A quantum chemical study on the formation of phosphorus mononitride

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electrochemical kinetic study of surface layer growth on natural pyrite in acid medium

This paper presents electrochemical experiments on natural pyrite that combine potentiostatic and voltammetric techniques. X-ray microanalysis is used as an auxiliary technique. The layer growth on pyrite surface is conducted in a wide range of pH and potential range: 3.4 <= pH <= 5.9 with E = 0.80 V (versus SHE), and 0.80 V <= E <= 1.00 V with pH 4.5 (versus SHE) in acetic acid-acetate buffer. This work is unique for two reasons: (1) phenomenological model about layer growth is applied and mathematical-physic consistence is verified and (2) Meyer's hypotheses of chemical mechanism are used to explain kinetic parameters of the phenomenological model. (c) 2005 Elsevier B.V. All rights reserved.

Chemical evolution in the Asteraceae. The Oxidation-Reduction mechanism and production of secondary metabolites

This work describes the application of partial least squares (PLS) regression to variables that represent the oxidation data of several types of secondary metabolite isolated from the family Asteraceae. The oxidation states were calculated for each carbon atom of the involved compounds after these had been matched with their biogenetic precursor. The states of oxidation variations were named oxidation steps. This methodology represents a new approach to inspect the oxidative changes in taxa. Partial least square (PLS) regression was used to inspect the relationships among terpenoids, cournarins, polyacetylenes, and flavonoids from a data base containing approximately 27,000 botanical entries. The results show an interdependence between the average oxidation states of each class of secondary metabolite at tribe and sub tribe levels.

Interaction mechanism of poly (o-ethoxyaniline) and collagen blends

Blend films of poly (o-ethoxyaniline) (POEA) and collagen were fabricated by casting under optimized conditions and characterized by Raman scattering and UV-vis absorption spectroscopies. The UV-vis spectra showed that the addition of collagen in the aqueous solution of POEA promotes a dedoping of the POEA. This effect was also observed for the blend films as supported by Raman scattering and a mechanism for the chemical interaction between POEA-collagen is proposed. The influences of different percentage of collagen as well as the pH of stock solutions during the fabrication process of the blend films were also investigated. It was found that the preparation method plays an important role in the flexibility and freestanding properties of the films. Complementary, the surface morphology was studied by atomic force microscopy and the conductivity by dc measurements. (C) 2003 Elsevier Ltd. All rights reserved.

Iron phthalocyanine in non-aqueous medium forming layer-by-layer films: growth mechanism, molecular architecture and applications

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

The reactivity of oytho-methoxy-substituted catechol radicals with sulfhydryl groups: Contribution for the comprehension of the mechanism of inhibition of NADPH oxidase by apocynin

Redox processes are involved in the mechanism of action of NADPH oxidase inhibitors such as diphenyleneiodonium and apocynin. Here, we studied the structure-activity relationship for apocynin and analogous ortho-methoxy-substituted catechols as inhibitors of the NADPH oxidase in neutrophils and their reactivity with peroxidase. Aiming to alter the reduction potential, the ortho-methoxy-catechol moiety was kept constant and the substituents at para position related to the hydroxyl group were varied. Two series of compounds were employed: methoxy-catechols bearing electron-withdrawing groups (MC-W) such as apocynin, vanillin, 4-nitroguaiacol, 4-cyanoguaiacol, and methoxy-catechol bearing electron-donating groups (MC-D) such as 4-methylguaiacol and 4-ethylguaiacol. We found that MC-D were weaker inhibitors compared to MD-W. Furthermore, the radicals generated by oxidation of MC-W via MPO/H(2)O(2), but not for MC-D, were able to oxidize glutathione (GSH) as verified by the formation of thiyl radicals, depletion of GSH, and recycling of the ortho-methoxy-catechols during their oxidations. The capacity of oxidizing sulfhydryl (SH) groups was also verified when ovalbumin was incubated with MC-W, but not for MC-D. Since the effect of apocynin has been correlated with inactivation of the cytosolic fractions of the NADPH oxidase complex and its oxidation during the inhibitory process develops a special role in this process, we suggest that the close relationship between the reactivity of the radicals of MC-W compounds with thiol groups and their efficacy as NADPH oxidase inhibitor could be the chemical pathway behind the mechanism of action of apocynin and should be taken into account in the design of new and specific NADPH oxidase inhibitors. (c) 2007 Elsevier B.V. All rights reserved.

