Direct hydroxylation of benzene to phenol using molecular oxygen is a green route with high atom economy but still a great challenge when compared with the existing method of production. The activation of oxygen is necessary and reductive agents were used to activate dioxygen in a so-called “reductive activation” process. Here, nano vanadium oxides that consist mainly of low valence vanadium to activate dioxygen were prepared under different conditions via a hydrothermal method. Under the optimized conditions, an excellent phenol selectivity of 96.3% with benzene conversion of 4.2% was achieved over the VOC2O4–N-5 without reductive agents. Characterizations revealed that VOC2O4–N-5 was composed of a mesoporous nanosphere structure with medium strong acid sites and low valence vanadium species. A mechanism was proposed as follows: dioxygen was activated by low valence vanadium in VOC2O4–N-5 to produce the active oxygen species which oxidized acetic acid to peracetic acid. Then the active oxygen species was subsequently transferred from peracetic acid to benzene and inserted into the C–H bond to give phenol.
The catalytic conversion of furan derivatives, furfural and 5‐hydroxymethylfurfural (HMF), to valuable chemicals is of great importance due to the increase in carbon emissions and decrease in fossil fuels. In this manuscript, 1,2,5‐hexanetriol was transformed to HMF through a two steps procedure. The HMF was first hydrogenated to 1‐hydroxyhexane‐2,5‐dione (HHD). The reaction scale could be enlarged from 1 mmol to 50 mmol of the reactant with a similar yield of HHD, and the purity of HHD was over 95 % after a simple extraction. Then the HHD was hydrogenated to 1,2,5‐hexanetriol on Ru/C at very mild reaction conditions. The parameters of pressure, solvent, the concentration of HHD, reaction time and temperature on the hydrogenation of HHD were investigated to find the optimal reaction conditions. The 1,2,5‐hexanetriol could be obtained from HMF in a one‐pot reaction by removing the Pd/C and adding Ru/C after the HMF hydrogenation step. The fresh and used Pd/C and Ru/C were characterized by XRD, TEM, XPS, and the Ru/C was further characterized by EDS mappings. The characterization showed partial agglomeration of Pd occurred after the Pd/C was used. The Ru/C had a narrow Ru distribution and was stable under the reaction conditions. The Ru/C could be used at least 5 times. This manuscript showed an easy route for the production of valuable chemicals from renewable biomass furan derives.
29 April 2016 in Journal of Thermal Analysis and Calorimetry
In this work, we report a pseudo-circular DNA walker (PDW) integrated with G-quadruplex (G4) and triplex DNA to construct an electrochemical biosensor for ultrasensitive detection of apolipoprotein E4 (T-e4). PDW contains double embedded DNAzyme sequences, leveraging the intrinsic advantages of enhanced structural rigidity for stable spatial conformation, continuous autonomous rolling capability, and efficient cyclic cleavage of hairpin probes due to its closed-loop topology. After binding to the target, the catalytic domain of the PDW is activated, rolling and cutting the hairpin probe in the presence of Mg2+. The triplex helix hairpin orbital (THO) serves as a rigid scaffold to immobilize hairpin DNA probes, enhancing interfacial stability and signal probe loading efficiency. The cleavage releases G-rich DNA fragments, which subsequently self-assemble into hemin/G-quadruplex (HG4) nanostructures. This design achieves label-free detection with exceptional sensitivity, exhibiting a linear range of 0.05–10 pM and a detection limit of 27 fM. This strategy opens up a new way for the sensitive detection of neurodegenerative disease biomarkers and shows broad application prospects in the fields of early disease screening and clinical monitoring.
7 January 2015 in Journal of Coordination Chemistry
Two heptanuclear trigonal prismatic polyhedra, [EuCu6(μ-OH)3(Gly)6Im6](ClO4)6·3H2O and [SmCu6(μ-OH)3(Gly)6Im6](ClO4)6·3H2O were synthesized through self-assembly of Eu3+(Sm3+), Cu2+, glycine, and imidazole in aqueous solution and characterized by X-ray single crystal diffraction. Both complexes crystallize in the rhombohedral R3 space group (a = b = 15.8673 Å, c = 23.4038 Å, V = 5103.0(6) Å3, Z = 3) and (a = b = 15.8749 Å, c = 23.455 Å, V = 5119.1(8) Å3, Z = 3). In the clusters, Sm3+ and Eu3+ ions are situated in the center of a prism formed by six copper ions and coordinate to nine oxygens with a tricapped trigonal prismatic coordination polyhedron. Six glycinato ligands and six imidazole terminal ligands (each coordinates to one Cu2+) construct the cluster. The fluorescent excitation and emission spectra showed that the complexes have strong ligand-based fluorescence.