Medicinal bismuth: Bismuth-organic frameworks as pharmaceutically privileged compounds

Historically organometallic compounds have been used to cure certain diseases with limited applications. Although bismuth belongs to the category of heavy metals, many of its derivatives have found applications in modern drug discovery research, mainly because of its low toxicity and higher bioavailability. Being an eco-friendly mild Lewis acid, compounds having bismuth as a central atom are capable of binding several proteins in humans and other species. Bismuth complexes demonstrated antibacterial potential in syphilis, diarrhea, gastritis, and colitis. Apart from antibacterial activities, bismuth compounds exhibited anticancer, antileishmanial, and some extent of antifungal and other medicinal properties. This article discusses major synthetic methods and pharmacological potentials of bismuth complexes exhibiting in vitro activity to significant clinical performance in a systematic and timely manner.Copyright © 2022 Elsevier Ltd

Electrochemical sensing of dual biomolecules in live cells and whole blood samples: A flexible gold wire-modified copper-organic framework-based hybrid composite.

For clinical research, the precise measurement of hydrogen peroxide (H2O2) and glucose (Glu) is of paramount importance, due to their imbalanced concentrations in blood glucose, and reactive oxygen species (ROS) play a huge role in COVID-19 viral disease. It is critical to construct and develop a simple, rapid, flexible, long-term, and sensitive detection of H2O2 and glucose. In this paper, we have developed a unique morphological structure of MOF(Cu) on a single-walled carbon nanotube-modified gold wire (swnt@gw). Highly designed frameworks with nanotube composites enhance electron rate-transfer behavior while extending conductance and electroactive surface area.The composite sensing system delivers wide linear-range concentrations, low detection limit, and interference-free performance in co-existence with other biomolecules and metal ions. Endogenous quantitative tracking of H2O2 was performed in macrophage live-cells with the help of a strong stimulator lipopolysaccharide.The composite device was effectively utilized for the measurement of H2O2 and glucose in turbid samples of whole blood and milk samples without a pretreatment process. The practical results of biofluids showed favorable voltammetric results and acceptance recovery percentage levels between 97.49 and 98.88%. Finally, a flexible MOF-based hybrid system may provide a suitable detection platform in the construction of electro-biosensors and hold potential promise for clinical-sensory applications.

Covalent organic frameworks and metal-organic frameworks against pathogenic viruses and antibiotic-resistant bacteria: Diagnostic and therapeutic applications

Antimicrobial resistance and antiviral infections statistics show that the number of global cases has been exponentially increasing;thus there is an unmet need for developing alternatives rather than to continue conventional strategies such as antibiotic administration, since they failed to show promise especially during the past few decades. Among different porous materials, metal-organic frameworks (MOFs) are a class of porous coordination polymers broadly explored in nano- and biomedicine due to their desirable properties, including excellent surface area, structural variability, the richness of their crystal structures/architectures, allowing for engineering synergies between metal nodes, functional linkers, encapsulated substrates or nanoparticles, heterogeneous catalysis, ion exchange, controlled and targeted drug delivery, energetics, etc. MOF-based sensing platforms have shown suitable potentials for specific viral detection. Covalent organic frameworks (COFs) are porous crystalline organic materials with two- or three-dimensional structures, which can be employed for reducing the interaction between the spike protein of SARS-CoV-2 and angiotensin-converting enzyme 2 (ACE2) in addition to other inhibitory effects. These frameworks can be applied for encapsulating antibiotics or antiviral agents against pathogens;they have been also studied for photodynamic inactivation of pathogenic bacteria. Herein, the most recent advancements pertaining to the applications of these frameworks for specific detection and inhibition of pathogenic viruses and antibiotic-resistant bacteria are cogitated, focusing on important challenges and perspectives. This review also provides expert recommendations on the future development and utility of these frameworks to manage antimicrobial resistance and infectious diseases more efficiently. © 2023 Elsevier Ltd

Electrochemical Sensing of Favipiravir with an Innovative Water-Dispersible Molecularly Imprinted Polymer Based on the Bimetallic Metal-Organic Framework: Comparison of Morphological Effects.

