Hydrogen adsorption in a copper ZSM5 zeolite: an inelastic neutron scattering study

Currently microporous oxidic materials including zeolites are attracting interest as potential hydrogen storage materials. Understanding how molecular hydrogen interacts with these materials is important in the rational development of hydrogen storage materials and is also challenging theoretically. In this paper, we present an incoherent inelastic neutron scattering (INS) study of the adsorption of molecular hydrogen and hydrogen deuteride (HD) in a copper substituted ZSM5 zeolite varying the hydrogen dosage and temperature. We have demonstrated how inelastic neutron scattering can help us understand the interaction of H-2 molecules with a binding site in a particular microporous material, Cu ZSM5, and by implication of other similar materials. The H-2 molecule is bound as a single species lying parallel with the surface. As H-2 dosing increases, lateral interactions between the adsorbed H-2 molecules become apparent. With rising temperature of measurement up to 70 K (the limit of our experiments), H-2 molecules remain bound to the surface equivalent to a liquid or solid H-2 phase. The implication is that hydrogen is bound rather strongly in Cu ZSM5. Using the simple model for the anisotropic interaction to calculate the energy levels splitting, we found that the measured rotational constant of the hydrogen molecule is reduced as a consequence of adsorption by the Cu ZSM5. From the decrease in total signal intensity with increasing temperature, we were able to observe the conversion of para-hydrogen into ortho-hydrogen at paramagnetic centres and so determine the fraction of paramagnetic sites occupied by hydrogen molecules, ca. 60%. (c) 2006 Elsevier B.V. All rights reserved.

On the catalytic hydrogenation of polycyclic aromatic hydrocarbons into less toxic compounds by a facile recoverable catalyst

Here we present the catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) to less toxic mixtures of saturated and partial unsaturated polycyclic hydrocarbons under mild reaction conditions using a magnetically recoverable rhodium catalyst and molecular hydrogen as the exclusive H source. The catalyst is easily recovered after each reaction by placing a permanent magnet on the reactor wall and it can be reused in successive runs without any significant loss of catalytic activity. As an example, anthracene was totally converted into the saturated polycyclic hydrocarbon form (ca. 60%) and the partially hydrogenated form, 1,2,3,4,5,6,7,8-octahydroanthracene (ca. 40%). The catalyst operates in a broad range of temperature and H(2) pressure in both organic and aqueous/organic solutions of anthracene and it also exhibits significant activity at low substrate concentrations (20 ppm). This can be an efficient recycling process for hydrogenation of PAHs present in contaminated fluid waste streams. (C) 2009 Elsevier B.V. All rights reserved.

Spectroscopic and theoretical studies of some N,N-diethyl-2-[(4 `-substituted)phenylsulfonyl]acetamides

The analysis of the IR carbonyl band of the N,N-diethyl-2-[(4`-substituted)phenylsulfonyl]acetamides Et(2)NC(O)CH(2)S(O)(2)-C(6)H(4)-Y (Y = OMe 1, Me 2,1-13, Cl 4, Br 5, NO(2) 6) supported by B3LYP/6-31G(d,p) calculations for 3, indicated the existence of three pairs (anti and syn) of cis (c) and gauche (g(1) and g(2)) conformers in the gas phase, being the gauche conformers significantly more stable than the cis ones. The anti geometry is more stable than the syn one, for each pair of cis and gauche conformers. The summing up of the orbital (NBO analysis) and electrostatic interactions justifies quite well the populations and the v(CO) frequencies of the anti and syn pairs of c, g(1) and g(2) conformers. The IR higher carbonyl frequency component whose population is ca. 10%, in CCl(4), may be ascribed to the least stable and most polar cis conformer pair (in the gas phase) and the lower frequency component whose population is ca. 90%, to the summing up of the populations of the two most stable and least polar gauche conformer pairs (g(1) and g(2)) (in the gas phase). The reversal of the cis(c)/gauche (g(1) + g(2)) population ratio observed in chloroform ca. 60% (cis)/40% (gauche) and the occurrence of the most polar cis(c) conformer only, in acetonitrile, strongly suggests the coalescence of the two gauche components in a unique carbonyl band in solution. A further support to this rationalization is given by the single point PCM solvation model performed by HF/6-31G(d,p) method, which showed a progressive increase of the c/(g(1) + g(2)) ratio going from gas to CCl(4), to CHCl(3) and to CH(3)CN. X-ray single crystal analysis of 4 indicates that this compound assumes, in the solid state, the syn-clinal (gauche) conformation with respect to the [O=C-CH(2)-S] moiety, and the most stable anti geometry relative to the [C(O)N(CH(2)CH(3))(2)] fragment. In order to obtain larger energy gain from the crystal packing the molecules of 4 are linked in centrosymmetric dimers through two C-H center dot center dot center dot O interactions (C-H([O-Ph])center dot center dot center dot O([SO2])) forming a step ladder. (C) 2011 Elsevier B.V. All rights reserved.

