Metal-organic frameworks (MOFs) are materials with potential applications in fields such as gas adsorption and separation, catalysis, and biomedicine. Attempts to enhance the utility of MOFs have involved the preparation of various composites, including polymer-grafted MOFs. By directly grafting polymers to the external surface of MOFs, issues of incompatibility between polymers and MOFs can be overcome. Polymer brushes grafted from the surface of MOFs can serve to stabilize the MOF while enabling particle assembly into self-assembled metal-organic framework monolayers (SAMMs) via polymer-polymer interactions. Control over the chemical composition and molecular weight of the grafted polymer can allow for tuning of the SAMM characteristics. In this work, instructions are provided on how to immobilize a chain transfer agent (CTA) onto the surface of the MOF UiO-66 (UiO = Universitetet i Oslo). The CTA serves as initiation sites for the growth of polymers. Once polymer chains are grown from the MOF surface, the formation of SAMMs is achieved through self-assembly at an air-water interface. The resulting SAMMs are characterized and shown to be freestanding by scanning electron microscopy imaging. The methods presented in this paper are expected to make the preparation of SAMMs more accessible to the research community and thereby expand their potential use as a MOF-polymer composite.

UNASSIGNED: Genotyping and amyloid fibril detection in tissues are generally considered the diagnostic gold standard in transthyretin-related amyloidosis. Patients carry less stable TTR homotetramers prone to dissociation into non-native monomers, which rapidly self-assemble into oligomers and, ultimately, amyloid fibrils. Thus, the initial event of the amyloid cascade produces the smallest transthyretin species: the monomers. This creates engineering opportunities for diagnosis that remain unexplored.
UNASSIGNED: We hypothesise that molecular sieving represents a promising method for isolating and concentrating trace TTR monomers from the tetramers present in plasma samples. Subsequently, immunodetection can be utilised to distinguish monomeric TTR from other low molecular weight proteins within the adsorbed fraction. A two-step assay was devised (ImmunoSieve assay), combining molecular sieving and immunodetection for sensing monomeric transthyretin. This assay was employed to analyse plasma microsamples from 10 individuals, including 5 pre-symptomatic carriers of TTR-V30M, the most prevalent amyloidosis-associated TTR variant worldwide, and 5 healthy controls.
UNASSIGNED: The ImmunoSieve assay enable sensitive detection of monomeric transthyretin in plasma microsamples. Moreover, the circulating monomeric TTR levels were significantly higher in carriers of amyloidogenic TTR mutation.
UNASSIGNED: Monomeric TTR can function as a biomarker for evaluating disease progression and assessing responses to therapies targeted at stabilising native TTR.

Heavy metal ions and antibiotic contamination have become a major environmental concern worldwide. The development of efficient recognition strategies of these pollutants at ultra-low concentrations in aqueous solutions as well as the elucidation of the intrinsic sensing mechanism are challenging tasks. In this work, unique luminescent Ln-MOF materials (NIIC-3-Ln) were assembled by rational ligand design. Among them, NIIC-3-Tb demonstrated highly selective luminescence quenching response toward Hg2+ and sulfadiazine (SDI) at subnanomolar concentrations in less than 7 s. In addition, a Hg2+ sensing mechanism through chelation was proposed on the basis of single-crystal X-ray diffraction analysis and Hg2+ adsorption study. The interaction mechanism of NIIC-3-Tb with SDI was revealed using a newly developed approach involving a (TD-)DFT based quantification of the charge transfer of a MOF-analyte supramolecular complex model in the ground and excited states. Effect of ultrasonic treatment on the surface morphology important for MOF sensing performance was revealed by gas adsorption experiments. The presented results indicate that NIIC-3-Ln is not only an advanced sensing material for the efficient detection of Hg2+ and SDI at ultra-low concentrations, but also opens up a new approach to study the sensing mechanism at the molecular level at ultra-low concentrations.

