A General Catalyst Based on Cobalt Core–Shell Nanoparticles for the Hydrogenation of N-Heteroarenes Including Pyridines

Herein, we report the synthesis of specific silica-supported Co/Co₃O₄ core–shell based nanoparticles prepared by template synthesis of cobalt-pyromellitic acid on silica and subsequent pyrolysis. The optimal catalyst material allows for general and selective hydrogenation of pyridines, quinolines, and other heteroarenes including acridine, phenanthroline, naphthyridine, quinoxaline, imidazo[1,2-a]pyridine, and indole under comparably mild reaction conditions. In addition, recycling of these Co nanoparticles and their ability for dehydrogenation catalysis are showcased.     

Threshold electrical switching in As45Te55-xInx and As50Te50-xInx glasses

The electrical switching behaviour of As₄₅Te_55-xIn_x (5≤x≤15) and As₅₀Te_50-xIn_x (2.5≤x≤11.5) has been studied over a wide range of compositions. These glasses are found to exhibit threshold switching. The composition dependence of switching voltage (V_t) has been found to exhibit a change in slope and a local minimum at compositions x=10 and 12.5 for As₄₅Te_55-xIn_x and x=7.5 and 10.8 for As₅₀Te_50-xIn_x, respectively. The slope change in V_t verses x and the local minimum have been identified using two network topological effects, namely the rigidity percolation threshold and the chemical threshold. Received: 23 August 2001 / Accepted: 27 August 2001 / Published online: 11 February 2002     

Electronic structure of CeAl2 thin films studied by X-ray absorption spectroscopy

We report X-ray absorption near edge structures (XANES) study of CeAl₂ thin films of various thicknesses, 40-120 nm, at Al K- and Ce L₃-edges. The threshold of the absorption features at the Al K-edge shifts to the higher photon energy side as film thickness decreases, implying a decreased in Al p-orbital charges. On the other hand, from Ce L₃-edge spectra, we observed a decrease in the 5d4f occupancy as the surface-to-bulk ratio increases. The valence of Ce in these thin films, as revealed by the Ce L₃-edge spectral results, is mainly trivalent. From a more detailed analysis we found a small amount of Ce⁴⁺ contribution, which increases with decreasing film thickness. Our results indicate that the surface-to-bulk ratio is the key factor which affects the electronic structure of CeAl₂ thin films. The above observations also suggest that charge transfer from Al to Ce is associated with the decrease of the film thickness.     

Influence of the distal his in imparting imidazolate character to the proximal his in heme peroxidase: (1)h NMR spectroscopic study of cyanide-inhibited his42-->ala horseradish peroxidase

The functional higher oxidation states of heme peroxidases have been proposed to be stabilized by the significant imidazolate character of the proximal His. This is induced by a "push-pull" combination effect produced by the proximal Asp that abstracts ("pulls") the axial His ring N(delta)H, along with the distal protonated His that contributes ("pushes") a strong hydrogen bond to the distal ligand. The molecular and electronic structure of the distal His mutant of cyanide-inhibited horseradish peroxidase, H42A-HRPCN, has been investigated by NMR. This complex is a valid model for the active site hydrogen-bonding network of HRP compound II. The (1)H and (15)N NMR spectral parameters characterize the relative roles of the distal His42 and proximal Asp247 in imparting imidazolate character to the axial His. 1D/2D spectra reveal a heme pocket molecular structure that is highly conserved in the mutant, except for residues in the immediate proximity of the mutation. This conserved structure, together with the observed dipolar shifts of numerous active site residue protons, allowed a quantitative determination of the orientation and anisotropies of the paramagnetic susceptibility tensor, both of which are only minimally perturbed relative to wild-type HRPCN. The quantitated dipolar shifts allowed the factoring of the hyperfine shifts to reveal that the significant changes in hyperfine shifts for the axial His and ligated (15)N-cyanide result primarily from changes in contact shifts that reflect an approximately one-third reduction in the axial His imidazolate character upon abolishing the distal hydrogen-bond to the ligated cyanide. Significant changes in side chain orientation were found for the distal Arg38, whose terminus reorients to partially fill the void left by the substituted His42 side chain. It is concluded that 1D/2D NMR can quantitate both molecular and electronic structural changes in cyanide-inhibited heme peroxidase and that, while both residues contribute, the proximal Asp247 is more important than the distal His42 in imparting imidazole character to the axial His 170.     

A Clean and Expedient Synthesis of Pyrido[1,4]oxazepino Spiropyrrolidines Through One-Pot,Three-Component [3 + 2] Cycloaddition Reaction

One-pot three component synthesis of novel pyrido[1,4]-oxazepine fused spiropyrrolidines has been accomplished in good yields by 1,3-dipolar cycloaddition reaction of azomethine ylide, derived from paraformaldehyde and sarcosine with (E)-4-benzylidene-hexahydro-1H-pyrido[2,1-c][1,4]-oxazepine-3(7H)-one as dipolarophiles derived from Baylis-Hillman adducts. The effect of solvent on the [3 + 2]-cycloaddition reaction is also studied.     

Heterotrophic Nitrifying and Oxygen Tolerant Denitrifying Bacteria from Greenwater System of Coastal Aquaculture

In this work, herbivorous fish Mugil cephalus has been cultured to secrete protein rich green slime, which helps nitrifying and oxygen tolerant denitrifying bacteria to grow and colonize. Four strains representing Alcaligenaceae family have been isolated from greenwater system and characterized using biochemical test, fatty acid methyl ester (GC-FAME) analysis, 16S rRNA and functional gene approaches. They were tested for an ability to nitrify ammonia and nitrite aerobically. Two strains showed notable nitrification activity, when grown in a mineral salts medium containing ammonium sulfate and potassium nitrite. Functional gene analysis confirmed the presence of nitrous oxide reductase (nosZ) gene showing that they have an oxygen-tolerant denitrification system. It has been proposed that Alcaligenes faecalis strains heterotrophically nitrify ammonia into nitrite via formation of hydroxyl amine, which is oxidized to nitrous oxide using oxygen or nitrite as electron acceptor. These results provide a possible advantage of having nitrification and denitrification capabilities in the same organism, which plays an important role in biological wastewater system.     

Effect of 60Co γ-irradiation on structural and optical properties of thin films of Ga10Se80Hg10

Thin films of Ga₁₀Se₈₀Hg₁₀ have been deposited onto a chemically cleaned Al₂O₃ substrates by thermal evaporation technique under vacuum. The investigated thin films are irradiated by ⁶⁰Co γ-rays in the dose range of 50–150 kGy. X-ray diffraction patterns of the investigated thin films confirm the preferred crystallite growth occurs in the tetragonal phase structure. It also shows, the average crystallite size increases after γ-exposure, which indicates the crystallinity of the material increases after γ-irradiation. These results were further supported by surface morphological analysis carried out by scanning electron microscope and atomic force microscope which also shows the crystallinity of the material increases with increasing the γ-irradiation dose. The optical transmission spectra of the thin films at normal incidence were investigated in the spectral range from 190 to 1100 nm. Using the transmission spectra, the optical constants like refractive index (n) and extinction coefficient (k) were calculated based on Swanepoel’s method. The optical band gap (E_g) was also estimated using Tauc’s extrapolation procedure. The optical analysis shows: the value of optical band gap of investigated thin films decreases and the corresponding absorption coefficient increases continuously with increasing dose of γ-irradiation.