Influence of stocking densities in the nursery phase on the growth of Macrobrachium amazonicum reared in net pens

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

Effects of probiotic bacteria, isoflavones and simvastatin on lipid profile and atherosclerosis in cholesterol-fed rabbits: a randomized double-blind study

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

Assessment of cumulative damage by using ultrasonic C-scan on carbon fiber/epoxy composites under thermal cycling

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

Valor nutricional da silagem de grãos úmidos de milho com diferentes graus de moagem para leitões na fase de creche

Utilizaram-se 72 leitões mestiços (Landrace x Large White), com peso inicial médio de 7,1kg, no experimento de desempenho e 20 leitões mestiços, com peso inicial médio de 18,9kg, no experimento de digestibilidade para avaliar a silagem de grãos úmidos de milho com diferentes granulometrias para leitões em fase de creche. O delineamento experimental foi em blocos ao acaso. em ambos os experimentos avaliaram-se o valor nutricional das silagens com diâmetro geométrico médio (DGM) das partículas de 979, 1168 e 2186µm e do milho seco com DGM das partículas de 594µm. Na fase de zero ao oitavo dia, a silagem proporcionou menor consumo diário de ração (CDR) em relação ao milho seco, e foi verificado aumento linear no CDR com o aumento da granulometria da silagem. A silagem com granulometria média e grossa proporcionou melhora na conversão alimentar (CA) em relação ao milho seco, mas não foi observada diferença no ganho diário de peso (GDP). Para o período total, não foram observadas diferenças estatísticas para CDR e GDP, entretanto a silagem proporcionou melhora na CA em relação ao milho seco havendo efeito linear crescente da granulometria da silagem sobre a CA. A granulometria da silagem não influenciou nos coeficientes de digestibilidade aparente (CDA) da matéria seca e da proteína bruta, porém proporcionou maiores CDA do fósforo e valores de energia digestível em relação ao milho seco. O CDA do cálcio e os valores de energia metabolizável foram maiores para a silagem com granulometria fina e média, comparado ao do milho seco. Houve redução linear do CDA do cálcio com o aumento da granulometria da silagem.

Crystallization and preliminary diffraction data of BaP1, a haemorrhagic metalloproteinase from Bothrops asper snake venom

BaP1 is a metalloproteinase isolated from the venom of the Central American snake Bothrops asper (terciopelo). It is a 24 kDa protein consisting of a single chain which includes the metalloproteinase domain only, therefore being classified as a class P-I snake-venom metalloproteinase. BaP1 induces prominent local tissue damage, such as haemorrhage, myonecrosis, blistering, dermonecrosis and oedema. In order to elucidate its structure, BaP1 was crystallized by the hanging-drop vapour-diffusion technique in 0.1 M bicine pH 9.0, 10% PEG 20 000 and 2%(v/v) dioxane. Diffraction data were observed to a resolution of 2.7 Angstrom. Crystals belong to space group P2(1)2(1)2(1), with unit-cell parameters a = 38.22, b = 60.17, c = 86.09 Angstrom.

Surface structure and electronic properties of Pt-Fe/C nanocatalysts and their relation with catalytic activity for oxygen reduction

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

Study of the enthalpy-entropy mechanism from water sorption of orange seeds (C. sinensis cv. Brazilian) for the use of agro-industrial residues as a possible source of vegetable oil production

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

Persistence of conidia of Entomophthora muscae in relation to age, temperature, and humidity

In this paper, the effect of age, humidity, and temperature on the conidial survival of Entomophthora muscae was evaluated. E. muscae was obtained from Musca domestica in a dairy in Itatiba (São Paulo, Brazil) and maintained in the laboratory by continuous passage through flies. Furthermore, the ability of conidia to infect flies at three temperatures (17, 21, and 27 degrees C), four ages of conidia (12, 72, 96, and 154 hours) and two humidities (100 and 60% RH) was evaluated. The temperature of 21 degrees C was the most favorable for the infection of house flies. Humidity was a cause of variation at 27 degrees C when the conidia were up to 12 hours old, but had no effect at lower temperatures. Conidia held at 100% RH and aged 72 hours caused no infection at 17 degrees C, but were infective at 21 degrees C. In the present study, conidia retained viability much longer than previously observed. Finally, the effect of humidity, temperature, and conidial age is discussed.

