Field-scale spatial correlation between contents of iron oxides and CO2 emission in an Oxisol cultivated with sugarcane

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effects of humidity on the electrical properties of thermal inkjet-printed films of copper tetrasulfonated phthalocyanine (CuTsPc) onto paper substrates

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Thermal inkjet printing of copper tetrasulfonated phthalocyanine (CuTsPc) as a semiconducting layer on flexible MIS capacitors

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Alterations of protein expression in conditions of copper-deprivation for Paracoccidioides lutzii in the presence of extracellular matrix components

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Preparation and thermal decomposition of solid state cobalt, nickel, copper and zinc chelates of ethylenediaminetetraacetic acid

Solid state chelates of general formula H-2[M(EDTA)] . nH2O, where M is Co, Ni, Cu or Zn, and EDTA is ethylenediaminetetraacetate, were prepared. Thermogravimetry-derivative thermogravimetry (TG-DTG), differential thermal analysis (DTA) and complexometry were used to characterize and to study the thermal stability and thermal decomposition of these compounds.

The crystal field strength parameter and the maximum splitting of the 7F1 manifold of the Eu3+ ion in oxides

We examine, from both the experimental and theoretical point of view, the behavior of the maximum splitting ΔE, of the 7F1 manifold of the Eu3+ ion as a function of the so-called crystal field strength parameter, Nv, in a series of oxides. In connection with the original theory that describes the relation between ΔE and Nv, a more consistent procedure to describe this relation is presented for the cases of small total angular momentum J. Good agreement is found between theory and experiment. © 1995.

Effects of copper vapor laser irradiation (λ = 510.6 nm) on the enamel and dentine of human teeth: An ultra-structural morphologic study

Objective: A morphological and ultra-structural study of copper vapor laser (λ = 510.6 nm) effects on enamel and dentine was performed to show the effects of this radiation. Methods: A total of 15 human molars were cut in half; 15 pieces were separated for irradiation on enamel and 15 for dentine. These two groups were further divided into five experimental groups, including a control group, comprised of three half-sections each, irradiated by a CVL laser with a power of 7 W, a repetition rate of 15,000 pulses/sec and exposed at 500, 600, and 800 msec and 1 sec irradiation times with a 5-sec interval between irradiations. Results: In an ultra-structural SEM exam, we observed that on the enamel surfaces irradiated for 1 sec there was morphological alteration that consisted of catering, flaking, and melting on the surfaces. There was no alteration for the other exposure times. On the dentine teeth irradiated for 1 sec, we observed an evident ultra-structural alteration of melted tissue and loss of morphological characteristics. In the dentine group irradiated by 800 msec, we observed ablation and a partial loss of morphological characteristics. In the dentine groups irradiated by 500 and 600 msec, no alteration was observed. Conclusions: The results showed that irradiation with CVL promoted morphologic changes in the enamel as well as in the dentine and demonstrated a need for future studies in order to establish a safe protocol for further use in the odontological practice.

Correlation between i.r. spectra and thermal decomposition of cobalt(II), nickel(II), copper(II) and mercury(II) complexes with piperidinedithiocarbamate and pyrrolidinedithiocarbamate

The thermal decomposition of pyrrolidinedithiocarbamate and piperidinedithiocarbamate complexes of CoII, NiII, CuII and HgII have been studied by thermogravimetry and differential scanning calorimetry. The decomposition intermediates and final products were identified by their X-ray diffraction patterns. The i.r. spectra are discussed in terms of the thermal decomposition pathways.

Structural study of copper oxide supported on a ceria-modified titania catalyst system

A structural study of CuO supported on a CeO2-TiO2 system was undertaken using X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) techniques. The results of XRD revealed the presence of only two phases, TiO2 anatase and CeO2 cerianite. A trend towards smaller TiO2 crystallites was observed when cerium content increased. When the amount of cerium increased, Ti K-edge XANES analysis showed an increasing distortion of Ti sites. The results of Ce LIII-edge EXAFS showed that Ce atoms are coordinated by eight oxygen atoms at 2.32 Å. For the sample containing a small amount of cerium, the EXAFS analysis indicated that the local structure around Ce atoms was highly distorted. The catalysts presented quite different Cu K-edge XANES spectra compared to the spectra of the CuO and Cu2O reference compounds. The Cu-O mean bond length was close to that of the CuO and the Cu atoms in the catalysts are surrounded by approximately four oxygen atoms in their first shell. Copper supported on the ceria-modified titania support catalysts displayed a better performance in the methanol dehydrogenation when compared to copper supported only on titania or on ceria. © 2002 Plenum Publishing Corporation.

