Theoretical study on the molecular mechanism for the reaction of VO2+ with C2H4

The complex reaction between VO2+ ((1)A(1)/(3)A) and C2H4 (Ag-1(g)/(3)A(1)) to yield VO+ ((1)Delta/(3)Sigma) and CH3CHO ('A'/(3)A) has been studied by means of B3LYP/6-31G* and B3LYP/6-311G(2d,p) calculations. The structures of all reactants, products, intermediates, and transition structures of this reaction have been optimized and characterized at the fundamental singlet and first excited triplet electronic states. Crossing points are localized, and possible spin inversion processes are discussed by means of the intrinsic reaction coordinate approach. Relevant stationary points along the most favorable reaction pathways have been studied at the CCSD/6-311G(2d,p)//B3LYP/6-311G(2d,p) calculation level. The theoretical results allow the development of thermodynamic and kinetic arguments about the reaction pathways of the title process. In the singlet state, the first step is the barrierless obtention of a reactant complex associated with the formation of a V-C bond, while in the triplet state a three-membered ring addition complex with the V bonded to the two C atoms is obtained. Similar behavior is found in the exit channels: the product complexes can be formed from isolated products without barriers. The reactant and product complexes are the most stable stationary points in the singlet and triplet electronic states. From the singlet state reactant complex, two reaction pathways are posssible to reach the triplet state product complex. (i) A mechanism in which a hydrogen transfer process is the first and rate limiting step and the second step is an oxygen transfer between vanadium and carbon atoms with a concomitant change in the spin state. The crossing point between singlet and triplet spin states is not kinetically relevant because it takes place at a later stage occurring in the exit channel. (ii) A mechanism in which the first stage renders a four-membered ring between vanadyl cation and the ethylene fragment and an oxygencarbon bond is formed; on going from this minimum to the second transition structure, associated with a carbon-vanadium bond breaking process, the crossing point between singlet and triplet spin states is reached. The final step is the hydrogen transfer between both carbon atoms to yield the product complex. In this case the spin change opens a lower barrier pathway. The transition structures with larger values of relative energies for both reactive channels of VO2+ ((1)A(1)) + C2H4 (Ag-1) --> VO+ ((3)Sigma) + CH3CHO ((1)A') present similar energies, and the two reaction pathways can be considered as competitive.

DFT study of the water-assisted tautomerization process between hydrated oxide, MO(H2O)(+), and dihydroxide, M(OH)(2)(+) cations (M = V, Nb and Ta)

Density functional theory (DFT) calculations point out that the participation of water can effectively lower the barrier height for the isomerization process between hydrated oxide cation, MO(H2O)(+), and dihydroxide cation, M(OH)(2)(+), (M = V, Nb and Ta). The catalytic effect is achieved by a water-assisted mechanism in which water acts as proton donor and acceptor, via a transition structure corresponding to a six-membered ring. In the case of vanadium atom, the presence of two water molecules has been taken into account and the tautomerization becomes nearly barrierless, decreasing both the stability of the transition structures relative to intermediates and the depths of wells associated with the intermediates. (C) 2003 Elsevier B.V. All rights reserved.

Variabilidade espacial de MO, P, K e CTC do solo sob diferentes usos e manejos

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

Recuperação de área degradada por construção de hidroelétrica com adubação verde e corretivo

As áreas de empréstimo em hidrelétricas são as áreas remanescentes da construção da fundação da barragem e podem ser consideradas áreas degradadas, pois delas foram retirados os horizontes superficiais do solo. Este trabalho teve como objetivo estudar a recuperação de um Latossolo Vermelho distrófico, degradado por construção civil (Usina Hidrelétrica de Ilha Solteira-SP), por meio de adubação verde e aplicação de calagem e gessagem. Os tratamentos constituíram-se de: testemunha (solo mobilizado e vegetação espontânea); mucuna-preta e guandu até 1994. Depois foram substituídos por feijão-de-porco; calcário + mucuna-preta; calcário + guandu até 1994. Nova substituição foi feita por feijão-de-porco; calcário + gesso + mucuna-preta e calcário + gesso + guandu até 1994. Outra substituição foi feita por feijão-de-porco. Esses tratamentos foram estabelecidos em blocos casualizados com quatro repetições: após quatro anos com os adubos verdes, um ano com milho, um ano com aveia-preta e dois anos com braquiária. Foram avaliados: pH, teores de Ca2+, Mg2+, P, K, capacidade de troca catiônica, saturação por bases e teor de matéria orgânica. Os tratamentos adotados estão recuperando os atributos químicos do solo degradado, e a mucuna-preta apresentou os melhores resultados, quando comparada ao guandu e feijão-de-porco. Os efeitos da recuperação dos atributos químicos do solo alcançaram a profundidade de 0,0-0,2 m. As técnicas adotadas para recuperação desses atributos químicos (adubação verde, calagem e gessagem) no primeiro ano atingiram a profundidade do solo de 0,0-0,1 m e, somente após cinco anos, de 0,0-0,2 m.

