-BI-fcu-MOF system. The findings pave the way for the development of composite materials with a seamless interface.

Successful synthesis of eco-friendly Metal-Organic framework ([Ni(BDC)]n) allows efficient extraction of multiresidues pesticides and dyes from fish samples

Contaminants such as pesticides and dyes pose substantial challenges to environmental and human health, especially when found in aquatic ecosystems and ingested through the food chain. This requires the development of methods that are efficient, safe and environmentally friendly. In this scenario, this study presents the synthesis and characterization of a metal–organic framework (MOF), specifically [Ni(BDC)]n, designed as a solid adsorbent for the determination of pesticides, including atrazine, bifenthrin, chlorpyrifos, endrin, heptachlor, flutriafol and permethrin, as well as dyes such as crystal violet (CV) and Congo red (CR) in fish samples. Using Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), Thermogravimetric Analysis (TGA), X-ray Diffraction (XRD), and Brunauer-Emmett-Teller (BET), we verified the success of the MOF synthesis. BET analysis indicated MOF surface area and total pore volume of 2700 m2/g and 0.0136 cm3 g−1, respectively. The adsorption study revealed high affinity of the MOF for the target analytes, with qmax = 208.33 mg g−1 for pesticides and qmax = 4.18 mg g−1 for dyes. The kinetic study demonstrated that the adsorption mechanism follows a pseudo-second order model for all analytes. Furthermore, employing [Ni(BDC)]n, we have developed an efficient extraction method using Matrix-Solid Phase Dispersion (MSPD) combined with Gas Chromatography-Mass Spectrometry (GC–MS) and UV/Vis spectrophotometry for determination of pesticide and dyes, respectively, with pre-concentration factor ranging from 10 to 100 times for the studied analytes. The methods showed satisfactory linearity for both contaminants (pesticides and dyes), with recovery efficiency ranging from 81-103 % and precision < 13 % (n = 3) for the analytes. Linear ranges covering 10.0–500.0 μg L−1 (R2 > 0.995) for pesticides and 100.0–1000.0 μg L−1 (R2 > 0.988) for dyes. The limits of detection (LOD) and quantification (LOQ) ranged from 0.5-1.6 μg L−1 and 1.7–5.6 μg L−1 for pesticides, respectively, while for dyes, LOD and LOQ ranged from 2.0-12.0 μg L−1 and 7.6–39.6 μg L−1, respectively. These results highlight the potential of [Ni(BDC)]n as a promising material for efficient and selective extraction in the sustainable determination of pesticides and dyes in fish samples, with satisfactory reuse.

Molecular Insights into Sequence-Specific Protein Hydrolysis by a Soluble Zirconium-Oxo Cluster Catalyst.

The development of catalysts for controlled fragmentation of proteins is a critical undertaking in modern proteomics and biotechnology. {Zr6O8}-based metal-organic frameworks (MOFs) have emerged as promising candidates for catalysis of peptide bond hydrolysis due to their high reactivity, stability, and recyclability. However, emerging evidence suggests that protein hydrolysis mainly occurs on the MOF surface, thereby questioning the need for their highly porous 3D nature. In this work, we show that the discrete and water-soluble [Zr6O4(OH)4(CH3CO2)8(H2O)2Cl3]+ (Zr6) metal-oxo cluster (MOC), which is based on the same hexamer motif found in various {Zr6O8}-based MOFs, shows excellent activity toward selective hydrolysis of equine skeletal muscle myoglobin. Compared to related Zr-MOFs, Zr6 exhibits superior reactivity, with near-complete protein hydrolysis after 24 h of incubation at 60 °C, producing seven selective fragments with a molecular weight in the range of 3-15 kDa, which are of ideal size for middle-down proteomics. The high solubility and molecular nature of Zr6 allow detailed solution-based mechanistic/interaction studies, which revealed that cluster-induced protein unfolding is a key step that facilitates hydrolysis. A combination of multinuclear nuclear magnetic resonance spectroscopy and pair distribution function analysis provided insight into the speciation of Zr6 and the ligand exchange processes occurring on the surface of the cluster, which results in the dimerization of two Zr6 clusters via bridging oxygen atoms. Considering the relevance of discrete Zr-oxo clusters as building blocks of MOFs, the molecular-level understanding reported in this work contributes to the further development of novel catalysts based on Zr-MOFs.

Phosphine-incorporated Metal-Organic Framework for Palladium Catalyzed Heck Coupling Reaction.

