Activation of N2O reduction by the fully reduced micro4-sulfide bridged tetranuclear Cu Z cluster in nitrous oxide reductase

J. Am. Chem. Soc., 2003, 125 (51), pp 15708–15709 DOI: 10.1021/ja038344n

Ni(II), Cu(II), AND Zn(II) COMPLEXES DERIVED FROM A NEW SCHIFF BASE 2-((Z)-(3-METHYLPYRIDIN-2- YLEIMINO)METHYL)PHENOL AND SYNTHESIS OF NANO SIZED METAL OXIDE PARTICLES FROM THESE COMPOUNDS

Synthesis, spectral identification, and magnetic properties of three complexes of Ni(II), Cu(II), and Zn(II) are described. All three compounds have the general formula [M(L)2(H2O)2], where L = deprotonated phenol in the Schiff base 2-((z)-(3-methylpyridin-2-yleimino)methyl)phenol. The three complexes were synthesized in a one-step synthesis and characterized by elemental analysis, Fourier transform infrared spectroscopy, electronic spectra, X-ray diffraction (XRD), and room temperature magnetic moments. The Cu(II) and Ni(II) complexes exhibited room temperature magnetic moments of 1.85 B.M. per copper atom and 2.96 B.M. per nickel atom. The X-band electron spin resonance spectra of a Cu(II) sample in dimethylformamide frozen at 77 K (liquid nitrogen temperature) showed a typical ΔMS = ± 1 transition. The complexes ([M(L)2(H2O)2]) were investigated by the cyclic voltammetry technique, which provided information regarding the electrochemical mechanism of redox behavior of the compounds. Thermal decomposition of the complexes at 750 ºC resulted in the formation of metal oxide nanoparticles. XRD analyses indicated that the nanoparticles had a high degree of crystallinity. The average sizes of the nanoparticles were found to be approximately 54.3, 30.1, and 44.4 nm for NiO, CuO, and ZnO, respectively.

Studies on Chemical Bath Deposited Semiconducting Copper Selenide and Iron Sulfide Thin Films Useful For Photovoltaic Applications

Chemical bath deposition (CBD)is one of the simplest, very convient and probably the cheapest method for thin film preparation. Photovoltaic is the cleanest and the most efficient mode of conversion of energy to electrical power. Silicon is the most popular material in this field. The present study on chemical bath deposited semiconducting copper selenide and iron sulfide thin films useful for photovoltaic applications. Semiconducting thin films prepared by chemical deposition find applications as photo detectors, solar control coatings and solar cells. Copper selenide is a p-type semiconductor that finds application in photovolitics. Several heterojunction systems such as Cu2-xSe/ZnSe (for injection electro luminescence), Cu2Se/AgInSe2 and Cu2Se/Si (for photodiodes), Cu2-xSe/CdS, Cu2-xSe/CdSe, CuxSe/InP and Cu2-xSe/Si for solar cells are reported. A maximum efficiency of 8.3% was achieved for the Cu2-xSe/Si cell, various preparation techniques are used for copper selenide like vacuum evaporation, direct reaction, electrodeposition and CBD. Instability of the as-prepared films was investigation and is accounted as mainly due to deviation from stoichiometry and the formation of iron oxide impurity. A sulphur annealing chamber was designed and fabricated for this work. These samples wee also analysed using optical absorption technique, XPS (X-ray Photoelectron Spectroscopy) and XRD.(X-Ray Diffraction).The pyrite films obtained by CBD technique showed amorphous nature and the electrical studies carried out showed the films to be of high resistive nature. Future work possible in the material of iron pyrite includes sulphur annealing of the non-stochiometric iron pyrite CBD thin films in the absence of atmospheric oxygen

Development of pure and doped gamma ferric oxide

Optimum conditions and experimental details for the formation of v-Fe203 from goethite have been worked out. In another method, a cheap complexing medium of starch was employed for precipitating acicular ferrous oxalate, which on decomposition in nitrogen and subsequent oxidation yielded acicular y-Fe203. On the basis of thermal decomposition in dry and moist nitrogen, DTA, XRD, GC and thermodynamic arguments, the mechanism of decomposition was elucidated. New materials obtained by doping ~'-Fe203 with 1-16 atomic percent magnesium, cobalt, nickel and copper, were synthesised and characterized

Copper deposition on TiO2 from copper(II)hexafluoroacetylacetonate

The authors have studied the adsorption of CuII(hfac)2 on the surface of a model oxide system, TiO2(110), and probed the molecular stability with respect to thermal cycling, using atomic scale imaging by scanning tunneling microscopy supported by x-ray photoemission spectroscopy. They find that at 473 K, the adsorbed metal-organic molecules begin to dissociate and release Cu atoms which aggregate and form Cu nanoparticles. These Cu nanoparticles ripen over time and the size (height) distribution develops into a bimodal distribution. Unlike other organometallic systems, which show a bimodal distribution due to enhanced nucleation or growth at surface step edges, the nanoparticles do not preferentially form at steps. The reduced mobility of the Cu islands may be related to the co-adsorbed ligands that remain in very small clusters on the surface.