Influence of organic-mineral fertilization of an oxisol on soil chemical properties and Bracharia brizantha production

A utilização de fertilizante organomineral da indústria produtora dos aminoácidos lisina e treonina pode melhorar a fertilidade de solos tropicais. O presente trabalho teve como objetivo avaliar a influência de diferentes dosagens do fertilizante organomineral denominado Ajifer L-14 nos atributos químicos e no aumento de produção de forragem de um Latossolo Vermelho do noroeste paulista. O delineamento utilizado foi em blocos casualizados, com sete tratamentos e quatro repetições. Os tratamentos foram: T1- testemunha (sem aplicação de Ajifer L-14); T2- testemunha com vegetação natural; T3- adubação mineral de acordo com a necessidade da cultura e a análise do solo (usando 1,35 kg de ureia, 2,20 kg de superfosfato simples e 0,51 kg de KCl por parcela, o que corresponde a 60 kg de N, 40 kg de P2O5 e 30 kg ha-1 de K2O, respectivamente); T4- adubação com Ajifer L-14 de acordo com a recomendação da análise química do solo (40 L parcela-1, o que corresponde a 60 kg ha-1 N); T5- adubação com Ajifer L-14 em dosagem 50 % acima da recomendação (60 L parcela-1, o que corresponde a 90 kg ha-1 N; T6- adubação com Ajifer L-14 em dosagem 50 % abaixo da recomendação (20 L parcela-1, o que corresponde a 30 kg ha-1 N); T7- adubação com Ajifer L-14 em dosagem 25 % acima da recomendação (50 L parcela-1, o que corresponde a 75 kg ha-1 N); e T8- adubação com Ajifer L-14 em dosagem 25 % abaixo da recomendação (30 L parcela-1, o que corresponde a 45 kg ha-1 N). Nas profundidades de 0,0-0,1 e 0,1-0,2 m, avaliaram-se os seguintes atributos químicos do solo:, teor de matéria orgânica (MO), pH, K+, Ca2+, Mg2+, capacidade de troca catiônica (CTC), acidez potencial e saturação por bases. A aplicação do fertilizante organomineral não influenciou os atributos químicos do solo. Na análise de regressão, houve relação polinomial entre as doses de aplicação do fertilizante organomineral e a produção de massa seca e proteína bruta de Bracharia brizantha.

Revegetation and Soil Management Effects on Chemical Properties of a Saprolite Resulting from Deep Soil Removal

During the building of a hydroelectrical power plant at Ilha Solteira in the Parana River (Brazil), materials of a highly weathered soil Oxisol were extracted from a depth between 5 and 8 m for engineering works. This resulted in an abandoned depression area. The topsoil was not salvaged and the open pit was not backfilled, and as result vegetation hardly or not at all recovered. on the residual saprolite materials, an experimental field was established to assess different soil rehabilitation treatments. Field experiments were initiated in 1992. After soil tillage, two different crops and three different liming strategies were compared, giving six combinations. In addition, two uncropped control treatments, tilled and no-tilled, were established so that a total of eight treatments were assessed. The experimental design consisted of four randomized experimental blocks, which included a total of 32 plots with a plot area of 100 m(2). This experiment was used to study the effectiveness of the soil-reclamation treatments after a 9-year period. Soil samples were taken at three different depths (0-10, 10-20, and 20-40 cm), and they were analyzed routinely for pH, organic-matter content, and cation exchange capacity (CEC). Revegetation of the abandoned saprolite material increased soil organic-matter content and cation exchange capacity (CEC), and to some extent small differences between treatments were evidenced. Exchangeable calcium (Ca) and magnesium (Mg) recovered faster than organic-matter content. A significant linear relationship was found between organic-matter content and CEC, suggesting continued addition of organic material will further approach the value of these parameters to those levels corresponding to natural soils under "Cerrado" vegetation.