As an emerging material with the potential to combine the high efficiency of homogeneous catalysts and high stability and recyclability of heterogeneous catalysts, metal-organic frameworks (MOFs) have been viewed as one of the candidates to produce catalysts of the next generation. Herein, we heterogenized the highly active mono(phosphine)-Pd complex on surface of UiO-66 MOF, as a catalyst for Suzuki and Heck cross coupling reactions. The successful immobilization of these Pd-monophosphine complexes on MOF surface to form UiO-66-PPh2-Pd was characterized and confirmed via comprehensive set of analytical methods. UiO-66-PPh2-Pd showed high activity and selectivity for both Suzuki and Heck Cross Coupling Reactions. This strategy enabled facile access to mono(phosphine) complexes which are challenging to design and require multistep synthesis in homogeneous systems, paving the way for future MOF catalysts applications by similar systems.

Enhanced oxygen evolution reaction of 2-dimensional metal-organic frameworks with tunable nitrogen functionalities by ion beam sputtering

Modification of metal–organic frameworks (MOFs) is recently under the spotlight due to their versatile properties and potential applications in electrochemical catalysis. Here, we successfully demonstrate nitrogen doping into the MOF electrocatalyst without noble metals using a facile, tunable ion beam sputtering (IBS) process for the first time and evaluate the role of the incorporated heteroatom. Two-dimensional Ni-naphthalene-2,6-dicarboxylic acid MOF (NiNDC) with large surface area was subjected to nitrogen IBS (NIBS) and exhibited significantly improved performance for oxygen evolution reaction (OER) with a low overpotential of 222 mV at 10 mA cm−2; a Tafel slope of 88 mV dec-1; and over 120 h of stability at 100 mA cm−2. The relationship between the nitrogen functionalities and catalytic activity was elucidated by spectroscopic analysis and electrochemical measurements, i.e., (i) pyridinic N as an electron-withdrawing group that directly enhances the reaction kinetics, (ii) pyrrolic N to stabilize the catalyst and (iii) graphitic N to enhance the electrical conductivity. We found that the electrocatalytic performance was affected by the ratio of the three nitrogen species, which was controllable by the accelerating potential (AP) of NIBS. This study provides insights into the influence of the chemical state of MOF surfaces on catalytic reactions and presents a novel method for effective nitrogen doping.

In situ Synthesis of Single Layered Metal-Organic Frameworks via Inkjet Printing on a Cellulose Nanofiber Film.

The inkjet printing is a simple method to develop pattern-controlled 2D metal-organic frameworks (MOFs) due to its cost-effectiveness and ease of operation. Despite the sophisticated structures of MOF crystals, the MOF surfaces are easily contaminated by the adsorption of an ink solution, and the printing nozzle can be clogged by the aggregates of MOFs during printing. Unlike the mixture inks of MOFs and a carrier medium, the surface-specific patterning by in situ synthesis provides the film surface with the controlled patterns of an MOF single layer having different morphologies of MOFs without changing the ink cartridges. It enables facile printing due to the low viscosity of inks and escapes the risk of nozzle clogging because MOFs are synthesized at the printed patterns on the substrates. The ion-exchanged cellulose nanofiber (CNF) films form strong coordination with metal ions enhancing the stability of the MOFs on the film surface. It also demonstrates the controlled coverage of the MOFs by the printing pass number and the carboxylate content of CNF and the tunable adsorption of the guest molecules for different loading capacities of the printed patterns.

Detection of Ammonium Ion by An Electrochemical Sensor Based on Cu-BTC

There is a growing interest in utilizing metal-organic frameworks (MOFs) for the development of electrochemical sensors with superior performance. In this work, a study on the detection of ammonium ion (NH4 +) on metal-organic frameworks (MOFs) Cu-BTC surface has been conducted by using both experimental and computational methods. By using DFT calculation, the adsorption energy of ammonium ion (NH4 +) on the MOF surfaces was determined. The calculation result showed that NH4 + molecules can be adsorbed on the surface of Cu-BTC with an adsorption energy value of -1.51 eV. Additionally, we performed the synthesis of Cu-BTC and, using CV (Cyclic Voltammetry), we obtained a working area of around -0.113 V. Furthermore, chronoamperometry tests revealed that the addition of ammonium at concentrations of 0.05, 0.1, and 0.15 mM resulted in changes in the current. The sensor also showed good stability and an increase in peak current at each tested concentration. This confirms that the MOFs tested can be utilized as ammonium ion sensors.