Glass-to-Vitroceramic Transition in the Yttrium Aluminoborate System: Structural Studies by Solid-State NMR

The crystallization of laser glasses in the system (B(2)O(3))(0.6){(Al(2)O(3))(0.4-y)(Y(2)O(3))(y)} (0.1 <= y <= 0.25) doped with different levels of ytterbium oxide has been investigated by X-ray powder diffraction, differential thermal analysis, and various solid-state NMR techniques. The homogeneous glasses undergo major phase segregation processes resulting in crystalline YBO(3), crystalline YAI(3)(BO(3))(4), and residual glassy B(2)O(3) as the major products. This process can be analyzed in a quantitative fashion by solid-state (11)B, (27)Al, and (89)Y NMR spectroscopies as well as (11)B{(27)Al} rotational echo double resonance (REDOR) experiments. The Yb dopants end up in both of the crystalline components, producing increased line widths of the corresponding (11)B, (27)Al, and (89)Y NMR resonances that depend linearly on the Yb/Y substitution ratio. A preliminary analysis of the composition dependence suggests that the Yb(3+) dopant is not perfectly equipartitioned between both crystalline phases, suggesting a moderate preference of Yb to substitute in the crystalline YBO(3) component.

Copper hexacyanoferrate nanoparticles modified electrodes: A versatile tool for biosensors

Copper hexacyanoferrate nanoparticles of about 30 nm in size have been prepared by the sonochemical irradiation of a mixture of aqueous potassium ferricyanide and copper chloride solutions. The nanoparticles were immobilized onto fluorine doped tin oxide (FTO) electrodes by using the electrostatic deposition layer-by-layer technique (LbL), obtaining electroactive films with electrocatalytic properties towards H2O2 reduction, providing higher currents than those observed for electrodeposited bulk material, even in electrolytes containing NH4+, Na+ and K+. The nanoparticles assembly was used as mediator in a glucose biosensor by immobilizing glucose oxidase enzyme by both, cross-linking and LbL. techniques. Sensitivities obtained were dependent on the immobilization method ranging from 1.23 mu A mmol(-1) L cm(-2) for crosslinking to 0.47 mu A mmol(-1) L cm(-2) for LbL; these values being of the same order than those obtained with electrodes where the amount of enzyme used is much higher. Moreover, the linear concentration range where the biosensors can operate was 10 times higher for electrodes prepared with the LbL immobilization method than with the conventional crosslinking one. (C) 2008 Elsevier B.V. All rights reserved.

FIA determination of ascorbic acid at low potential using a ruthenium oxide hexacyanoferrate modified carbon electrode

The anodic oxidation of ascorbic acid on a ruthenium oxide hexacyanoferrate modified electrode was characterized by cyclic voltammetry. On this modified surface, the electrocatalytic process allows the determination of ascorbic acid to be performed at 0.0 V and pH 6.9 with a limit of detection of 2.2 mu M in a flow injection configuration. Under this experimental condition, no interference from glucose, nitrite and uric acid was noticed. Lower detection limit values were obtained by measuring flow injection analysis (FIA) responses at 0.4 V (0.14 mu M), but a concurrent loss of selectivity is expected at this more positive potential. Under optimal FIA operating conditions, the linear response of the method was extended up to 1 mM ascorbic acid. The repeatability of the method for injections of a 1.0 mM ascorbic acid solution was 2.0% (n=10). The usefulness of the method was demonstrated by an addition-recovery experiment with urine samples and the recovered values were in the 98-104% range. (c) 2007 Elsevier B.V. All rights reserved.

Synthesis and characterization of lanthanum- and yttrium-doped Fe2O3 pigments

MELO, D. M. A. et al. Synthesis and charactezarion of lanthanum and yttrium doped Fe2O3 pigments. Cerâmica, São Paulo, v. 53, p. 79-82, 2007.