Molecularly imprinted polymers (MIPs) are widely used as modifiers in electrochemical sensors due to their high sensitivity and promise of inexpensive mass manufacturing. Here, we propose and demonstrate a novel MIP-sensor that can measure the electrochemical activity of favipiravir (FAV) as an antiviral drug, thereby enabling quantification of the concentration of FAV in biological and river water samples and in real-time. MOF nanoparticles' application with various shapes to determine FAV at nanomolar concentrations was described. Two different MOF nanoparticle shapes (dodecahedron and sheets) were systematically compared to evaluate the electrochemical performance of FAV. After carefully examining two different morphologies of MIP-Co-Ni@MOF, the nanosheet form showed a higher performance and efficiency than the nanododecahedron. When MIP-Co/Ni@MOF-based and NIP-Co/Ni@MOF electrodes (nanosheets) were used instead, the minimum target concentrations detected were 7.5 × 10-11 (MIP-Co-Ni@MOF) and 8.17 × 10-9 M (NIP-Co-Ni@MOF), respectively. This is a significant improvement (>102), which is assigned to the large active surface area and high fraction of surface atoms, increasing the amount of greater analyte adsorption during binding. Therefore, water-dispersible MIP-Co-Ni@MOF nanosheets were successfully applied for trace-level determination of FAV in biological and water samples. Our findings seem to provide useful guidance in the molecularly imprinted polymer design of MOF-based materials to help establish quantitative rules in designing MOF-based sensors for point of care (POC) systems.

Synthesis and performance evaluation of copper and magnesium-based metal organic framework supported ionic liquid membrane for CO2/N2 separation

The CO2 emission is enhancing drastically because of the continuous emission from industries and transport sector. Although the CO2 emission had decreased in the first half of 2020 by 8.8% due to COVID-19 restrictions however, it is again on the rise and it might exceed the estimated level in 2030. The current methods used for CO2 separation have serious operational and environmental constraints. To overcome these problems we have devised a supported ionic liquid membrane (SILM) incorporated with the blend of bimetallic metal-organic framework (MOF) of copper and magnesium ions (CuxMgx) and Trihexyltetradecylphosphonium chloride [P66614] [Cl] ionic liquid (IL). CuxMgx MOF were synthesized and characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), and energy dispersive X-ray analysis (EDX). CuxMgx MOF with [P66614] [Cl] IL were immobilized on a flat sheet of polytetrafluoroethylene (PTFE) membrane. Single gas permeation tests of membranes loaded with 0.2/0.8 wt/wt% MOF/IL solution showed the highest CO2 permeability of 2937 Barrer and CO2/N2 selectivity of 33.26. The performance of SILM was also investigated with different water loadings of (30 wt % and 50 wt %) in addition to MOF/IL solution and at different feed pressure varying from 0.5 to 2 bars. Membranes showed enhancement in CO2 permeability to 3738 and 4628 Barrer whereas CO2/N2 selectivity decreased to 23.53 and 21.8 with membranes loaded with 30 and 50 wt % water, respectively, at a feed pressure of 2 bar. The gas permeation results show that the incorporation of CuxMgx MOF with IL in polymeric membrane enhances the CO2/N2 separation under humid conditions but slightly decreases CO2/N2 selectivity with an increase in feed pressure. The SILM synthesized in this research is highly viable for industrial flue gases because of the incorporation of phosphonium-based ILs that have high thermal stability. © 2022

Coronavirus-like Core-Shell-Structured Co@C for Hydrogen Evolution via Hydrolysis of Sodium Borohydride.

