DFT studies of the characteristics of Pd−Pt core-shell clusters

It is reported that Pd?Pt core-shell type nanoclusters in which the inner atoms of the Pd cluster are substituted by Pt significantly enhance the catalytic activity for cycloocatdiene hydrogenation. In order to discuss the electronic states of core-shell clusters, DFT calculations were carried out for Pd₁₃, Pt₁₃, Pt/Pd₁₂, Pd/Pt₁₂ Pd₃₈ and Pd₆/Pt₃₂ clusters. From these calculations, it was found that the charge transfer between the core atoms and the shell atoms played an important role for the modification of the electronic state of the surface atoms in them.     

Survey of residual tetracyclines in kidneys of diseased animals in Aichi Prefecture, Japan (1985-1997)

A survey was conducted to determine the incidence of tetracycline antibiotic (TCAs) residues in the kidneys of slaughtered animals that did not pass inspection for human consumption by the Japanese Food Sanitation Law and the Meat Inspection Law at the slaughterhouses in Aichi Prefecture, Japan, from April 1985 to March 1998. The kidneys were analyzed by the AOAC Official Method 995.09. Among 424 animals (147 cattle and 277 pigs), 131 (30.9%) were contaminated with TCAs, including 69 (16.3%) with chlortetracycline (CTC), 61 (14.4%) with oxytetracycline (OTC), 3 (0.7%) with tetracycline (TC), and 1 (0.2%) with doxycycline (DC). One sample (cattle kidney) was contaminated with both OTC and DC. The frequencies of OTC and TC residues were significantly higher (p < 0.05) in cattle than in pigs, whereas, the frequency of CTC was significantly higher (p < 0.01) in pigs. Pig kidney samples collected in 1991-1997 had significantly higher incidences of TCAs and CTC (p < 0.01) residues than those in 1985-1986.     

Carbon Monoxide Oxidation by Polyoxometalate‐Supported Gold Nanoparticulate Catalysts: Activity,Stability, and Temperature‐ Dependent Activation Properties

Nanoparticulate gold supported on a Keggin‐type polyoxometalate (POM), Cs₄[α‐SiW₁₂O₄₀]?n H₂O, was prepared by the sol immobilization method. The size of the gold nanoparticles (NPs) was approximately 2 nm, which was almost the same as the size of the gold colloid precursor. Deposition of gold NPs smaller than 2 nm onto POM (Au/POM) was essential for a high catalytic activity for CO oxidation. The temperature for 50 % CO conversion was ?67 °C. The catalyst showed extremely high stability for at least one month at 0 °C with full conversion. The catalytic activity and the reaction mechanism drastically changed at temperatures higher than 40 °C, showing a unique behavior called a U‐shaped curve. It was revealed by IR measurement that Au^δ+ was a CO adsorption site and that adsorbed water promoted CO oxidation for the Au/POM catalyst. This is the first report on CO oxidation utilizing Au/POMs catalysts, and there is a potential for expansion to various gas‐phase reactions.     

Oxidative dimerization of aromatic amines using tBuOI: entry to unsymmetric aromatic azo compounds

It's all the hype: An oxidative dimerization reaction of aromatic amines utilizing tert-butyl hypoiodite (tBuOI) under mild reaction conditions leads to aromatic azo compounds. The method allows access to unsymmetric aromatic azo compounds, which are difficult to prepare by conventional synthetic methods, in a selective manner.     

Metal-Support Interaction Which Controls the Oxidation State, Structure and Catalysis of Pd

A metal-support interaction between Pd and various kinds of zeolite and metal oxide supports was studied, which were active in the catalytic combustion and selective reduction of NO. The acid-base properties of supports affected the oxidation state, structure and catalytic activity of Pd. The acid sites of zeolite played the role to anchor the dispersed PdO as evidenced by the dynamic structural change of Pd. It was found that the metal-support interaction is an important factor, affecting the oxidation state, structure and catalytic performance of Pd.     

n-sigma charge-transfer interaction and molecular and electronic structural properties in the hydrogen-bonding systems consisting of p-quinone dianions and methyl alcohol

Molecular and electronic structural properties of the hydrogen-bonded complexes of p-quinone dianions (PQ(2)(-)) were investigated by electrochemistry and spectroelectrochemistry of PQ in MeCN combined with ab initio MO calculations. Hydrogen bonding between PQ(2)(-) and MeOH was measured as the continuous positive shift of the apparent second half-wave reduction potentials with increasing concentrations of MeOH. Detailed analyses of the behavior reveal that PQ(2)(-) forms the 1:2 hydrogen-bonded complexes at low concentrations of MeOH and the 1:4 complexes at high concentrations, yielding the formation constants. Temperature dependence of the formation constants allows us to yield the formation energy as 76.6 and 118.9 kJ mol(-)(1) for the 1:2 and 1:4 complex formation of the 1,4-benzoquinone dianion (BQ(2)(-)) with MeOH, respectively. These results show that the pi-dianions involving the quinone carbonyl groups exhibit very strong hydrogen-accepting ability. The longest wavelength band of the spectra of BQ(2)(-) and the chloranil dianion (CL(2)(-)) is assigned to the (1)B(3u) <-- (1)A(g) band mainly contributed from an intramolecular charge-transfer (CT) configuration. Hydrogen bonding allows the band of BQ(2)(-) and CL(2)(-) to be blue-shifted, depending on the strength of the hydrogen bonds. CNDO/S-CI calculations reveal that the blue shift is ascribed to stabilization of the ground state by the hydrogen bonding involving strong n-sigma-type CT interaction. The HF/6-31G(d) calculation results show that the structure of PQ(2)(-) is characterized by a lengthening of the C=O bonds and a benzenoid ring. The geometrical properties of the hydrogen-bonded complexes of PQ(2)(-) are a slight lengthening of the C=O bonds and a short distance of the hydrogen bonds. It is demonstrated that this situation is due to the strong n-sigma CT interaction in the hydrogen bonds. The results suggest that the differing functions and properties of biological quinones are conferred by the n-sigma CT interaction through hydrogen bonding of the dianions with their protein environment.     

Application of phenolic compounds in plants for green chemical materials

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