Synthesis and properties of cuboid-shaped ZnO hierarchical structures

Cuboid-shaped ZnO hierarchical structures constructed with quasi-single-crystalline ZnO nanosheets were fabricated through a mixed surfactants mediated hydrothermal method. The products were characterized by XRD, SEM, TEM, and ED methods. Room temperature photoluminescence spectrum of the as-obtained ZnO hierarchitectures was recorded showing multiple peaks of visible emissions in blue-green region. The synergetic effect of citrate and surfactants SDBS and OP was believed to play a key role in controlling the construction features of ZnO nanosheets. The ZnO hierarchitectures showed effective photocatalytic activity for the decomposition of methyl orange.     

ILL-POSEDNESS FOR THE NONLINEAR DAVEY-STEWARTSON EQUATION

The nonlinear D-S equations on R^d, with general power nonlinearity and with both the focusing and defocusing signs, are proved to be ill-posed in the Sobolev space H^s whenever the exponent s is lower than that predicted by scaling or Galilean invariance, or when the regularity is too low to support distributional solutions. Authors analyze a class of solutions for which the zero-dispersion limit provides good approximations.     

Bioinspired polymer functionalized with a diiron carbonyl model complex and its assembly onto the surface of a gold electrode via “click” chemistry

A complex pendant with two ethynyl groups, [Fe₂(μ‐SCH₂CCH)₂(CO)₆] ( 2 ), as a model of the diiron subunit of [FeFe]‐hydrogenase was polymerized and the {Fe₂(CO)₆} core was successfully incorporated into the polymer matrix. The polymer was characterized by a variety of spectroscopic techniques, TGA, FTIR, SEM, TEM, and NMR. The resultant polymer was immobilized via “click” chemistry using its terminal C?CH bond onto the surface of a gold electrode, which was premodified with azidothiol by self‐assembled monolayer (SAM). The assembled electrode showed electrochemical responses. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2410–2417, 2010     

Stereoselective synthesis of novel N-(α-l-arabinofuranos-1-yl)-l-amino acids

In lead detoxification, the α-anomer of N-glycocyl-l-amino acid is more potent than its β-anomer. Here a six-step-reaction route for stereoselectively preparing N-(α-l-arabinose-1-yl)-l-amino acids is reported. Treating l-arabinose with acetic anhydride and sodium acetate provided 1,2,3,5-tetra-O-acetyl-l-arabinofuranose in 90% yield. After removing the 1-acetyl group, the thus formed 2,3,5-tri-O-acetyl-l-arabinofuranose and N-(2-nitrophenylsulfonyl)-l-amino acid t-butylesters were treated with triphenylphosphine to perform Mitsunobu dehydration and form 2,3,5-tri-O-acetyl-l-arabinofuranosyl-l-[N-(2-nitrophenylsulfonyl)]amino acid t-butylesters 2a–f, and the ratios of their α- to β-anomer ranged from 8/1 to 9/1. Chromatographic separation provided epimerically pure 2a–f-α and 2a–f-β. In the presence of CF₃CO₂H, 2a–f-α and 2a–f-β were converted to α- and β-anomers of N-(2,3,5-tri-O-acetyl-l-arabinofuranosyl)-N-(2-nitrobenzenesulfonyl)-l-amino acids, 3a–f-α and 3a–f-β, in 87–92% yields. While in the presence of NaOCH₃, 3a–f-α and 3a–f-β were converted to α- and β-anomers of N-(l-arabinofuranosyl)-N-(2-nitrobenzenesulfonyl)-l-amino acids, 4a–f-α and 4a–f-β, in 90–96% yields. Treating 4a–f-α and 4a–f-β with N-ethyldiisopropylamine (DIPEA) and thiophenol, their 2-nitrophenylsulfonyl groups were removed, and the α- and β-anomers of N-(l-arabinose-1-yl)-l-amino acids were formed in 70–79% yields. The bioassay confirmed that the lead detoxification activity of the α-anomer was significantly higher than that of the β-anomer.     

Coaction of sub-band and doped nitrogen on visible light photoactivity of N-doped TiO2

We found in our previous work that the high photoactivity of N-doped TiO₂ for the oxidation of propylene under visible light was attributed to the photoactive center V_o^•-NO-Ti and the formation of sub-band originated from a large amount of single-electron-trapped oxygen vacancies (denoted as V_o^•; C. X. Feng, Y. Wang, Z. S. Jin, J. W. Zhang, S. L. Zhang, Z. S. Wu, Z. J. Zhang [2008], New J. Chem. 32 , 1038). In the present study, the structure of the sub-band within E_g of a representative sample N-NTA-400 was investigated by means of photoluminescence (PL) spectrometry and ultraviolet-visible light-near infrared diffuse reflectance spectra. The coaction of the sub-band and doped nitrogen on visible light photocatalytic activity of N-doped TiO₂ was also investigated. The electron spin resonance spectra measured under laser irradiation (λ = 532 nm) indicate that the doped nitrogen may contribute to stabilize the trapping electron center, i.e. surface oxygen vacancy (V_o^••), and hence suppress the PL, enhancing the photocatalytic activity.     

Synthesis and characterisation of polymeric materials consisting of {Fe2(CO)5}-unit and their relevance to the diiron sub-unit of [FeFe]-hydrogenase

By using "click" chemistry between a diazide and a diiron model complex armed with two alkynyl groups, two polymeric diiron complexes (Poly-Py and Poly-Ph) were prepared. The two polymeric complexes were investigated using infrared spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), M?ssbauer spectroscopy, and cyclic voltammetry (Poly-Py only, due to the insolubility of Poly-Ph). To probe the coordinating mode of the diiron units in the two polymeric complexes, two control complexes (3 and 4) were also synthesised using a monoazide. Complexes 3 and 4 were well characterised and the latter was further crystallographically analysed. It turns out that in both complexes (3 and 4) and the two polymeric diiron complexes, one of the two iron atoms in the diiron unit coordinates with one of the triazole N atoms. Our results revealed that both morphologies and properties of Poly-Py and Poly-Ph are significantly affected by the organic moiety of the diazide. Compared to the protonating behaviour of the complexes 3 and 4, Poly-Py exhibited proton resistance. In electrochemical reduction, potentials for the reduction of the diiron units in Poly-Py and hence its catalytic reduction of proton in acetic acid-DMF shifted by over 400 mV compared to those for complexes 3 and 4. It is likely that the polymeric nature of Poly-Py offers the diiron units a "protective" environment in an acidic medium and more positive reduction potential.     

Thermal loading induced near-infrared broadband upconversion emission of Sm-doped β-NaYbF4 nano-phosphors

A non-closed hydrothermal synthetic processing is improved to synthesize Sm³⁺ doped β-NaYbF₄ nano-phosphors at 98 °C without any high-temperature and high-pressure treatments as a final step. Novel green, red, and near-infrared broadband (799-873 nm) upconversion emissions of Sm³⁺-doped β-NaYbF₄ nano-phosphors under 980 nm excitation are observed. These UC emissions can be assigned to the Sm³⁺ transitions of ⁴G_J, ⁴F_3/2 and ⁶F_11/2→⁶H_J. The half-width of 873 nm emission band is broadened nearly two-fold through the annealing treatment for nano-phosphors. The upconversion process in Yb³⁺-Sm³⁺ system is discussed based on energy transfer mechanisms.