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.

Profiling the Proteome of the Venom from the Social Wasp Polybia paulista: A Clue to Understand the Envenoming Mechanism

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

New Insight into the Mechanism of Action of Wasp Mastoparan Peptides: Lytic Activity and Clustering Observed with Giant Vesicles

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Tracing source and evolution of suspended particles in the Rio Negro Basin (Brazil) using chemical species of iron

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Mechanism for interplay between electron and ionic fluxes in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds

This paper develops a framework for the interpretation of ionic insertion/deinsertion reactions in an aqueous environment taking place in transition-metal hexacyanoferrates of the general formula KhFek3+ [Fe2+ (CN)(6)](l)center dot mH(2)O, also called Prussian Blue. Three different processes were fully separated in the electrochemistry of these films. It was clearly identified that one of these electrochemical processes involves the insertion/deinsertion of H3O+ (hydrated protons) through the channels of the KhFek3+ [Fe2+ (CN)(6)](l) center dot mH(2)O structure to reach the film electroneutrality during the electron transfer between Everitt's Salt and Prussian Blue. The other electrochemical processes involve K+ or H+ (proton) exchange through the water crystalline structure existing in the channels of the KhFek3+ [Fe2+(CN)(6)](l)center dot mH(2)O structure.

Influence of cerium (IV) ions on the mechanism of organosilane polymerization and on the improvement of its barrier properties

In this work, the effect of cerium (IV) ammonium nitrate (CAN) addition on the polymerization of bis-[triethoxysilyl]ethane (BTSE) film applied on carbon steel was studied. The electrochemical characterization of the films was carried out in 0.1 mol L(-1) NaCl solution by open-circuit potential measurements, anodic and cathodic polarization curves and electrochemical impedance spectroscopy (EIS). Morphological and chemical characterization were performed by atomic force microscopy (AFM), contact angle measurements, infrared-spectroscopy, nuclear magnetic resonance and thermogravimetric analysis. The results have clearly shown the improvement on the protective properties of the Ce(4+) modified film as a consequence of the formation of a more uniform and densely reticulated silane film. A mechanism is proposed to explain the accelerating role of Ce(4+) ions on the cross-linking of the silane layer. (C) 2008 Elsevier Ltd. All rights reserved.

Formation Mechanism via a Heterocoagulation Approach of FePt Nanoparticles Using the Modified Polyol Process

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

Electrochromic Switching Mechanism of Iron Hexacyanoferrates Molecular Compounds: The Role of Fe2+(CN)(6) Vacancies

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

Chemical modulation on heterogeneous growth in Prochilodus lineatus (Valenciennes, 1847) (Pisces; Characiformes)

No presente trabalho, testou-se o efeito de fatores químicos liberados por coespecíficos sobre o crescimento e sua variabilidade no grupo (crescimento heterogêneo, CHet), numa espécie gregária, o curimbatá, Prochilodus lineatus. O CHet foi avaliado pelo coeficiente de variação do peso dos animais, em dois períodos consecutivos de 21 dias. Os peixes foram agrupados em aquários (4 peixes cada) que receberam água corrente, com vazão constante, de tanques contendo (C) ou não (N) coespecíficos. Quatro condições foram delineadas de acordo com a água que abastecia os aquários: a) água com contato prévio com coespecíficos durante todo o experimento (CC); b) água sem contato prévio com coespecíficos durante todo o experimento (NN); c) água com contato prévio com coespecíficos apenas no primeiro período, 0 a 21 dias (CN); e d) apenas no período de 21 a 42 dias (NC). Ao término dos experimentos, verificou-se que ocorre modulação química sobre a variabilidade de crescimento em P. lineatus: os peixes que receberam água com contato prévio com coespecífico (C) apresentaram exacerbação do CHet. Fato que corrobora a idéia de que o mecanismo predominante da determinação da variação intra-específica do crescimento, em espécies gregárias, está associado à ação de fatores químicos liberados por coespecíficos.