The ortho-substituent effect regulating the separation of photogenerated carriers to efficiently photodegrade tetracycline on the surface of FeCo-based MOFs

It is feasible to improve the photodegradation efficiency of organic pollutants by metal-organic frameworks (MOF)-based semiconductors via ligand engineering. In this work, three (Fe/Co)-XBDC-based MOFs were synthesized by introducing different ortho-functional groups X (X = –H, –NO2, –NH2) next to the carboxyl group of the organic ligand (i.e., terephthalic acid). The analysis focused on the influence mechanism of the adjacent functional group effect of the ligand on the physicochemical properties of the material and the actual photodegradation activity of TC. Multiple pieces of evidences suggested that the differences in electron-induced and photocharge-transfer mechanisms of the above ortho functional groups affect the crystal morphology and photocatalytic activity of FeCo-MOF during pyrolysis. Interestingly, (Fe/Co)–NH2BDC exhibited the highest photocatalytic activity under neutral conditions. The results of density functional theory show that the introduction of a strong donor-NH2 group can enhance light absorption and act as an “electron pump” to supply electrons to the iron center, accelerating the separation and efficient transport of photogenerated carriers on the ligand-metal bridge. In conclusion, this study is a proposal for a strategy of structural regulation for the enhancement of the catalytic activity of (Fe/Co)-MOFs in the photodegradation of TC.

Conversion of PET Bottle Waste into a Terephthalic Acid-Based Metal-Organic Framework for Removing Plastic Nanoparticles from Water

Micro- and nanoparticles of plastic waste are considered emerging pollutants with significant environmental and health impacts at high concentrations or prolonged exposure time. Here we report the synthesis and characterization of a known metal-organic framework (MOF) using terephthalic acid (TPA) recovered from the hydrolysis of polyethylene terephthalate (PET) bottle waste. This approach adds value to the existing large amounts of bottle waste in the environment. Fully characterized zinc-TPA MOF (MOF-5) was used for the extraction and removal of engineered polyvinyl chloride (PVC) and polymethylmethacrylate (PMMA) nanoparticles from water with a high efficiency of 97% and 95%, respectively. Kinetic and isotherm models for the adsorption of polymer nanoparticles (PNPs) on the MOF surface were investigated to understand the mechanism. The Qmax for PVC and PMMA NPs were recorded as 56.65 mg/g and 33.32 mg/g, respectively. MOF-5 was characterized before and after adsorption of PNPs on the surface of MOF-5 using a range of techniques. After adsorption, the MOF-5 was successfully regenerated and reused for the adsorption and removal of PNPs, showing consistent results for five adsorption cycles with a removal rate of 83–85%. MOF-5 was characterized before and after adsorption of PNPs on the surface using a range of techniques. The MOF-5 with PNPs on the surface was successfully regenerated and reused for the adsorption and removal of polymer nanoparticles, showing consistent results for five extraction cycles. As a proof of concept, MOF-5 was also used to remove plastic particles from commercially available body scrub gel solutions. Such methods and materials are needed to mitigate the health hazards caused by emerging micro- and nanoplastic pollutants in the environment.

Sustainable Gold Nanoparticle (Au-NP) Growth within Interspaces of Porphyrinic Zirconium-Based Metal-Organic Frameworks: Green Synthesis of PCN-224/Au-NPs and Its Anticancer Effect on Colorectal Cancer Cells Assay.

In this work, a simple green synthesis method of the novel metal-organic framework (MOF) nanocomposite PCN-224/Au-NPs (Au-NPs = gold nanoparticles) is described. In this regard, initially, PCN-224 was synthesized. Afterward, in a single-step, one-pot procedure, under visible-light irradiation, Au-NPs were fabricated on PCN-224. The cytotoxicity effect of the synthesized PCN-224/Au-NPs nanocomposite was investigated in human colon cancer cells. Determination of the apoptosis induction was done by the Annexin- V/propidium iodide flow cytometry method. Besides, to ascertain the biocompatibility of the synthesized sample, the cytotoxicity of PCN-224/Au-NPs was evaluated on the human embryonic kidney (HEK)-293 cell line. The substantial anticancer activity with the biocompatibility of the structure, the green facile synthesis, and the MOF surface of the synthesized nanocomposite make it special for utilization in therapeutic applications.

