An optimised synthesis of the metal-organic framework (MOF) UiO-66(Ce) is reported using a modulator-free route, yielding ~5 g of material with high crystallinity and 22% ligand defect. Two methods developed for loading gold nanoparticles onto the MOF. The first uses a double-solvent method to introduce HAuCl4 onto UiO-66(Ce), followed by reduction under 5% H2 in N2, while the second is a novel one-pot method where HAuCl4 is added to the synthesis mixture, forming Au nanoparticles within the pores of the UiO-66(Ce) during crystallisation. Analysis using powder X-ray diffraction (PXRD), nitrogen adsorption isotherms, transmission electron microscopy and small-angle X-ray scattering (SAXS) reveals that the two-step double-solvent method yields gold crystallites on the external surface of the MOF particles that are visible by PXRD. In contrast, the one-pot method forms smaller gold crystallites, with a distribution of sizes centred on ~4 nm diameter as seen by SAXS, with evidence from PXRD for the smallest particles being present within the MOF structure. The Au-loaded UiO-66(Ce) materials are evaluated for the catalytic oxidation of vanillyl alcohol to vanillin at 60 °C. Our findings indicate that incorporating Au nanoparticles via the one-pot synthesis method, enhances redox activity, achieving 43% conversion and 90% selectivity towards vanillin.

Layered silicates, including clay minerals, can be used as liquid-phase adsorbents in many important applications. However, because their two-dimensional interlayer space is narrow and not entirely opened due to the presence of interlayer species, guest species are forced to penetrate while expanding the interlayer space, which limits their adsorption performances compared with microporous materials such as MOFs and zeolites. Herein, as reported for the adsorption of gaseous species on flexible MOFs, we report a layered silicate that exhibits gate-opening adsorption in liquid phases. This layered silicate, synthesized via dilute acid treatment of the parent sodium-type, exhibits an abrupt increase in the basal spacing (layer thickness + interlayer space) to reach a plateau even at an earlier stage of benzoic acid adsorption from acetonitrile, whereas a typical layered silicate, magadiite, exhibits a gradual increase in the basal spacing as adsorption progress under identical conditions. The layered silicate shows an excellent adsorption capacity and rate for benzoic acid uptake from acetonitrile, which is considerably higher than that of magadiite. With comprehensive adsorption tests using different adsorbates and solvents, we propose that the layered silicate has zeolite-like but distorted, flexible open microchannels within each layer, and the intralayer microchannels can effectively and rapidly accommodate the solvent (acetonitrile) molecules, which are capable of expanding the framework to initiate the adsorption of aromatic compounds. The density function theory calculation revealed the adsorption mechanism, where the layered silicate accommodates acetonitrile in the intralayer microchannel followed by the interlayer space, and the former selectively plays a role as the adsorption site of aromatic compounds via exchange with acetonitrile.

Cyclin-dependent kinase 9 (CDK9), a catalytic subunit of the positive transcription elongation factor b (P-TEFb) complex, is a global transcriptional elongation factor associated with cell proliferation. CDK9 activity is regulated by certain histone acetyltransferases, such as p300, GCN5 and P/CAF. However, the impact of males absent on the first (MOF) (also known as KAT8 or MYST1) on CDK9 activity has not been reported. Therefore, the present study aimed to elucidate the regulatory role of MOF on CDK9. We present evidence from systematic biochemical assays and molecular biology approaches arguing that MOF interacts with and acetylates CDK9 at the lysine 35 (i.e. K35) site, and that this acetyl-group can be removed by histone deacetylase HDAC1. Notably, MOF-mediated acetylation of CDK9 at K35 promotes the formation of the P-TEFb complex through stabilizing CDK9 protein and enhancing its association with cyclin T1, which further increases RNA polymerase II serine 2 residues levels and global transcription. Our study reveals for the first time that MOF promotes global transcription by acetylating CDK9, providing a new strategy for exploring the comprehensive mechanism of the MOF-CDK9 axis in cellular processes.