This work investigated the feasibility of applying headspace solid phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC/MS) combining olfactory visualization for flavor characterization of black garlic. Volatile organic compounds (VOCs) analysis was performed to select important differential VOCs during black garlic processing. A multi-channels nanocomposite CSA assembled with two porous metal-organic frameworks was then developed to characterize flavor profiles changes during black garlic processing, and garlic samples during processing could be divided into five clusters, consistent with VOCs analysis. Artificial neural network (ANN) model outperformed other pattern recognition methods in discriminating processing stages. Furthermore, SVR model for odor sensory scores with the correlation coefficient for prediction set of 0.8919 exhibited a better performance than PLS model, indicating a preferable prediction ability for odor quality. This work demonstrated that the nanocomposite CSA combining appropriate chemometrics can offer an effective tool for objectively and rapidly characterizing flavor quality of black garlic or other food matrixes.

Aluminum hypophosphite (AHP) has been used as a flame retardant for a long time. Previous studies about AHP employed in flame retardant materials mostly focus on coating, modification, and complex system. It is valuable to explore simple experimental steps to prepare nano hybrids with AHP and metal-organic frameworks (MOFs). We found acidic substances could etch zeolitic imidazolate framework-67 (ZIF-67) to obtain MOF derivatives. Unfortunately, AHP and ZIF-67 could not directly form a hybrid. Therefore, carboxymethylcellulose (CMC) is introduced as a dual function layer (buffer and support). The CMC resists the complete conversion of ZIF-67 etched by phosphoric acid to amorphous cobalt phosphate hydrate (ACP). Meanwhile, CMC containing hydroxyl groups combines with AHP through electrostatic interaction and coordination bonds. A double-layer hollow MOF derivative is synthesized through this one-stone-two-birds strategy. Due to multiple flame retardant elements and unique nanostructure, this MOF derivative endows epoxy (EP) resin with excellent flame retardancy. With 2.0 wt% addition, the peak heat release rate (pHRR) and total heat release (THR) of EP/AHP/ACP@CMC are decreased by 47.8 and 21.0 %, respectively. This study proposes a novel scheme that converts AHP into MOF derivatives as high-performance FRs.

Combining the physical advantages of two-dimensional (2D) inorganic nanosheets and the modular design and programmed structure of metal-organic frameworks (MOFs), 2D MOFs remain at the forefront of functional material research. Despite tremendous efforts, precise control in the synthesis of 2D nonlayered MOFs with predesigned topology for desired applications remains challenging. Success in the bottom-up synthesis of 2D nonlayered MOFs via ligand exchange motivated us to incorporate partial BTC (BTC = 1,3,5-benzenetricarboxylate) ligand dissociation and CO2 capped coordination into the top-down treatment of bulk Cu-BTC MOF, leading to successful conversion of a 3D nonlayered network to a 2D Cu-based topological structure. Notably, a supercritical CO2-containing solvent mixture is employed to provide the desired defect and coordination engineering. Thus, our work introduces a new top-down concept based on modulated synthesis to fabricate high-quality 2D nonlayered MOFs for the first time.

2,6-pyridine dicarboxylic acid (DPA) is an exceptional biomarker of notorious anthrax spores. Therefore, the rapid, sensitive, and selective quantitative detection of DPA is extremely significant and urgent. This paper reports a Zn(II) metal-organic framework with the formula of {[Zn6(NDA)6(DPBT)3] 2H2O·3DMF}n (MOF-1), which consists of 2,6-naphthalenedicarboxylic acid (2,6-NDA), 4,7-di(4-pyridyl)-2,1,3-benzothiadiazole (DPBT), and Zn(II) ions. Structural analysis indicated that MOF-1 is a three-dimensional (3D) network which crystallized in the monoclinic system with the C2/c space group, revealing high pH, solvent, and thermal stability. Luminescence sensing studies demonstrated that MOF-1 had the potential to be a highly selective, sensitive, and recyclable fluorescence sensor for the identification of DPA. Furthermore, fluorescent test paper was made to detect DPA promptly with color changes. The enhancement mechanism was established by the hydrogen-bonding interaction and photoinduced electron transfer transition between MOF-1 and DPA molecules.