Vapor-phase zeolitic imidazolate framework-8 growth on fibrous polymer substrates

The use of metal-organic frameworks (MOFs) in practical applications is often hindered by synthesis related challenges. Conventional solution-based approaches rely on hazardous solvents and often form powders that are difficult to integrate into practical devices. On the other hand, vapor-phase approaches generally result in MOF films on silicon substrates that make it difficult to characterize the MOF surface area, which is an important quality indicator. We address these challenges by introducing a solvent-free synthesis method to form MOF–fiber composites, which can be more easily integrated into devices. Additionally, these vapor-phase-formed MOF–fiber composites are compatible with Brunauer–Emmett–Teller surface area analysis to characterize MOF quality. Atomic layer deposition is used to form a ZnO film on polypropylene, polyester, and nylon fibrous substrates, which is subsequently converted to zeolitic imidazolate framework-8 (ZIF-8) using 2-methylimidazole vapor. We describe the effects of the ZnO film thickness and MOF conversion conditions on MOF crystallinity and surface area. We report a ZIF-8 surface area of ∼1300 m2/gMOF, which is comparable to reported surface areas of ∼1250–1600 m2/gMOF from conventional synthesis techniques, demonstrating good quality of the solvent-free MOF–fiber composites. We expect these results to extend vapor-phase MOF formation to new, practical substrates for advanced sensing and catalytic applications.

Antibacterial, antibiofilm, and antioxidant activities of two novel metal-organic frameworks (MOFs) based on 4,6-diamino-2-pyrimidinethiol with Zn and Co metal ions as coordination polymers.

In the present era, the increase in free radical species (FRs) and multidrug-resistant (MDR) bacteria represents a major worldwide concern for public health. Biofilm development and the overuse and misuse of antibiotics could lead to the adaptation of bacteria to antimicrobial agents. Consequently, finding novel multifunctional species with antibacterial, antioxidant, and antibiofilm properties has become crucial in the fight against challenging bacterial infections and chronic inflammatory conditions. Metal-organic frameworks (MOFs) with zinc and cobalt metal centers are widely utilized in biological and environmental remediation owing to their versatility. In this study, multifunctional Zn-MOFs and Co-MOFs were successfully synthesized with zinc and cobalt as metal centers and 4,6-diamino-2-pyrimidinethiol as an organic linker using a hydrothermal technique. Numerous characterization techniques were used to fully examine the MOF structure, functionality, chemical makeup, crystalline structure, surface appearance, thermal behavior, and magnetic characteristics; the techniques included XPS, PXRD, FTIR, FESEM, EDX, UV-visible, BET, BJH, TGA/DTG, DSC, and magnetic susceptibility measurement. The antioxidant, antibacterial, and antibiofilm activities of the MOFs were examined, and they demonstrated potent activity in each of these aspects. The proposed mechanisms of antibacterial activity suggest that bacterial cell death results from multiple toxic effects, including electrostatic interaction and lipid peroxidation, when MOFs are attached to bacteria, leading to the formation of reactive oxygen species (ROSs). Zn-MOFs exhibit high antibacterial and antibiofilm efficacy owing to their large surface-to-volume ratio and porous nature, while Co-MOFs exhibit high antioxidant capacity owing to their redox properties.

Empowering the Water Oxidation Activity of the Bimetallic Metal-Organic Framework by Annexing Gold Nanoparticles over the Catalytic Surface.

Electrocatalytic water splitting to an anodic oxygen evolution reaction (OER) and a cathodic hydrogen evolution reaction (HER) is believed to be the most important application for sustainable hydrogen generation. Being a four-electron, four-proton transfer process, the OER plays the main obstacle for the same. Therefore, designing an effective electrocatalyst to minimize the activation energy barrier for the OER is a research topic of prime importance. The metal-organic framework (MOF) with a highly porous network is considered an appropriate candidate for the OER in alkaline conditions. Apart from several MOFs, the bimetallic one has an advantageous electrocatalytic performance due to the synergistic electronic interaction between two metal ions. However, most bimetallic MOFs have an obstacle to electrocatalytic application due to their low conductive nature, and therefore, they possess a barrier for charge transfer kinetics at the interface. Surface functionalization via various nanoparticles (NPs) is believed to be the most effective strategy for nullifying the conductive issue. In this work, we have designed a CoNi-based bimetallic MOF that was surface-functionalized by Au NPs (Au@CoNi-Bpy-BTC) for the OER under alkaline conditions. Au@CoNi-Bpy-BTC required an overpotential of just 330 mV, which is 56 mV lower as compared to the pristine MOF. Impedance analysis confirms an improved conductivity and charge transfer at the interface, where Au@CoNi-Bpy-BTC possesses a lower Rct value than CoNi-Bpy-BTC materials. Moreover, the Au-decorated MOF shows an 8.5 times increase in the TOF value compared to the pristine MOF. Therefore, this noble strategy toward the surface functionalization of MOFs via noble metal NPs is believed to be the most effective strategy for developing effective electrocatalysts for electrocatalytic application in energy-related fields. Overall, this report displays an exceptional correlation between the decorated NPs over the MOF surface, which can regulate the OER activity, as confirmed by experimental analysis.