Gamma phases in Cu-Al alloys and the influence of a square shaped phase in the electrochemical behavior of a Cu-13.6wt% Al alloy

The electrochemical behavior of Cu-xAl alloys, with 11 wt%less than or equal to x less than or equal to 15wt%, in 0.5 M H2SO4 was studied by means of open-circuit potential decay measurements, quasi-stationary and fast cyclic voltammetry, and electrochemical impedance spectroscopy. Some of the alloys (x less than or equal to 14%), when quenched formed martensitic structures. Alloys with greater than or equal to 13% showed a little square-shaped phase when quenched from temperatures around 800 degrees C. It was observed that in sulfuric medium, these formations were dealuminized differently than the martensitic phase. The values of the rest potentials are more influenced by the heat treatment rather than by the alloy composition. An anodic Tafel slope of ca. 60 mV/decade was observed for all the alloys, independently of the heat treatment. This is explained in terms of a competition between two processes: copper oxidation and copper(I) deproportionation. In the cyclic voltammetric experiments it was observed an anodic current peak, related with copper oxidation with a possible formation of some interfacial species, and a cathodic current peak during the reverse potential scan, associated with the reduction of soluble species and/or of the film. The AC Impedance data were interpreted in terms of electric equivalent circuits.

Processamento e caracterização de snack extrudado a partir de farinhas de quirera de arroz e de bandinha de feijão

Este trabalho teve por objetivo desenvolver nova formulação de snack por extrusão termoplástica a partir de mistura de farinhas de quirera de arroz e de bandinha de feijão, bem como avaliar o potencial nutricional, tecnológico e sensorial do novo produto. A farinha de bandinha de feijão carioca foi incorporada à farinha de quirera de arroz na proporção de 30%. O snack foi produzido em extrusora monorrosca, escala piloto. Os parâmetros de extrusão foram fixos, utilizando-se três zonas de extrusão com temperaturas de 40, 60 e 85 °C; velocidade do parafuso de 177 rpm; taxa de alimentação de 292 g.min-1, e matriz circular de 3,85 mm de diâmetro. A amostra de snack foi submetida a caracterizações fisicoquímica, tecnológica e sensorial. Observou-se efeito significativo da farinha de bandinha de feijão no aumento dos teores proteico e de fibras no snack obtido, quando comparada à farinha de quirera de arroz. Em relação às características tecnológicas do produto, obteve-se 0,17 g.cm-3 para densidade aparente, 7,75 para o índice de expansão e 435, g.f para a dureza instrumental. A formulação estudada foi aceita sensorialmente, com índice de aceitação para impressão global de 76%. Conclui-se que é possível produzir snacks por extrusão a partir da incorporação de 30% de farinha de bandinha de feijão à farinha de quirera de arroz, resultando em produto aceito sensorialmente e com adequado valor nutricional.

Polyphenol oxidase from sweet potato: Purification and properties

Polyphenol oxidase (PPO, EC 1.14.18.1) extracted from sweet potato root [Ipomoea batatas (L.) Lam.] was purified 189-fold by precipitation with ammonium sulfate and elution from columns of Sephadex G-25, DEAE-cellulose, and Sephadex G-100. Polyacrylamide gel electrophoresis of the purified preparation revealed that PPO was highly purified by the procedure adopted. The purified enzyme had an estimated molecular weight of 96 000 and Km values of 26, 8, 5, and 96 mM for 4-methylcatechol, chlorogenic acid, caffeic acid, and catechol, respectively. The optimum pH varies from about 4.0 to 6.5, depending on the substrate. PPO activity was inhibited by p-coumaric and cinnamic acids, sodium metabisulfite, dithioerythritol, ascorbic acid, L-lysine, D-phenylalanine, L-methionine, glycine, L-isoleucine, and L-glutamine. Heat inactivation between 60 and 80 °C was biphasic. Sucrose, (NH4)2SO4, NaCl, and KCl appeared to be protective agents of sweet potato PPO against thermal denaturation. © 1992 American Chemical Society.

Effect of humidity and solvent vapor phase on cellulose esters films

In the present study the effect of relative humidity (RH) during spin-coating process on the structural characteristics of cellulose acetate (CA), cellulose acetate phthalate (C-A-P), cellulose acetate butyrate (CAB) and carboxymethyl cellulose acetate butyrate (CMCAB) films was investigated by means of atomic force microscopy (AFM), ellipsometry and contact angle measurements. All polymer solutions were prepared in tetrahydrofuran (THF), which is a good solvent for all cellulose esters, and used for spin-coating at RH of (35 +/- A 5)%, (55 +/- A 5)% or (75 +/- A 5)%. The structural features were correlated with the molecular characteristics of each cellulose ester and with the balance between surface energies of water and THF and interface energy between water and THF. CA, CAB, CMCAB and C-A-P films spin-coated at RH of (55 +/- A 5)% were exposed to THF vapor during 3, 6, 9, 60 and 720 min. The structural changes on the cellulose esters films due to THF vapor exposition were monitored by means of AFM and ellipsometry. THF vapor enabled the mobility of cellulose esters chains, causing considerable changes in the film morphology. In the case of CA films, which are thermodynamically unstable, dewetting was observed after 6 min exposure to THF vapor. On the other hand, porous structures observed for C-A-P, CAB and CMCAB turned smooth and homogeneous after only 3 min exposure to THF vapor.