Constructing a reliable and robust cobalt-based catalyst for hydrogen evolution via hydrolysis of sodium borohydride is appealing but challenging due to the deactivation caused by the metal leaching and re-oxidization of metallic cobalt. A unique core-shell-structured coronavirus-like Co@C microsphere was prepared via pyrolysis of Co-MOF. This special Co@C had a microporous carbon coating to retain the reduced state of cobalt and resist the metal leaching. Furthermore, several nano-bumps grown discretely on the surface afforded enriched active centers. Applied in the pyrolysis of NaBH4, the Co@C-650, carbonized at 650 °C, exhibited the best activity and reliable recyclability. This comparable performance is ascribed to the increased metallic active sites and robust stability.

Surfactant-Impregnated MOF-Coated Fabric for Antimicrobial Applications.

Since the onset of the SARS-CoV-2 pandemic, the world has witnessed over 617 million confirmed cases and more than 6.54 million confirmed deaths, but the actual totals are likely much higher. The virus has mutated at a significantly faster rate than initially projected, and positive cases continue to surge with the emergence of ever more transmissible variants. According to the CDC, and at the time of this manuscript submission, more than 77% of all current US cases are a result of the B.5 (omicron). The continued emergence of highly transmissible variants makes clear the need for more effective methods of mitigating disease spread. Herein, we have developed an antimicrobial fabric capable of destroying a myriad of microbes including betacoronaviruses. We have demonstrated the capability of this highly porous and nontoxic metal organic framework (MOF), γ-CD-MOF-1, to serve as a host for varied-length benzalkonium chlorides (BACs; active ingredient in Lysol). Molecular docking simulations predicted a binding affinity of up to -4.12 kcal·mol-1, which is comparable to that of other reported guest molecules for this MOF. Similar Raman spectra and powder X-ray diffraction patterns between the unloaded and loaded MOFs, accompanied by a decrease in the Brunauer-Emmett-Teller surface area from 616.20 and 155.55 m2 g-1 respectively, corroborate the suggested potential for pore occupation with BAC. The MOF was grown on polypropylene fabric, exposed to a BAC-loading bath, washed to remove excess BAC from the external surface, and evaluated for its microbicidal activity against various bacterial and viral classes. Significant antimicrobial character was observed against Pseudomonas aeruginosa, Staphylococcus aureus, Escherichia coli, bacteriophage, and betacoronavirus. This study shows that a common mask material (polypropylene) can be coated with BAC-loaded γ-CD-MOF-1 while maintaining the guest molecule's antimicrobial effects.

Materials for a changing planet

About 700 scientists from 45 countries gathered in Dresden for the first time since the start of the COVID-19 pandemic to share their latest findings on metal-organic frameworks and open frameworks compounds.

Functionalized biological metal-organic framework with nanosized coronal structure and hierarchical wrapping pattern for enhanced targeting therapy.

Inefficient tumor-targeted delivery and uncontrolled drug release are the major obstacles in cancer chemotherapy. Herein, inspired by the targeting advantage of coronavirus from its size and coronal structure, a coronal biological metal-organic framework nanovehicle (named as corona-BioMOF) is constructed for improving its precise cancer targeting ability. The designed corona-BioMOF is constructed as the carriers-encapsulated carrier model by inner coated with abundant protein-nanocaged doxorubicin particles and external decorated with high-affinity apoferritin proteins to form the spiky surface for constructing the specific coronal structure. The corona-BioMOF shows a higher affinity and an enhanced targeting ability towards receptor-positive cancer cells compared to that of MOF-drug composites without spiky surface. It also exhibits the hierarchical wrapping pattern-endowed controlled lysosome-specific drug release and remarkable tumor lethality in vivo. Moreover, water-induced surface defect-based protein handle mechanism is first proposed to shape the coronal-BioMOF. This work will provide a better inspiration for nanovehicle construction and be broadly useful for clinical precision nanomedicine.