Electrochemical behaviour of copper electrode in concentrated sulfuric acid solutions

The electrochemical behaviour of copper in 6.0 mol 1-1 sulfuric acid at 30°C, was studied by means of the potentiodynamic method. At low potential sweep rates, v < 200 m V s-1, the data reveal that the anodic process is basically constituted of copper dissolution and a film formation which inhibits further metal oxidation and which may undergo further dissolution. For higher potential sweep rates, a modification in the passivation region of the voltammogram is observed. It can be ascribed to a change in the passivation mechanism which possibly involves different surface species. The kineticrelationships derived from the potentiodynamic I/E curves obtained at low v suggest a film formation via a dissolution/precipitation mechanism. © 1993.

Structure of copper complexes adsorbed on a silica gel surface chemically modified with benzimidazole

Silica gel having a particle size between 0.2 and 0.05 mm and a specific surface area, S BET = 473 m 2 g -1, was chemically modified with benzimidazole. Adsorption isotherms of CuX 2 (X = Cl, Br or ClO 4) from ethanol and acetone solutions were studied at 298 K. The metal is bonded to the surface through the free nitrogen atom of the attached benzimidazole. The average number of ligands co-ordinated to the central metal ion was shown to depend on the solid surface loading by the solute. At low loading the electronic and ESR spectral parameters indicated that the copper ion is in a distorted-tetragonal symmetry field.

The homeostasis of iron, copper, and zinc in paracoccidioides brasiliensis, cryptococcus neoformans var. Grubii, and cryptococcus gattii: a comparative analysis

Iron, copper, and zinc are essential for all living organisms. Moreover, the homeostasis of these metals is vital to microorganisms during pathogenic interactions with a host. Most pathogens have developed specific mechanisms for the uptake of micronutrients from their hosts in order to counteract the low availability of essential ions in infected tissues. We report here an analysis of genes potentially involved in iron, copper, and zinc uptake and homeostasis in the fungal pathogens Paracoccidioides brasiliensis, Cryptococcus neoformans var. grubii, and Cryptococcus gattii. Although prior studies have identified certain aspects of metal regulation in Cryptococcus species, little is known regarding the regulation of these elements in P. brasiliensis. We also present amino acid sequences analyses of deduced proteins in order to examine possible conserved domains. The genomic data reveals, for the first time, genes associated to iron, copper, and zinc assimilation and homeostasis in P. brasiliensis. Furthermore, analyses of the three fungal species identified homologs to genes associated with high-affinity uptake systems, vacuolar and mitochondrial iron storage, copper uptake and reduction, and zinc assimilation. However, homologs to genes involved in siderophore production were only found in P. brasiliensis. Interestingly, in silico analysis of the genomes of P. brasiliensis Pb01, Pb03, and Pb18 revealed significant differences in the presence and/or number of genes involved in metal homeostasis, such as in genes related to iron reduction and oxidation. The broad analyses of the genomes of P. brasiliensis, C. neoformans var. grubii, and C. gattii for genes involved in metal homeostasis provide important groundwork for numerous interesting future areas of investigation that are required in order to validate and explore the function of the identified genes and gene pathways.

