A Cu(II) MOF with laccase-like activity for colorimetric detection of 2,4-dichlorophenol and p-nitrophenol.

Metal-organic framework (MOF) materials with aqueous stability have a good potential application in the field of mimetic enzymes. However, most of them have poor robustness in aqueous solution due to competitive coordination effects between water molecules and central metal ions. Herein, a copper-based MOF (Cu-SM MOF) was prepared using copper ions and 5-(sulfomethyl) isophthalic acid (5-SMIPA) by a hydrothermal process. Considering the similarity of coordination and morphology with HKUST-1, the aqueous stability and laccase-like activity of the Cu-SM MOF were investigated using HKUST-1 as the reference. The Cu-SM MOF shows superior aqueous stability to HKUST-1 after immersion in buffer solutions, especially under alkaline conditions. Moreover, the Cu-SM MOF possesses higher catalytic activity than HKUST-1 at a high salt concentration, high temperature, etc., because the Cu-SM MOF exhibits lower Km and higher Vmax values than those of laccase and reported mimetic enzymes. The mimetic enzyme behavior of the Cu-SM MOF is demonstrated in the oxidation of phenols, as well as in the detection of 2,4-dichlorophenol (2,4-DP) and p-nitrophenol with linear ranges of 1-100 µM and 2-250 µM, and limits of detection of 0.53 µM and 1.62 µM, respectively. Owing to the excellent aqueous stability and laccase-like activity of the Cu-SM MOF, it has great application prospects in many fields, such as the determination of phenols and the treatment of industrial wastewater.

Metal-Organic Framework with Near-Infrared Luminescence for "Switch-on" Determination of Kaempferol and Quercetin by the Antenna Effect.

The establishment of a reliable and sensitive method for the detection of flavonoids, such as kaempferol (Kae) and quercetin (Que), is important and challenging in food chemistry and pharmacology because numerous structural analogues may interfere with the detection. Until now, designing an efficient switch-on fluorescence sensing strategy for Kae and Que was still in the unachievable stage. In this work, a switch-on near-infrared (NIR) luminescence sensing assay for Kae and Que was fabricated based on a metal-organic framework (MOF) called IQBA-Yb for the first time. The fluorescence enhancing mechanism was that analytes served as additional "antenna" of Yb3+, leading to the efficient switch-on NIR emission under excitation at 467 nm. Meanwhile, the combination results of experiment and theoretical calculation revealed that there existed hydrogen bonds between Kae, Que, and the MOF skeleton, further promoting the energy transfer between the analyte and Yb3+ and facilitating fluorescence enhancement response. The developed probe possessed excellent sensing capability for Kae and Que, accompanied by a wide linear range (0.04-70, 0.06-90 µM), low detection limit (0.01, 0.06 µM), and short response time (20 min, 6 min), which was used to determine the Kae and Que contents in Green Lake and eatable Que samples with satisfactory results.

Preparation of MSNs@Keratin as pH/GSH dual responsive drug delivery system.

Designing a drug delivery system that is responsive in a tumor microenvironment is important to potentiate the efficacy and reduce the side effects of antitumor drugs. In this study, the surface of mesoporous silica nanoparticles (MSNs) were aminated with 3-aminopropyl triethoxysilane (APTES) and then coupled with keratin, as a gatekeeper, to afford MSNs-NH2@Keratin. The average sizes and morphologies of MSNs and MSNs-NH2@Keratin were characterized with dynamic light scattering and transmission electron microscopy, respectively. The loading content and encapsulation efficiency of doxorubicin (DOX) were calculated to be 17.1 ± 1.7% and 71.3 ± 2.1%. Drug-loaded MSNs-NH2@Keratin exhibited pH and glutathione (GSH) dual responsiveness under tumor microenvironment. The nanoparticles could be uptaken by tumor cells to effectively inhibit tumor cell growth. Moreover, the sizes of nanoparticle were stable in the serum. Collectively, our findings demonstrated the potential of DOX-loaded MSNs-NH2@Keratin in the treatment of cancer.

Denitrification of Permeable Sand Sediment in a Headwater River Is Mainly Influenced by Water Chemistry, Rather Than Sediment Particle Size and Heterogeneity.

Sediment particle size and heterogeneity play an important role in sediment denitrification through direct and indirect effects on, for example, the material exchange rate, environmental gradients, microbial biomass, and grazing pressure. However, these effects have mostly been observed in impermeable sediments. On the other hand, the material exchange of permeable sediments is dominated by advection instead of diffusion, with the exchange or transport rates exceeding those of diffusion by two orders of magnitude relative to impermeable sediments. The impact of permeable sediment particle size and heterogeneity on denitrification remains poorly understood, especially at the millimeter scale. Here, we conducted an in situ control experiment in which we sorted sand sediment into four homogeneous-particle-sizes treatments and four heterogeneous treatments. Each treatment was deployed, in replicate, within the riffle in three different river reaches with contrasting physicochemical characteristics. After incubating for three months, sediment denitrifier communities (nirS, nirK, nosZ), denitrification gene abundances (nirS, nirK, nosZ), and denitrification rates in all treatments were measured. We found that most of the denitrifying microbes in permeable sediments were unclassified denitrifying microbes, and particle size and heterogeneity were not significantly correlated with the functional gene abundances or denitrification rates. Water chemistry was the key controlling factor for the denitrification of permeable sediments. Water NO3--N directly regulated the denitrification rate of permeable sediments, instead of indirectly regulating the denitrification rate of sediments by affecting the chemical characteristics of the sediments. Our study fills a knowledge gap of denitrification in permeable sediment in a headwater river and highlights that particle size and heterogeneity are less important for permeable sediment denitrification.

Morphology-Dependent Peroxidase Mimicking Enzyme Activity of Copper Metal-Organic Polyhedra Assemblies.

The morphology of nanomaterials (geometric shape and dimension) play a significant role in its various physical and chemical properties. Thus, it is essential to link morphology with performance in specific applications. For this purpose, the morphology of copper metal-organic polyhedra (Cu-MOP) can be modulated through distinct assembly process, which facilitates the exploration of the relationship between morphology and catalytic performance. In this work, the assemblies of Cu-MOP with three different morphologies (nanorods, nanofibers and nanosheets) were facilely prepared by the variation of solvent mixture of N, N-dimethylformamide (DMF) and methanol, revealed the important role of the interaction between the surface group and the solvent on the morphology of these assemblies. Cu-MOP nanofibers exhibited the highest mimetic peroxidase enzyme activity over the Cu-MOP nanosheets and nanorods, which have been utilized in the detection of glucose. Cu-MOPs assemblies with tunable morphology accompanied with adjustable mimic peroxidase activity, had great potential applications in the field of bioanalytical chemistry and biomedicals.

Stability of the V and Co atomic wires: a first-principles study.

We employ density-functional theory calculations plus pseudopotentials with the projector-augmented wave method to investigate the structural stability and electromagnetic characteristics of two infinite atomic wires made of vanadium (V) and cobalt (Co). We identify five stable V atomic wires and four stable Co atomic wires. The H structure of the V atomic wire shows semiconductor characteristics, and the other four structures show metallic properties. None of the V chains has magnetism. On the other hand, the four stable Co atomic wires have metal properties. The dimerized Co atomic chain is shown to be ferromagnetic with a maximum spin magnetic moment.