Natural tea extract coated porous MOF nano/microparticles for highly enhanced and selective adsorption of cationic dyes from aqueous medium

A simple, sustainable method was developed for boosting the dye adsorption capability of porous metal organic frameworks (MOFs) by coating them with natural tea extract. Nano/microparticles of zinc-terephthalic acid (ZnTPA) MOFs exhibited only 40% rhodamine B (Rh B) dye adsorption. The dye adsorption capability was strongly enhanced (up to 95%) after coating with natural tea extract and highly selective cationic dye adsorption. The coating of multifunctional biomolecules onto the ZnTPA matrix was expected to facilitate strong intermolecular interaction between MOF surface and organic dyes, which contributed to strongly enhanced dye adsorption. ZnTPA/Tea MOFs not only exhibited enhanced dye adsorption but also showed high retention capability. The broader scope of tea extract coating methodology for cationic dye adsorption was also demonstrated using other MOFs matrix. The exhausted ZnTPA MOF was easily regenerated by sonication followed by re-dipping into tea extract. Tea extract coated ZnTPA MOFs was also used as column packing materials for removing cationic dyes by filtration. Thus, the present work reported a facile strategy for efficient cationic organic dyes removal from the aqueous medium.

Metal-organic frameworks: Drug delivery applications and future prospects.

Metal-organic frameworks (MOFs) have gained incredible consideration in the biomedical field due to their flexible structural configuration, tunable pore size and tailorable surface modification. These inherent characteristics of MOFs portray numerous merits as potential drug carriers, depicting improved drug loading, site-specific drug delivery, biocompatibility, biodegradability, etc. The current review article sheds light on the synthesis and use of MOFs in drug delivery applications. In the beginning, a brief overview of the key components and efficient fabrication techniques for MOF synthesis, along with its characterization methods, have been presented. The MOFs-based formulations have been critically discussed. The application of the design of experiments (DoE) approach to optimize MOFs has been elucidated. The MOFs-based formulations, especially the application of stimuli-responsive MOFs for site-specific drug delivery, have been deciphered. Along with drug release kinetic models, several administration methods for MOFs have also been enunciated. Subsequently, MOFs as future potential drug carriers have been elaborated. Recently, MOFs have emerged as versatile drug delivery carriers possessing customization potential and meeting the needs of spatio-temporal drug delivery. Researchers have devised several environment-friendly approaches for MOF construction and surface modification. Owing to stimuli-responsive potential, MOFs have demonstrated their prominent therapeutic efficacy via several routes of administration. The numerous benefits of MOFs would certainly open up a new vista for its novel drug delivery applications.

Metal-organic framework (MOF)-derived flower-like Ni-MOF@NiV-layered double hydroxides as peroxidase mimetics for colorimetric detection of hydroquinone

BackgroundNanozymes are one of the ideal substitutes for natural enzymes because of their excellent chemical stability and simple preparation methods. However, due to the limited catalytic ability of most reported nanozymes, constructing nanomaterials with low cost and high activity is gradually becoming an exploration focus in the field of nanozymes. Heteroatom doping of metal-organic frameworks is one of potential approaches to design nanozymes with high catalytic performance. Due to their multiple valence states properties, V-doped metal-organic framework (MOF)-derived LDH is expected to be a good enzyme-like catalyst. To our knowledge, the V-doped MOF-derived LDH as nanozyme is not explored before. ResultsWe report the in-situ synthesis of NiV-layered double hydroxides (LDHs) on nickel-based MOF, i.e. Ni-MOF@NiV-LDHs. The MOF surface is covered by 2D nanosheets. This unique structural design increases the specific surface area of the material, enables more exposure of catalytic active sites to participate in reactions and accelerates the electron transfer rate. The Ni-MOF@NiV-LDHs have high peroxidase-like activity able to catalyze TMB oxidation by H2O2 via the generation of •OH and O2•−. Relative to Ni-MOF, the Ni-MOF@NiV-LDHs shows 47-fold peroxidase-like activity rise. It had good affinity to TMB and H2O2, with the Michaelis-Menten constants of 0.12 mM and 0.007 mM, respectively. The hydroquinone (HQ) consumed the reactive oxygen species generated in the TMB + H2O2+Ni-MOF@NiV-LDHs system to inhibit the TMB oxidation. On this basis, a sensitive and rapid assay for determining HQ was developed, with a linear range of 0.50–70 μM and a LOD of 0.37 μM. SignificanceThis work provided some clues for the further development of novel nanozymes with high catalytic performance via a strategy of heteroatom doping. And the constructed colorimetric analysis method was successfully utilized for the determination of HQ in actual waters, which has the potential for practical application in the analysis of environmental pollutants.