Gastroprotective Effect of Serjania erecta Radlk (Sapindaceae): Involvement of Sensory Neurons, Endogenous Nonprotein Sulfhydryls, and Nitric Oxide

The present study reveals the pharmacological action of Serjania erecta Radlk. (Family Sapindaceae), an important medicinal plant species used in the Brazilian Pantanal against gastric pain. The methanolic (Me) and chloroformic (Se) extracts obtained from leaves of S. erecta were challenged by a very strong necrotizing agent in rodents, absolute ethanol. Se was also confronted with a nitric oxide synthase inhibitor (N(G)-nitro-l-arginine methyl ester), a capsaicin cation channel transient receptor potential vanilloid type 1 antagonist (ruthenium red), or a sulfhydryl-blocker (N-ethylmaleimide) to evaluate the participation of these cytoprotective factors in gastroprotection. In an in vivo experimental model, Me and Se presented several degrees of gastroprotective action without signs of acute toxicity. The best gastroprotective effect was restricted to all doses of Se. The mechanisms involving the gastroprotective action of Se are related to an augmented defense mechanism of the gastrointestinal mucosa consisting of sensory neurons, nitric oxide, and sulfhydryl groups that prevent and attenuate the ulcer process. The presence of polyisoprenoids in the Se explains the potent gastroprotective action of this medicinal species. Effective gastroprotective action and the absence of acute toxicity indicate this species may be a promising herbal drug against gastric disease.

(1-x)PMN-xPT ceramics prepared by conventional and modified columbite route: Effect on electrical properties

This study aims to demonstrate how the chemical homogeneity of B cations affects the microstructure and electrical responses of (1-x) PMN-xPT ceramics. Two methodologies were employed to synthesize three different compositions, with x assuming the values 0.10, 0.28, and 0.35. If compared to conventional method, the Ti-modified columbite route, which is characterized by higher B cation homogeneity, leads to PMN-PT powders and ceramics with lower content of PNT pyrochlore phase and, for 0.65PMN-0.35PT composition, minor amount of tetragonal phase is found. Conclusively, PMN-PT ceramics obtained by modified route favors B cations homogeneity, enhancing the dielectric, ferroelectric and piezoelectric properties.

Effect of lithium additive on the microstructure and electrical responses of 0.9PMN-0.1PT ceramics

Structural effects of lithium additive on 0.9PMN-0.1PT powders prepared by Ti-modified columbite route were studied. The substitution of Li+ ions for Mg2+ ions in the B-site sub-lattice of 0.9PMN-0.1PT perovskite structure was explained in terms of lead and oxygen vacancies generation originated as consequence of the ionic compensation of negatively charged Li'(Mg) sites. The rise in mass transport as consequence of the increasing of Pb2+ and O2- vacancies produces more agglomerated particles during the powder synthesis and changes the mechanical characteristics between grain and grain boundary of sintered ceramic. The relation between K-m and T-m values, the difference between ionic radii of B cation and the molar volume were used to explain the changes in the relaxor behavior and diffusiveness of phase transition as function of lithium doping, which are corroborated by the results obtained through the ferroelectric characterization.

Synergistic effect in the catalytic activity of lipase Rhizomucor miehei immobilized on zeolites for the production of biodiesel

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

Purification and characterization of a new alkaline serine protease from the thermophilic fungus Myceliophthora sp.

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

Caracterização da matéria-prima cerâmica da Mina Tabajara (Limeira, SP)

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

Weathering rates at Alto Sorocaba basin, Brazil, using U-isotopes and major cations

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

Amino acid, Antioxidant and Ion Profiles of Carpolobia lutea Leaf (Polygalaceae)

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

Antioxidant activity, ascorbic acid and total phenol of exotic fruits occurring in Brazil

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