A molecularly imprinted electrochemical sensor MIP/Cu-MOF/rGO/AuNPs/GCE for highly sensitive detection of electroneutral organophosphorus pesticide residues.

A novel electrochemical sensor, MIP/Cu-MOF/rGO/AuNPs/GCE, was developed by depositing gold nanoparticles, coating Cu-MOF/GO on the surface of glassy carbon electrode (GCE) before electroreducing graphene oxide (GO) to rGO and covering molecularly imprinted membrane by electropolymerization for highly sensitive detection of electroneutral organophosphorus pesticide residues in agricultural product. Cyclic voltammetry, differential pulse voltametry, scanning electron microscopy, energy-dispersive spectroscopy, and atomic force microscopy were used to characterize the imprinted sensor. Several key factors such as chitosan concentration, suspension volume, pH of polymerization solution, and polymerization scanning rate during preparation of the imprinted sensor were optimized in detail. When electroneutral phosmet was used as a template, the linear range of MIP/Cu-MOF/rGO/AuNPs/GCE for detecting phosmet was 1.00 × 10-14-5.00 × 10-7 mol/L with the limit of detection of 7.20 × 10-15 mol/L at working potentials of - 0.2 to 0.6 V. The selectivity, reproducibility, and repeatability of MIP/Cu-MOF/rGO/AuNPs/GCE were all acceptable. The recoveries of this method for determining phosmet in real samples ranged from 94.2 to 106.5%. The MIP/Cu-MOF/rGO/AuNPs/GCE sensor could be applied to detect electroneutral pesticide residues in organisms and agricultural products.

Alkaloids from Zanthoxylum nitidum and their anti-proliferative activity against A549 cells by regulating the EGFR/AKT/mTOR pathway.

Zanthoxylum nitidum is frequently used as a traditional Chinese medicine and food supplement. Our previous study revealed that its constituent compounds were able to inhibit cancer cell proliferation. In our continuous exploration of bioactive compounds in Z. nitidum, we isolated ten alkaloids (1-10), including one new natural compound (1), and nine known alkaloids (2-10), from an ethanolic extract of the whole plant. The chemical structures were elucidated based on a combination of comprehensive NMR and HRESIMS analyses. Compounds 5, 8 and 10 exhibited significant antiproliferative effects against A549 cancer cell lines. We further elucidated the underlying molecular mechanisms of the antiproliferative activity of compound 8 in A549 human lung cancer cells. Compound 8 was found to induce cell cycle arrest in the G0/G1 phase via p53 activation and CDK4/6 suppression. Compound 8 also effectively inhibited cell migration through the modulation of the epithelial-mesenchymal transition (EMT), as indicated by the expression of biomarkers, such as N-cadherin downregulation and E-cadherin upregulation. Compound 8 significantly suppressed the activation of the EGFR/AKT/mTOR signalling pathway in A549 cells. These results indicate that alkaloid 8 from Z. nitidum has potential to be a lead antiproliferative compound in cancer cells.

Deep-Eutectic-Solvent-Based Mesoporous Molecularly Imprinted Polymers for Purification of Gallic Acid from Camellia spp. Fruit Shells.

To produce antioxidant substances from agricultural waste Camellia spp. fruit shells before their further utilization, gallic acid from five kinds of Camellia spp. fruit shells was separated on specific recognition by deep eutectic solvent molecularly imprinted polymers (DES@MIPs), which were prepared by bulk polymerization using gallic acid as the template and deep eutectic solvents (α-methylacrylic acid and choline chloride) as functional monomers. The optimized DES@MIPs were characterized by scanning electron microscopy, particle size analysis, nitrogen sorption porosimetry, elemental analysis, Fourier transform infrared spectroscopy, and thermal gravimetric analysis. The adsorptive behavior of gallic acid on DES@MIPs was also investigated. The results indicated that DES@MIPs were successfully prepared as mesoporous materials with average pore diameter of 9.65 nm and total pore volume of 0.315 cm3 g-1, and the adsorption behavior was multilayer adsorption and pseudo-second-order kinetics with the saturation adsorptive capacity of gallic acid reaching 0.7110 mmol g-1. Although the content of gallic acid in five fruit shells was quite different, the purification recovery of gallic acid was high, ranging from 87.85-96.75% with a purity over 80%. Thus, the purification of gallic acid from Camellia spp. fruit shells could be realized feasibly using DES@MIPs with favorable economic and environmental benefits.

Genome-wide characterization of soybean RALF genes and their expression responses to Fusarium oxysporum.

RALFs (RAPID ALKALINIZATION FACTORs) are small peptides required for plant growth, development and immunity. RALF has recently been discovered to regulate plant resistance to fungal infection. However, little is known in crops, particularly in soybean. Here, 27 RALFs were identified in the genome of Glycine max. All Glycine max RALFs (GmRALFs) and 34 Arabidopsis RALFs were classified into 12 clades via the phylogenetic analyses. Gene structures, conserved motifs, chromosome distribution and cis-elements were analyzed in this study. Furthermore, 18 GmRALFs were found in response to Fusarium oxysporum (F. oxysporum) infection in soybean and to have distinct expression patterns. Among them, secretory function of two GmRALFs were identified, and three GmRALFs were detected to interact with FERONIA in Glycine max (GmFERONIA, GmFER). Our current study systematically identified and characterized GmRALFs in the soybean genome, laying a groundwork for further functional analyses and soybean breeding.

Terpyridine copper(II) complexes as potential anticancer agents by inhibiting cell proliferation, blocking the cell cycle and inducing apoptosis in BEL-7402 cells.

Four mononuclear terpyridine complexes [Cu(H-La)Cl2]·CH3OH (1), [Cu(H-La)Cl]ClO4 (2), [Cu(H-Lb)Cl2]·CH3OH (3), and [Cu(H-Lb)(CH3OH)(DMSO)](ClO4)2 (4) were prepared and fully characterized. Complexes 1-4 exhibited higher cytotoxic activity against several tested cancer cell lines especially BEL-7402 cells compared to cisplatin, and they showed low toxicity towards normal human liver cells. ICP-MS detection indicated that the copper complexes were accumulated in mitochondria. Mechanistic studies demonstrated that the copper complexes induced G0/G1 arrest and altered the expression of the related proteins of the cell cycle. All copper complexes reduced the mitochondrial membrane potential while increasing the intracellular ROS levels and the release of Ca2+. They also up-regulated Bax and down-regulated Bcl-2 expression levels, caused cytochrome c release and the activation of the caspase cascade, and induced mitochondrion-mediated apoptosis. Animal studies demonstrated that complex 1 suppressed tumor growth in a mouse xenograft model bearing BEL-7402 tumor cells.