Metal-organic frameworks (MOFs) are promising materials for sample pretreatment. The performance improvement of powdered MOFs is hindered by their aggregation and difficult recovery. To overcome these issues, a biodegradable lightweight spherical aerogel was used as a support for the in situ growth of copper-based MOFs (MOF-199). Furthermore, Fe3O4 nanoparticles were incorporated into the aerogel to achieve magnetic properties. Thus, hybrid aerogel spheres containing MOF-199 supported on magnetic oxidized cellulose nanofiber/carboxymethyl chitosan (MOF-199@mag-CNF/CMC) were fabricated. The effects of Fe3O4 loading amount and organic-ligand concentration on the properties (spherical geometry and mechanical strength) of the hybrid aerogel spheres were studied. Their potential application in the extraction of benzodiazepines (BZPs) from urine samples prior to liquid chromatography-mass spectrometry was evaluated. The highly dispersed MOF-199 crystals on the spherical aerogel effectively overcame the inherent structural shrinkage of the bare aerogel spheres; thus, the MOF-199@mag-CNF/CMC aerogel spheres were robust and could withstand repeated use for at least eight consecutive extraction cycles. Further, MOF-199@mag-CNF/CMC exhibited improved BZP extraction efficiency, which was 2.5-11.6 times higher than that of bare Cu2+@mag-CNF/CMC aerogel spheres, primarily due to additional π-π interaction and H-bonding as well as improved specific surface area. Parameters influencing the extraction and desorption processes were also comprehensively investigated. Under optimal conditions, this method provided a wide linear range of 0.1-10 µg/L (R2 > 0.995) and good precision (2.8-6.7% for intra-day; 1.9-7.8 % for inter-day). The limits of detection and quantification ranged from 0.02 to 0.11 µg/L and from 0.06 to 0.33 µg/L, respectively. The recoveries for the urine samples spiked with three concentrations of BZPs ranged from 73.9 % to 114.1 %. The proposed method is simple, sensitive and eco-friendly and can be used for the determination of BZPs from urine for clinical and forensic examinations.

Encapsulating the enzyme in metal-organic frameworks (MOFs) is a convenient method to prepare MOF-enzyme biocomposite. In this study, Candida antarctica lipase B (CAL-B) was chosen to immobilize in Cu-BTC MOF under ultrasound irradiation. CAL-B was immobilized in Cu-BTC under ultrasound at 21 kHz and 11.4 W/cm2 and incubation. 98% of CAL-B was immobilized in Cu-BTC with 99 U/mg activity (threefold more active than the free CAL-B). The prepared biocomposite was characterized using FT-IR, XRD, TGA, SEM, EDX, and BET. The thermal and solvent stability of CAL-B@Cu-BTC was investigated. It was found that at a temperature of 55 ℃, CAL-B@Cu-BTC maintains its activity even after 2 h of incubation. Furthermore, in the presence of 20% and 50% concentrations of MeCN, THF, and DMF, CAL-B@Cu-BTC was found to have an activity of over 80%. A prepared biocatalyst was used to synthesize 1,3,4,5-tetrasubstituted pyrazole derivatives (50-75%) in a one-pot vessel, by adding phenyl hydrazine hydrochlorides, benzaldehydes, and dimethyl acetylenedicarboxylate.

Mo2CTx MXene materials, known for their high conductivity and abundant surface functional groups, are widely utilized as electrode materials in supercapacitors. However, their tendency to stack during electrochemical energy storage hinders their performance. The in situ growth of nanorod-shaped Ni,Co bimetallic metal-organic frameworks (Ni,Co-MOF) on Mo2CTx MXene effectively mitigates this stacking. With their porous structure and high specific surface area, MOFs excel in energy storage, and bimetallic MOFs outperform monometallic ones. The synergy between Mo2CTx MXene and Ni,Co-MOF yields an outstanding performance. In a three-electrode system with 1 M KOH, the Mo2CTx/Ni,Co-MOF composite shows a specific capacitance of 58 mAh g-1 (56.26 mAh cm-3) at 1 A g-1. When used in a Mo2CTx/Ni,Co-MOF//AC asymmetric supercapacitor, it achieves an energy density of 22.7 Wh kg-1(0.022 Wh cm-3) at a power density of 293 W kg-1 (0.284 W cm-3). Future work will focus on enhancing synthesis methods, exploring different bimetallic combinations, and optimizing electrode designs for gas sensors, batteries, fuel cells, biological sensors, and so on, with outstanding performance and sustainability.