Synthesis and performance evaluation of copper and magnesium-based metal organic framework supported ionic liquid membrane for CO2/N2 separation

The CO2 emission is enhancing drastically because of the continuous emission from industries and transport sector. Although the CO2 emission had decreased in the first half of 2020 by 8.8% due to COVID-19 restrictions however, it is again on the rise and it might exceed the estimated level in 2030. The current methods used for CO2 separation have serious operational and environmental constraints. To overcome these problems we have devised a supported ionic liquid membrane (SILM) incorporated with the blend of bimetallic metal-organic framework (MOF) of copper and magnesium ions (CuxMgx) and Trihexyltetradecylphosphonium chloride [P66614] [Cl] ionic liquid (IL). CuxMgx MOF were synthesized and characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), and energy dispersive X-ray analysis (EDX). CuxMgx MOF with [P66614] [Cl] IL were immobilized on a flat sheet of polytetrafluoroethylene (PTFE) membrane. Single gas permeation tests of membranes loaded with 0.2/0.8 wt/wt% MOF/IL solution showed the highest CO2 permeability of 2937 Barrer and CO2/N2 selectivity of 33.26. The performance of SILM was also investigated with different water loadings of (30 wt % and 50 wt %) in addition to MOF/IL solution and at different feed pressure varying from 0.5 to 2 bars. Membranes showed enhancement in CO2 permeability to 3738 and 4628 Barrer whereas CO2/N2 selectivity decreased to 23.53 and 21.8 with membranes loaded with 30 and 50 wt % water, respectively, at a feed pressure of 2 bar. The gas permeation results show that the incorporation of CuxMgx MOF with IL in polymeric membrane enhances the CO2/N2 separation under humid conditions but slightly decreases CO2/N2 selectivity with an increase in feed pressure. The supported ionic liquids membrane synthesized in this research is highly viable for industrial flue gases because of the incorporation of phosphorous-based ILs that have high thermal stability.

Functional metal-organic framework as high-performance adsorbent for selective enrichment of pharmaceutical contaminants in aqueous samples

Facile and sensitive analysis methods for pharmaceutical contaminants in aqueous environment are of vital importance for water safety, especially when large amounts of anti-viral drugs are being used, discharged and accumulated. In this work, we used functional metal-organic framework (MOF) as high-performance adsorbent for selective enrichment of such pharmaceutical contaminants in aqueous samples. The MOF was synthesized via a new synthesis method previously developed by our group and immobilized on paper membrane to be used in solid-phase extraction (SPE) device. Different metal ions were anchored by MOF to screen out the adsorbent with the best affinity. The targets were a potential anti-COVID-19 drug favipiravir, and its structural and functional analogues (ingredients or intermediates, other anti-viral drugs). To deeply understand the adsorption mechanisms, quantum calculation and computational fluid dynamics (CFD) simulation were both applied. The experimental and in-silico results together demonstrated that the as-prepared MOF adsorbent possessed high affinity and fast dynamics. The established SPE-based liquid chromatography (LC) method worked well in the range of 10-1000 ng/mL, with only 3 mg of adsorbent per device and 5 mL sample needed, and no mass spectrometer (MS) included, which was very efficient compared to commercial adsorbents. The results met the current detection needs in the application scenario, and inspirable for later design of well-behaved adsorbents.

Ultrasensitive and highly selective "turn-on" fluorescent sensor for the detection and measurement of melatonin in juice samples.

Melatonin (MLT), a hormone related to the regulation of brain functions, is directly related to sleep quality and is considered to be a possible adjuvant therapy for patients needing hospitalization for coronavirus disease 2019 pneumonia, and accurate measurement of MLT is crucial. Herein, a new, highly sensitive, and easy operation fluorescent probe was provided based on Zr metal-organic framework encapsulation into the molecularly imprinted polymer (MOF@MIP). By combining unique properties of MIP and fluorescent MOF, selectivity and operation of the applied method were significantly improved. Different characterization methods, such as XRD, FT-IR, and FE-SEM, were used to confirm the synthesis reliability. MOF@MIP was successfully used for the precise identification and ultrasensitive detection for trace amounts of MLT. The detection mechanism for the analytical system is based on the ''turn-on'' fluorescence (FL) signal in 404 nm. The findings proved that it is possible to detect trace amounts of MLT in real samples including grape, cherry, and sour cherry juice. The linear range and the limit of detection (LOD) for trace amounts of MLT were obtained as 1-100 ng/mL and 0.18 ng/mL, respectively.