Vacuum infiltration of copper aluminate by liquid aluminium

This paper studies attained microstructures and reactive mechanisms involved in vacuum infiltration of copper aluminate preforms with liquid aluminium. At high temperatures, under vacuum, the inherent alumina film enveloping the metal is overcome, and aluminium is expected to reduce copper aluminate, rendering alumina and copper. Under this approach, copper aluminate toils as a controlled infiltration path for aluminium, resulting in reactive wetting and infiltration of the preforms. Ceramic preforms containing a mixture of Al2O3 and CuAl2O4 were infiltrated with aluminium under distinct vacuum levels and temperatures, and the resulting reaction and infiltration behaviour is discussed. Copper aluminates stability ranges depend on vacuum level and oxygen partial pressure, which determine both CuAl2O4 and CuAlO2 ability for liquid aluminium infiltration. At 1100 °C and 0.76 atm vacuum level CuAl2O4 is stable, indicating pO2 above 0.11 atm. Reactive infiltration is achieved via reaction between aluminium and CuAl2O4; however, fast formation of an alumina film blocking liquid aluminium wicking results in incipient infiltration. At 1000 °C and 3.8 × 10−7 atm vacuum level, CuAlO2 decomposes to Cu and Al2O3 indicating a pO2 below 6.0 × 10−7 atm; infiltration of the ceramic is hindered by the non-wetting behaviour of the resulting metal alloy. At 1000 °C and 1.9 × 10−6 atm vacuum level CuAlO2 is stable, indicating pO2 above 6.0 × 10−7 atm. Extensive infiltration is achieved via redox reaction between aluminium and CuAlO2, rendering a microstructure characterised by uniform distribution of alumina particles amid an aluminium matrix. This work evidences that liquid aluminium infiltration upon copper aluminate-rich preforms is a feasible route to produce Al–matrix alumina-reinforced composites. The associated reduction reaction renders alumina, as fine particulate composite reinforcements, and copper, which dissolves in liquid aluminium contributing as a matrix strengthener.

I. Development of the In Situ Reductive Ozonolysis of Alkenes with Tertiary Amine N-Oxides. II. Progress toward the Asymmetric Synthesis of Peroxyplakoric Acid A3.

Ozone, first discovered in the mid 1800’s, is a triatomic allotrope of oxygen that is a powerful oxidant. For over a century, research has been conducted into the synthetic application and mechanism of reactions of ozone with organic compounds. One of the major areas of interest has been the ozonolysis of alkenes. The production of carbonyl compounds is the most common synthetic application of ozonolysis. The generally accepted mechanism developed by Rudolf Criegee for this reaction involves the 1,3-electrocyclic addition of ozone to the π bond of the alkene to form a 1,2,3-trioxolane or primary ozonide. The primary ozonide is unstable at temperatures above -100 °C and undergoes cycloreversion to produce the carbonyl oxide and carbonyl intermediates. These intermediates then recombine in another 1,3-electrocyclic addition step to form the 1,2,4-trioxolane or final ozonide. While the final ozonide is often isolable, most synthetic applications of ozonolysis require a subsequent reductive or oxidative step to form the desired carbonyl compound. During investigations into the nucleophilic trapping of the reactive carbonyl oxide, it was discovered that when amines were used as additives, an increased amount of reaction time was required in order to consume all of the starting material. Surprisingly, significant amounts of aldehydes and a suppression of ozonide formation also occurred which led to the discovery that amine N-oxides formed by the ozonation of the amine additives in the reaction were intercepting the carbonyl oxide. From the observed production of aldehydes, our proposed mechanism for the in situ reductive ozonolysis reaction with amine N-oxides involves the nucleophilic trapping of the carbonyl oxide intermediate to produce a zwitterionic adduct that fragments into 1O2, amine and the carbonyl thereby avoiding the formation of peroxidic intermediates. With the successful total syntheses of peroxyacarnoates A and D by Dr. Chunping Xu, the asymmetric total synthesis of peroxyplakorate A3 was investigated. The peroxyplakoric acids are cyclic peroxide natural products isolated from the Plakortis species of marine sponge that have been found to exhibit activity against malaria, cancer and fungi. Even though the peroxyplakorates differ from the peroxyacarnoates in the polyunsaturated tail and the head group, the lessons learned from the syntheses of the peroxyacarnoates have proven to be valuable in the asymmetric synthesis of peroxyplakorate A3. The challenges for the asymmetric synthesis of peroxyplakorate A3 include the stereospecific formation of the 3-methoxy-1,2-dioxane core with a propionate head group and the introduction of oxidation sensitive dienyl tail in the presence of a reduction sensitive 1,2-dioxane core. It was found that the stereochemistry of two of the chiral centers could be controlled by an anti-aldol reaction of a chiral propionate followed by the stereospecific intramolecular cyclization of a hydroperoxyacetal. The regioselective ozonolysis of a 1,2-disubstituted alkene in the presence of a terminal alkyne forms the required hydroperoxyacetal as a mixture of diastereomers. Finally, the dienyl tail is introduced by a hydrometallation/iodination of the alkyne to produce a vinyl iodide followed by a palladium catalyzed coupling reaction. While the coupling reaction was unsuccessful in these attempts, it is still believed that the intramolecular cyclization to introduce the 1,2-dioxane core could prove to be a general solution to many other cyclic peroxides natural products.