In this study, we developed a composite material comprising UIO-66-NH2 encapsulated tannic acid (TA) loaded on Ti3C2Tx to improve the corrosion resistance of water borne epoxy (WEP) coatings. The successful synthesis of the material was determined by FT-IR, XRD, XPS, EDS, TGA, SEM and TEM characterization. Furthermore, ultraviolet (UV)tests were conducted to evaluate the release rate of TA at varying pH levels, revealing a release rate of approximately 95 % at pH 2. Electrochemical impedance spectroscopy (EIS) results over 60 d indicated that the Rc value of TU-T/WEP remained unchanged at 3.934 × 108, demonstrating a two-order magnitude increase compared to those of pure epoxy coatings, attributed to the synergistic active and passive protection of TU-T materials. The self-healing ability of the TU-T/WEP coating was validated through manual scratch experiments. Additionally, the EIS test showed that the Rc value of TU-T/WEP coating increased to 3.5 × 105 after 72 h, representing a two-order magnitude increase over that of the WEP coating alone. This study introduces a novel approach using green tannic acid as a corrosion inhibitor and amino-functionalized Ti3C2Tx with UIO-66-NH2 to enhance corrosion resistance and self-healing aproperties of coatings.

Metal lithium negative electrodes are considered the \"holy grail\" of lithium battery negative electrodes due to their ultra-high energy density and low overpotential. However, the arbitrary growth of lithium dendrites during the cycling process hindered its industrialization process. We prepared porous carbon doped with zinc oxide nanoparticles (ZNC-MOF-5) by high-temperature carbonization of MOF-5, and coated ZNC-MOF-5 on the surface of commercial membranes (ZNC-MOF-5@PP). Used to improve the cycling stability of metal lithium negative electrodes. Zinc oxide nanoparticles in ZNC-MOF-5 have good lithium affinity and can promote Li+ deposition. The porous structure with a high specific surface area endows the electrode with high lithium loading capacity, reduces local current density, and obtains a dendrite-free metal lithium negative electrode. The electrochemical cycling performance of Li/Cu batteries indicates that, ZNC-MOF-5@PP. The separator can prevent the growth of dendrites and improve cycling stability, proving that ZNC-MOF-5 can effectively guide the deposition of Li and solve dendrite problems.

Mixed matrix membranes (MMMs) constitute a type of molecular separation membranes in which a nanomaterial type filler is dispersed in a given polymer to enhance its selective permeation ability. The key issue in MMMs is the establishing of a proper filler-polymer interaction to avoid non-selective transport paths while increasing permeability but also to improve other membrane properties such as aging and plasticization. Along the pass years several strategies have been applied to enhance the physicochemical interaction between the fillers (e.g. silicas, zeolites, porous coordination polymers, carbonaceous materials, etc.) and the membrane polymers: increase of external surface area, priming, use of intrinsically more compatible fillers, in situ synthesis of filler, in situ polymerization, polymer side-chain modification and post-synthetic modification of filler.

This work is primarily focused on overcoming the limitations of polymeric membranes in achieving the balance between permeability and selectivity of the separation performance. The filler, Zeolitic imidazole framework -67 (ZIF-67) nanoparticles were synthesised in cubical morphology using hexadecyltrimethylammonium bromide (CTAB) as a surfactant via the wet-chemical method. The uniform particles with particle sizes ranging between 120-180 nm were incorporated into the polyvinylidene fluoride (PVDF) matrix to fabricate mixed matrix membranes via the phase inversion method. These mixed matrix membranes were systematically characterised to confirm the chemical, structural and morphological properties of the materials and membranes. Furthermore, the membranes showed a 56.5% improvement in their mechanical properties. The results confirm that 5 wt.% ZIF-67/PVDF membrane showed the best separation results compared to its pure counterpart. The permeability of H₂ gas was reported to be 1,094,511 Barrer, with selectivities of 3.03 for H₂/CO₂ and 3.06 for H₂/N₂. This represents a 210.6% increase in the permeability of H₂ gas. These results demonstrate the influence of ZIF-67 loading in the PVDF polymer matrix along with the potential of ZIF-67/PVDF mixed matrix membranes in the field of hydrogen separation and purification.