Polymer Waste Surgical Masks Decorated by Superhydrophobic Metal-Organic Frameworks Towards Oil Spills Clean-Up

The pandemic of COVID-19 led to drastic increase in the production of polymer medical disposals, where surgical masks and hospital sheets, made from polypropylene (PP), bring large carbon footprints after burning as a dominant recycling scenario. Here, we offer an alternative strategy of functional recycling for medical disposals to prolong the life cycle of waste PP to oil spill sorbent. Simple deposition of the superhydrophobic fluorine-free metal-azolate framework (MAF-6) leads to the preparation of advanced materials PP-MAF6 for oil spill clean-up. Optimized procedures allow obtaining superhydrophobic oleophilic fabric with mechanical robustness and UV resistance. The prepared PP-MAF6 shows high adsorption capacity towards a wide range of oils in 4-10pH range, including straight-run diesel fuel (>25000mg/g) with the >99.9% oil removal efficiency. To complement adsorption performance, we scaled up the preparation procedure of PP-MAF6 to 65 cm2. Finally, enlarged samples were capable to fully clean up the simulated sample containing solid contaminants (total organic carbon content <0.0018g/L;Zn, Fe concentration < 0.3mg/L). The PP-MAF6 shows great potential in accident elimination of oil spills containing solid components in the contaminated water in a fast manner. The strategy of functional polymer recycling is promising for treating practical oil spills.

Preparation of Ag@ZIF-8@PP Melt-Blown Nonwoven Fabrics: Air Filter Efficacy and Antibacterial Effect.

Serving as matrices, polypropylene (PP) melt-blown nonwoven fabrics with 4% electrostatic electret masterbatch were incorporated with a 6%, 10%, 14%, or 18% phosphorus-nitrogen flame retardant. The test results indicate that the incorporation of the 6% flame retardant prevented PP melt-blown nonwoven fabrics from generating a molten drop, which, in turn, hampers the secondary flame source while increasing the fiber diameter ratio. With a combination of 4% electrostatic electret masterbatch and the 6% flame retardant, PP melt-blown nonwoven fabrics were grafted with ZIF-8 and Ag@ZIF-8. The antibacterial effect of ZIF-8 and Ag@ZIF-8 was 40% and 85%, respectively. Moreover, four reinforcing measures were used to provide Ag@ZIF-8 PP melt-blown nonwoven fabrics with synergistic effects, involving lamination, electrostatic electret, and Ag@ZIF-8 grafting, as well as a larger diameter because of the addition of phosphorus-nitrogen flame retardants. As specified in the GB2626-2019 and JIS T8151-2018 respiratory resistance test standards, with a constant 60 Pa, Ag@ZIF-8 PP melt-blown nonwoven membranes were tested for a filter effect against PM 0.3. When the number of lamination layers was five, the filter effect was 88 ± 2.2%, and the respiratory resistance was 51 ± 3.6 Pa.

Electrochemical investigations for COVID-19 detection-A comparison with other viral detection methods.

Virus-induced infection such as SARS-CoV-2 is a serious threat to human health and the economic setback of the world. Continued advances in the development of technologies are required before the viruses undergo mutation. The low concentration of viruses in environmental samples makes the detection extremely challenging; simple, accurate and rapid detection methods are in urgent need. Of all the analytical techniques, electrochemical methods have the established capabilities to address the issues. Particularly, the integration of nanotechnology would allow miniature devices to be made available at the point-of-care. This review outlines the capabilities of electrochemical methods in conjunction with nanotechnology for the detection of SARS-CoV-2. Future directions and challenges of the electrochemical biosensors for pathogen detection are covered including wearable and conformal biosensors, detection of plant pathogens, multiplexed detection, and reusable biosensors for on-site monitoring, thereby providing low-cost and disposable biosensors.