Nanostructures made by mixing Rh atoms on N-adsorbed Cu(001) surface

Nanostructures and nanopattern formation by mixing Rh atoms were studied on the N-saturated Cu(001) surface using scanning tunneling microscopy and X-ray photoemission spectroscopy. Most of the Rh atoms are in the topmost layer of the surface, and make a line structure of two atomic width in the <100> direction. Each Rh atom in the line is bonded to one N atom. The density of trench-like structures at the N-saturated surface decreases with increasing the density of the lines. This indicates that the line structure reduces the surface stress induced by N adsorption. When the Rh atoms cover more than a quarter of surface on average, the lines form a rectangular pattern at the surface. The average separation decreases with the increase of the Rh density, and is 4 nm for the 30% Rh coverage. The pattern formation is attributed to the efficient reduction of lattice strain as the grid pattern on the partially N-adsorbed Cu(001) surface.     

Self-assembled MnN superstructure

Self-assembled MnN nanoislands have been prepared on Cu(001) substrate. The nanoislands show a square shape and a well-defined size. They are regularly arrayed with a periodicity of (3.5+/-0.1) nanometer and form a two-dimensional square superstructure. The MnN island superstructure is stabilized by a short-range mechanism. A structural model has been proposed to explain the self-assembly and the high quality of the superstructure.     

Intermolecular asymmetric reductive aldol reaction of ketones as acceptors promoted by chiral Rh(Phebox) catalyst

[reaction: see text] The conjugate reduction of cinnamates with hydrosilane and chiral Rh(Phebox-ip) catalyst in the presence of excess acetone is shown to provide the corresponding intermolecular reductive aldol product in extremely high enantioselectivity (up to 98%). Several cinnamates and crotonate substrates and several ketone acceptors were also examined.     

The inhibition abilities of multifunctional polyelectrolytes for silica scale formation in cooling water systems: role of the nonionic functional group

The abilities of multifunctional polyelectrolytes to enhance aluminum hydroxide dispersion and inhibit silica scale formation were examined in a pilot cooling water system. The following multifunctional polyelectrolytes were studied: a terpolymer of acrylic acid (AA), 2-acrylamide-2-methyl propane sulfonic acid (SA) and N-vinylpyrrolidone (NVP) (P(AA/SA/NVP)), acrylic acid homopolymer (P(AA)) and a copolymer of AA and SA (P(AA/SA)). The order of inhibition ability was P(AA/SA/NVP)>P(AA/SA)>P(AA), and was consistent with that of the dispersing ability for aluminum hydroxide. Other terpolymers incorporating different nonionic monomers were also examined and factors affecting their inhibition abilities were investigated, based on interaction energies calculated by density functional theory. Based on the correlation between scale inhibition abilities and interaction energies, we elucidated that the effective nonionic monomer of terpolymer for silica scale inhibition had low affinity for aluminum hydroxide and high affinity for H(2)O and Si(OH)(3)O(-). The affinities of nonionic monomer for aluminum hydroxide and H(2)O suggested that there was proper conformation of polyelectrolyte adsorbed for effectively dispersing aluminum hydroxide. Also, high affinity of nonionic monomer for Si(OH)(3)O(-) suggested that interacting Si(OH)(3)O(-) is an important role of inhibition of silica scale formation.     

Complexation of Silicic Acid with Tiron in Aqueous Solution Under near Natural Condition

The formation of a silicic acid–tiron (a derivative of catechol) complex was investigated in aqueous solution with various molar ratios of tiron to silicic acid (tiron/Si) or with various pH using ²⁹Si NMR. Only the 1:3 silicic acid–tiron complex was detected in despite of the range of tiron/Si molar ratios. This complex is stable in the pH range from 6 to 10. This indicates that the formation of a hydrogen bond (SiOH⋅⋅⋅O− in tiron), due to dissociation of H⁺ from hydroxy groups of tiron, may be a trigger for the formation of the complex. Around pH=6, the formation of the complex occurs when the tiron/Si molar ratio is larger than 3 and most of silicic acid is converted to the complex when the ratio is larger than 25. Based on the temperature dependence of the ²⁹Si NMR spectra for the complex, the existence of two possible meridional and facial isomers was confirmed. The conditional formation constant for the 1:3 silicic acid–tiron complex was defined as Eq. 8 and estimated to be 2.0 mol⁻¹⋅dm³ for the facial complex and 4.1 mol⁻¹⋅dm³ for the meridional complex, respectively.     

Reaction of 2-aminobenzamide analogs and 2-aminothiophenol with ethyl 3-ethoxymethylene-2,4-dioxovalerate. Synthesis of pyrrolo[1,2-α]quinazoline and pyrrolo[1,2-a]benzothiazoline derivatives

The reaction of ethyl 3-ethoymethylene-2,4-dioxovalerate (EMDV) ( 1 ) with 2-aminobenzamide ( 2 ), 2-aminobenzthioamide ( 3 ), 2-aminobenzmethylamide ( 4 ) and 3-amino-2-methyl- or phenylpyrazole-4-carbox-amides ( 6 and 7 ) produced ethyl 3-aminomethylene-2,4-dioxovalerates ( 10, 15, 16, 18 and 19 ), which led to pyrrolo[1,2-a]quinazoline-1,5-diones ( 11, 22 and 23 ) and pyrrolo[1,2-a]pyrazolo[4,3-e]pyrimidine-1,5-diones ( 24 and 25 ) under the acidic condition, respectively. Analogously, 2-aminothiophenol reacted with 1 to give 21 , which was subsequently derived to pyrrolo[1,2-a]benzothiazolin-l-one ( 26 ) under the neutral condition. Furthermore, we prepared the heterocyclic steroidal molecules ( 41, 43, 45, 47, 49 and 51 ) by condensation of 11 and 26 with hydrazine, methylhydrazine and phenylhydrazine.     

Ring transformation of 6H-cyclopropa[e]pyrazolo[1,5-a]pyrimidine. VI. Substituent effect of 6-substituted 5a-acetyl-6a-ethoxycarbonyl-5a,6a- dihydro-6H-cyclopropa[e]pyrazolo[1,5-a]pyrimidine-3-carbonitriles

Synthesis and reactivity of 6-ethoxycarbonyl-, 6-phenyl- and 6-methyl-5a-acetyl-6a-ethoxycarbonyl-5a,6a-di-hydro-6H-cyclopropa[e]pyrazolo[1,5-a]pyrimidine-3-carbonitriles 4 , 5 , and 7 are described.