Selective-precursor reducing route to cobalt nanocrystals and ferromagnetic property

Cobalt nanocrystals were prepared by controlled chemical route at mild condition through selective-precursor reducing synthesis. Nanorod bundles and three-dimensional (3D) dendritic nanocrystal networks of Co were prepared by selecting different precursors. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) technologies. Field-emission scanning electron microscopy (FE-SEM), SEM, and TEM images indicate the nanorod bundles mainly consist of nanorods with the diameter of 70 nm. In 3D dendritic nanocrystal networks there are numerous secondary and sub-secondary branches were grown at right angles on each main stem. Room temperature magnetic measure of the Co samples demonstrates much enhanced ferromagnetic property, which might be attributed to their organization of specific shape. The possible formation mechanism of the cobalt nanocrystals with different morphologies was also discussed.     

Synthesis, characterization, and catalytic reactivity of a highly basic macrotricyclic aminopyridine

The synthesis methods, physicochemical and structural characteristics, and catalytic reactivity of new macrocyclic proton chelators, N,N',N'-tris(p-tolyl)azacalix[3](2,6)(4-pyrrolidinopyridine) and N,N',N'-tris(p-tolyl)azacalix[3](2,6)(4-piperidinopyridine), are studied. The introduction of pyrrolidino and piperidino groups into the pyridine unit enables the enhancement of the synergistic proton affinity of the cavity of the macrotricycle giving a high basicity (pK(BH+) = 28.1 and 27.1 in CD(3)CN), resulting in a catalytic activity for the Michael addition of nitromethane with α,β-unsaturated carbonyl compounds.     

Formation of highly ordered mesoporous titania films consisting of crystalline nanopillars with inverse mesospace by structural transformation

Highly ordered mesoporous titania films consisting of crystalline nanopillars with open-spaced, perpendicular, and continuous porosity have been prepared via structural transformation from a 3D hexagonal mesostructure during the thermal treatment. The mechanism of the structural transformation is explained by the crystallization of the titania framework and the large contraction of the initial 3D hexagonal mesostructured film upon calcination. This structural transformation provides a new approach to generate mesoporous thin-film materials with unique structures.     

Characterization and activity analysis of catalytic water oxidation induced by hybridization of [(OH(2))(terpy)Mn(mu-O)(2)Mn(terpy)(OH(2))](3+) and clay compounds

Hybridization of [(OH(2))(terpy)Mn(mu-O)(2)Mn(terpy)(OH(2))](3+) (terpy= 2,2':6',2' '-terpyridine) (1) and mica clay yielded catalytic dioxygen (O(2)) evolution from water using a CeIV oxidant. The reaction was characterized by various spectroscopic measurements and a kinetic analysis of O(2) evolution. X-ray diffraction (XRD) data indicates the interlayer separation of mica changes upon intercalation of 1. The UV-vis diffuse reflectance (RD) and Mn K-edge X-ray absorption near-edge structure (XANES) data suggest that the oxidation state of the di-mu-oxo Mn(2) core is Mn(III)-Mn(IV), but it is not intact. In aqueous solution, the reaction of 1 with a large excess Ce(IV) oxidant led to decomposition of 1 to form MnO(4-) ion without O(2) evolution, most possibly by its disproportionation. However, MnO(4-) formation is suppressed by adsorption of 1 on clay. The maximum turnover number for O(2) evolution catalyzed by 1 adsorbed on mica and kaolin was 15 and 17, respectively, under the optimum conditions. The catalysis occurs in the interlayer space of mica or on the surface of kaolin, whereas MnO(4-) formation occurs in the liquid phase, involving local adsorption equilibria of adsorbed 1 at the interface between the clay surface and the liquid phase. The analysis of O(2) evolution activity showed that the catalysis requires cooperation of two equivalents of 1 adsorbed on clay. The second-order rate constant based on the concentration (mol g(-1)) of 1 per unit weight of clay was 2.7 +/- 0.1 mol(-1) s(-1) g for mica, which is appreciably lower than that for kaolin (23.9 +/- 0.4 mol(-1) s(-1) g). This difference can be explained by the localized adsorption of 1 on the surface for kaolin. However, the apparent turnover frequency ((kO(2))app/s(-1)) of 1 on mica was 2.2 times greater than on kaolin when the same fractional loading is compared. The higher cation exchange capacity (CEC) of mica statistically affords a shorter distance between the anionic sites to which 1 is attracted electrostatically, making the cooperative interaction between adsorbed molecules of 1 easier than that on kaolin. The higher CEC is important not only for attaining a higher loading but also for the higher catalytic activity of adsorbed 1.     

Anti-inflammatory sesquiterpenes from Curcuma zedoaria

From the methanolic extract of the rhizome of Curcuma zedoaria, we isolated anti-inflammatory sesquiterpene furanodiene (1) and furanodienone (2) along with new sesquiterpene compound 3 and known eight sesquiterpenes, zederone (4), curzerenone (5), curzeone (6), germacrone (7), 13-hydroxygermacrone (8), dehydrocurdione (9), curcumenone (10), and zedoaronediol (11). Their structures were elucidated on the basis of spectroscopic data. The anti-inflammatory effect of isolated components on 12-O-tetradecanoylphorbol-13-acetate (TPA)-induced inflammation of mouse ears were examined. Compounds 1 and 2 suppressed the TPA-induced inflammation of mouse ears by 75% and 53%, respectively, at a dose of 1.0 micromol. Their activities are comparable to that of indomethacin, the normally used anti-inflammatory agent.     

Spectrophotometric analysis of 5-coordinate cobalt(II) species for ligand substitution of hexakis(acetonitrile)cobalt(II) with bulky 1,1,3,3-tetramethylurea in noncoordinating nitromethane.

The ligand substitution reaction of [Co(an)6]2+ (an = acetonitrile) with 1,1,3,3-tetramethylurea (TMU) in the noncoordinating solvent, nitromethane, was spectrophotometrically investigated by titration. The observed spectral changes were analyzed using a model with the four steps of ligand substitution. The component complexes involved in the substitution were found to be 6-coordinate [Co(an)6]2+ and [Co(an)5(tmu)]2+, 5-coordinate [Co(an)3(tmu)2]2+ and [Co(an)2(tmu)3]2+, and 4-coordinate [Co(tmu)4]2+. The logarithmic values of the stepwise equilibrium constant are 2.17 +/- 0.26, 1.06 +/- 0.15, 1.19 +/- 0.06, and -0.4 +/- 0.4 at 25 degrees C. The decrease in the coordination number of the Co(II) ion from 6 to 5 during the formation of [Co(an)3(tmu)2]2+ and from 5 to 4 during the formation of [Co(tmu)4]2+ is ascribed to the steric repulsion between the coordinating bulky TMU molecules.