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  • Drake Hayden posted an update 12 days ago

    Itaconic acid esters and hemiesters undergo Pd-catalyzed coupling reactions with arene diazonium salts in high to excellent yields. The coupling products of ortho-nitro arene diazonium salts can be converted in one or two steps to benzazepine-2-ones.In this paper, a molecularly imprinted two-dimensional photonic crystal hydrogel sensor (SMZ-MIPCH) for the sensitive and label-free recognition of sulfamethoxazole (SMZ) was prepared. The SMZ-MIPCH sensor response performance was investigated via measuring the diameter of the Debye ring (D). When the SMZ-MIPCH sensor recognized SMZ, the diameter of the Debye ring gradually decreased and the particle spacing (d) of the photonic crystals gradually increased. As the SMZ concentration increased from 0 to 10-4 mol L-1, the diameter decreased by 15.2 mm and the corresponding particle spacing increased by 131 nm. As the diffraction peak wavelength of the sensor gradually red-shifted, the color changed from blue to green and finally to orange-red. A good linear relationship was found between the variation of the particle spacing (Δd) and the value of the logarithm of the SMZ concentration (lg c) in the range from 10-16 mol L-1 to 10-10 mol L-1. The limit of detection of the SMZ-MIPCH sensor is 10-16 mol L-1. In the presence of analogues of SMZ, such as sulfisoxazole, sulfadiazine, and sulfamethazine, the diameter changed only slightly, indicating that the SMZ-MIPCH sensor had specific recognition abilities for SMZ. The SMZ-MIPCH sensor has the advantages of high sensitivity, specific recognition, and naked eye detection, and it can be used for the detection of SMZ in water samples.A novel and practical palladium-catalyzed aerobic oxyarylthiolation of alkynone O-methyloximes for the assembly of 4-sulfenylisoxazole derivatives using S8 and arylhydrazines as the S-aryl sources is accomplished. In the presence of 0.1 mol% of IPr-Pd-allyl-Cl as the catalyst and O2 (1 atm) as the sole oxidant, both alkynone O-methyloximes and arylhydrazines are suitable substrates, delivering diverse 4-sulfenyl isoxazoles in moderate to good yields with good functional group tolerance. Notably, the phenyl diazonium salt and sodium phenyl sulfinate are also suitable arylation reagents, providing an alternative synthetic strategy to access structurally diverse 4-sulfenyl isoxazoles.We report N,N-dimethylformamide-stabilised Pd nanoparticle (Pd NP)-catalysed transfer vinylation of alcohols from vinyl ether. Pd NPs combined with bathophenanthroline exhibited high catalytic activity. This reaction proceeded with low catalyst loading and the catalyst remained effective even after many rounds of recycling. The observation of the catalyst using transmission electron microscopy and dynamic light scattering implied no deleterious aggregation of Pd NPs.Metal hydride complexes are key intermediates for N-alkylation of amines with alcohols by the borrowing hydrogen/hydrogen autotransfer (BH/HA) strategy. Reactivity tuning of metal hydride complexes could adjust the dehydrogenation of alcohols and the hydrogenation of imines. Herein we report ruthenium(ii) complexes with hetero-bidentate N-heterocyclic carbene (NHC)-phosphine ligands, which realize smart pathway selection in the N-alkylated reaction via reactivity tuning of [Ru-H] species by hetero-bidentate ligands. In particular, complex 6cb with a phenyl wingtip group and BArF- counter anion, is shown to be one of the most efficient pre-catalysts for this transformation (temperature is as low as 70 °C, neat conditions and catalyst loading is as low as 0.25 mol%). A large variety of (hetero)aromatic amines and primary alcohols were efficiently converted into mono-N-alkylated amines in good to excellent isolated yields. Notably, aliphatic amines, challenging methanol and diamines could also be transformed into the desired products. Detailed control experiments and density functional theory (DFT) calculations provide insights to understand the mechanism and the smart pathway selection via [Ru-H] species in this process.Proteoglycans (PGs) play important roles in many biological processes including tumor progression, cell adhesion, and regulation of growth factor activities. With glycosaminoglycan chains attached to the core proteins in nature, PGs are highly challenging synthetic targets due to the difficulties in integrating the sulfated glycans with the peptide backbone. To expedite the synthesis, herein, the utility of human xylosyltransferase I (XT-I), the enzyme responsible for initiating PG synthesis, has been explored. XT-I was found to be capable of efficiently installing the xylose unit onto a variety of peptide structures on mg scales. Furthermore, an unnatural sugar, i.e., 6-azidoglucose can be transferred by XT-I introducing a reactive handle onto the glycopeptide for selective functionalization. XT-I can be coupled with β-4-galactosyl transferase-7 for one pot synthesis of glycopeptides bearing galactose-xylose disaccharide, paving the way toward efficient chemoenzymatic synthesis of PG glycopeptides and glycoproteins.As a component of extracellular matrix (ECM), hyaluronic acid (HA) has plenty of applications in the biomedical field such as tissue engineering. Due to its non-adhesive nature, HA requires further grafting of functional molecules for cell related study. find more RGD and YIGSR are two kinds of cell adhesion peptides. YIGSR enhances endothelial cell (EC) adhesion, which is important for endothelialization after implantation of stents to prevent in-stent restenosis. However, the effect of combined densities of these peptides for EC and smooth muscle cell (SMC) adhesion has not been explored in a quantitative and high-throughput manner. In this work, single or orthogonal gradient densities of RGD and YIGSR were grafted onto the HA hydrogel array surfaces using thiol-norbornene click chemistry. Optimized peptide combinations for EC preponderant adhesion were found in hydrogel arrays and confirmed by scaling samples.Osteogenesis and angiogenesis are both important for implant osseointegration, which can be tailored by immunomodulation of macrophages. Zn, a novel biodegradable material, can modulate macrophage functions in its ionic form. However, whether macrophage-derived exosomes, novel carriers of intracellular communication, participate in the process is still unclear. The present work shows that Zn ions in the concentration range of 0-100 μM have no significant influence on macrophage viability, proliferation, morphology, and secretion amount of exosomes, but generally downregulate the gene expression of both M1 and M2 markers. The exosomes can be ingested continuously by osteoblasts and endothelial cells. The osteoblasts show the highest alkaline phosphatase activity after ingesting the exosomes derived from macrophages upon 4 μM Zn ion stimulation. In contrast, the endothelial cells migrate the furthest distance after ingesting the exosomes upon 20 μM Zn ion stimulation. These results indicate that Zn ions may vary the composition of macrophage-derived exosomes, which in turn affects the osteogenesis and angiogenesis.

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