Efficient separation of CH4 from N2 is essential for the purification of methane from nitrogen. In order to address this problem, composite materials consisting of rod-shaped SBA-15-based UiO-66-Br2 were synthesized for the purpose of separating a CH4/N2 mixture. The materials were characterized via PXRD, N2 adsorption-desorption, SEM, TEM, FT-IR, and TGA. The adsorption isotherms of CH4 and N2 under standard pressure conditions for the composites were determined and subsequently compared. The study revealed that the composites were formed through the growth of MOF nanocrystals on the surfaces of the SBA-15 matrix. The enhancements in surface area and adsorption capacity of hybrid materials were attributed to the structural modifications resulting from the interactions between surface silanol groups and metal centers. The selectivity of the composites towards a gas mixture of CH4 and N2 was assessed utilizing the Langmuir adsorption equation. The results of the analysis revealed that the U6B2S5/SBA-15 sample exhibited the greatest selectivity for CH4/N2 adsorption compared to the other samples, with an adsorption selectivity parameter (S) of 20.06. Additional research is necessary to enhance the enrichment of methane from CH4/N2 mixtures using SBA-15-based metal-organic framework materials.

The oxidative esterification of aldehydes under mild conditions remains a significant challenge. This study introduces a unique defective UiO-66 to achieve gold nanoclusters (AuNCs) for efficient aldehyde oxidation under mild conditions. The construction and characterization of these materials are thoroughly investigated by techniques of XRD, SEM and TEM images, FT-IR, Raman, and XPS spectrum, emphasizing the unique microporous in defective UiO-66 are conducive to the fabrication of AuNCs. The catalytic performance of the prepared materials in aldehyde oxidation reactions is systematically evaluated, demonstrating the remarkable efficiency of dispersed Au@UiO-66-25 with high-content (9.09 wt%) Au-loading and ultra-small size (~2.7 nm). Moreover, mechanistic insights into the catalytic process under mild conditions (70 °C for 1 h) are provided, elucidating the determination of defective UiO-66 in the confined fabrication of AuNCs and subsequent furfural adsorption, which underlie the principles governing the observed enhancements. This study establishes the groundwork for the synthesis of highly dispersed and catalytically active metal nanoparticles using defective MOFs as a platform, advancing the catalytic esterification reaction of furfural to the next level.

In environmental chemistry, photocatalysts for eliminating organic contaminants in water have gained significant interest. Our study introduces a unique heterostructure combining MIL-101(Cr) and bismuth oxyiodide (Bi5O7I). We evaluated this nanostructure\'s efficiency in adsorbing and degrading tetracycline (TC) under visible light. The Bi5O7I@MIL-101(Cr) composite, with a surface area of 637 m2/g, prevents self-aggregation seen in its components, enhancing visible light absorption. Its photocatalytic efficiency surpassed Bi5O7I and MIL-101(Cr) by 33.4 and 9.2 times, respectively. Comprehensive analyses, including scanning electron microscopy (SEM) and transmission electron microscopy (TEM), confirmed the successful formation of the heterostructure with defined morphological characteristics. BET analysis demonstrated its high surface area, while X-ray diffraction (XRD) confirmed its crystallinity. Electron spin resonance (ESR) tests showed significant generation of reactive oxygen species (ROS) like h+ and·•O2- under light, crucial for TC degradation. The material maintained exceptional durability over five cycles. Density functional theory (DFT) simulations and empirical investigations revealed a type I heterojunction between Bi5O7I and MIL-101(Cr), facilitating efficient electron-hole pair separation. This study underscores the superior photocatalytic activity and stability of Bi5O7I@MIL-101(Cr), offering insights into designing innovative photocatalysts for water purification.