Peroxidase activity and total phenol content in citrus cuttings treated with different copper sources

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Thermal behavior of copper(II) pseudohalide complexes containing bidentate amines

Pseudohalide complexes of copper(II) with aliphatic bidentate amines, [Cu(N-3)(2)(N,N-diEten)](2) 1, [Cu(NCO)(2)(N,N-diEten)](2) 2, [Cu(NCO)(2)(N,N-diMeen)](2) 3, [Cu(N-3)(NCS)(N,N'-diMeen)](2) 4 and [Cu(N-3)(NCO)(N,N-diMeen)](2) 5 (N,N-diEten=N,N-diethylethylenediamine; N,N-diMeen=N,N- dimethyl-ethylenediamine and N,N'-diMeen = N,N'-dimethylethylenediamine), were prepared, characterized and their thermal behavior was investigated by TG curves. According to thermal analysis and X-ray diffraction patterns all compounds decomposed giving copper(II) oxide as final product. The mechanisms of decomposition were proposed and an order of thermal stability was established.

The influence of yttrium on a typical SnO2 varistor system: Microstructural and electrical features

The influence of yttrium oxide, Y2O3, on the microstructure development of the SnO(2)center dot Co(3)O(4)center dot Nb2O5 typical varistor system was studied with scanning (SEM) and transmission (TEM) electron microscopies. The different phases present in the studied samples were characterized through XRD, EDS and selected area diffraction patterns (SAD). Particles of Co2SnO4 were observed with TEM in every sample, whereas clusters of the pyrochlore phase T2Sn2O7 were observed with SEM in samples with 0.05, 0.10 and 0.25 mol% of Y2O3. The higher non-linearity (a = 16) was achieved with the addition of 0.05 mol% of Y2O3. The influence of the secondary phases on the electrical properties is also addressed in this work. (c) 2005 Published by Elsevier B.V.

Thermal studies of solid 4-chlorobenzylidenepyruvates of heavy lanthanides(III) and yttrium(III)

Solid-state compounds of general formula LnL(3).2H(2)O, where Ln is heavier trivalent lanthanides and yttrium, L is 4-chlorobenzylidenepyruvate have been synthetised.On heating these compounds decompose in steps. They lose the hydration water in the first step and the thermal decomposition of the anhydrous compounds occurs with the formation of oxochloride (Eu, Gd); mixture of oxide and oxochloride that decrease with increasing of atomic number of metal (Tb-Tm); or oxide (Yb, Lu, Y) as final residue, up to 900degreesC. The dehydration enthalpies found for terbium, holmium, ytterbium and yttrium compounds were: 34.93, 42.40, 57.39 and 62.24 kJ mol(-1), respectively.

Synthesis, characterization and thermal studies on solid compounds of 2-chlorobenzylidenepyruvate of heavier trivalent lanthanides and yttrium(III)

Solid-state compounds of general formula LnL(3)center dot nH(2)O, where Ln represents heavier lanthanides and yttrium and L is 2-chlorobenzylidenepyruvate, have been synthesized. Chemical analysis, simultaneous thermogravimetry-differential analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, elemental analysis and infrared spectroscopy have been employed to characterize and to study the thermal behaviour of these compounds in dynamic air atmosphere.On heating these compounds decompose in four (Gd, Tb, Ho to Lu, Y) or five (Eu, Dy) steps. They lose the hydration water in the first step and the thermal decomposition of the anhydrous compounds up to 1200 degrees C occurs with the formation of the respective oxide, Tb4O7 and Ln(2)O(3) (Ln=Eu, Gd, Dy to Lu and Y) as final residue. The dehydration enthalpies found for these compounds (Eu, to Lu and Y) were: 65.77, 55.63, 86.89, 121.65, 99.80, 109.59, 131.02, 119.78, 205.46 and 83.11 kJ mol(-1), respectively.

Research of new mixed-chelate copper complexes with quinoxaline N 1,N 4,-dioxide derivatives and alanine as ligands, potential antimycobacterial agents

Three new mixed-chelate copper complexes with 3-aminoquinoxaline-2-carbonitrile N 1,N 4-dioxide derivatives and alanine as ligands were synthesized in solid state. The spectroscopic characterization (FTIR, EPR, UV-Vis) showed that copper coordinated through the amine and the N-oxide groups of the quinoxaline derivatives and the amine and carboxylate moieties from alanine forming a dimeric species. The tree complexes showed in vitro activity against M. tuberculosis H 37Rv (ATCC 27294) similar to that of ethambutol while they are inactive against E. coli and S. aureus.