Hydrogen adsorption on boron doped graphene: an ab initio study

(i) The electronic and structural properties of boron doped graphene sheets, and (ii) the chemisorption processes of hydrogen adatoms on the boron doped graphene sheets have been examined by ab initio total energy calculations. In (i) we find that the structural deformations are very localized around the boron substitutional sites, and in accordance with previous studies (Endo et al 2001 J. Appl. Phys. 90 5670) there is an increase of the electronic density of states near the Fermi level. Our simulated scanning tunneling microscope (STM) images, for occupied states, indicate the formation of bright (triangular) spots lying on the substitutional boron (center) and nearest-neighbor carbon (edge) sites. Those STM images are attributed to the increase of the density of states within an energy interval of 0.5 eV below the Fermi level. For a boron concentration of similar to 2.4%, we find that two boron atoms lying on the opposite sites of the same hexagonal ring (B1-B2 configuration) represents the energetically most stable configuration, which is in contrast with previous theoretical findings. Having determined the energetically most stable configuration for substitutional boron atoms on graphene sheets, we next considered the hydrogen adsorption process as a function of the boron concentration, (ii). Our calculated binding energies indicate that the C-H bonds are strengthened near boron substitutional sites. Indeed, the binding energy of hydrogen adatoms forming a dimer-like structure on the boron doped B1-B2 graphene sheet is higher than the binding energy of an isolated H(2) molecule. Since the formation of the H dimer-like structure may represent the initial stage of the hydrogen clustering process on graphene sheets, we can infer that the formation of H clusters is quite likely not only on clean graphene sheets, which is in consonance with previous studies (Hornekaer et al 2006 Phys. Rev. Lett. 97 186102), but also on B1-B2 boron doped graphene sheets. However, for a low concentration of boron atoms, the formation of H dimer structures is not expected to occur near a single substitutional boron site. That is, the formation (or not) of H clusters on graphene sheets can be tuned by the concentration of substitutional boron atoms.

Role of the triad N46, S106 and T107 and the surface charges in the determination of the acidic pH optimum of digestive lysozymes from Musca domestica

Structures of digestive lysozymes 1 and 2 from housefly (MdL1 and MdL2) show that S106-T107 delimit a polar pocket around E32 (catalytic acid/base) and N46 contributes to the positioning of 050 (catalytic nucleophile), whereas those residues are replaced by V109-A110 and D48 in the non-digestive lysozyme from hen egg-white (HEWL). Further analyses revealed that MdL1 and MdL2 surfaces are less positively charged than HEWL surface. To verify the relevance of these differences to the acidic pH optimum of digestive lysozymes it was determined that pKas of the catalytic residues of the triple mutant MdL2 (N46D-S106V-T107A) are similar to HEWL pKas and higher than those for MdL2. In agreement, triple mutant MdL2 and HEWL exhibits the same pH optimum upon methylumbelliferylchitotrioside. In addition to that, the introduction of six basic residues on MdL1 surface increased by 1 unit the pH optimum for the activity upon bacterial walls. Thus, the acidic pH optimum for MdL2 and MdL1 activities upon methylumbelliferylchitotrioside is determined by the presence of N46, S106 and T107 in the environment of their catalytic residues, which favors pKas reduction. Conversely, acidic pH optimum upon bacterial walls is determined by a low concentration of positive charges on the MdL2 and MdL1 surfaces. (C) 2010 Elsevier Inc. All rights reserved.

Catalytic ethanolysis of soybean oil with immobilized lipase from Candida antarctica and (1)H NMR and GC quantification of the ethyl esters (biodiesel) produced

The catalytic ethanolysis of soybean oil with commercial immobilized lipase type B from Candida antarctica to yield ethyl esters (biodiesel) has been investigated. Transesterification was monitored with respect to the following parameters: quantity of biocatalyst, reaction time, amount of water added and turnover of lipase. The highest yields of biodiesel (87% by (1)H NMR; 82.9% by GC) were obtained after a reaction time of 24 h at 32 degrees C in the presence of lipase equivalent to 5.0% (w/w) of the amount of soybean oil present. The production of ethyl esters by enzymatic ethanolysis was not influenced by the addition of water up to 4.0% (v/v) of the alcohol indicating that it is possible to use hydrated ethanol in the production of biodiesel catalyzed by lipase. The immobilized enzyme showed high stability under moderate reaction conditions and retained its activity after five production cycles. The (1)H NMR methodology elaborated for the quantification of biodiesel in unpurified reaction mixtures showed good correlations between the signal areas of peaks associated with the alpha-methylene groups of the ethyl esters and those of the triacyl-glycerides in residual soybean oil. Monoacylglycerides, diacylglycerides and triglycerides could also be detected and quantified in the crude biodiesel using (1)H NMR spectroscopic and GC-FID chromatographic methods. The biodiesel production by enzymatic catalysis was promising. In this case, was produced a low concentration of glycerol (0.74%) and easily removed by water extraction. (C) 2010 Elsevier B.V. All rights reserved.

Solid phase microextraction as a reliable alternative to conventional extraction techniques to evaluate the pattern of hydrolytically released components in Vitis vinifera L. grapes

In present research, headspace solid-phase microextraction (HS-SPME) followed by gas chromatography–mass spectrometry (GC–qMS), was evaluated as a reliable and improved alternative to the commonly used liquid–liquid extraction (LLE) technique for the establishment of the pattern of hydrolytically released components of 7 Vitis vinifera L. grape varieties, commonly used to produce the world-famous Madeira wine. Since there is no data available on their glycosidic fractions, at a first step, two hydrolyse procedures, acid and enzymatic, were carried out using Boal grapes as matrix. Several parameters susceptible of influencing the hydrolytic process were studied. The best results, expressed as GC peak area, number of identified components and reproducibility, were obtained using ProZym M with b-glucosidase activity at 35 °C for 42 h. For the extraction of hydrolytically released components, HS-SPME technique was evaluated as a reliable and improved alternative to the conventional extraction technique, LLE (ethyl acetate). HS-SPME using DVB/CAR/PDMS as coating fiber displayed an extraction capacity two fold higher than LLE (ethyl acetate). The hydrolyzed fraction was mainly characterized by the occurrence of aliphatic and aromatic alcohols, followed by acids, esters, carbonyl compounds, terpenoids, and volatile phenols. Concerning to terpenoids its contribution to the total hydrolyzed fraction is highest for Malvasia Cândida (23%) and Malvasia Roxa (13%), and their presence according previous studies, even at low concentration, is important from a sensorial point of view (can impart floral notes to the wines), due to their low odor threshold (μg/L). According to the obtained data by principal component analysis (PCA), the sensorial properties of Madeira wines produced by Malvasia Cândida and Malvasia Roxa could be improved by hydrolysis procedure, since their hydrolyzed fraction is mainly characterized by terpenoids (e.g. linalool, geraniol) which are responsible for floral notes. Bual and Sercial grapes are characterized by aromatic alcohols (e.g. benzyl alcohol, 2-phenylethyl alcohol), so an improvement in sensorial characteristics (citrus, sweet and floral odors) of the corresponding wines, as result of hydrolytic process, is expected.

Estudo do crescimento, eficiência de biofiltração e cinética de absorção de nutrientes (N-NH, N-NO e P-PO4³) da macroalga Gracilaria cervicornis (Turner) J. Agardh

The objective of this study was to examine the growth of Gracilaria cervicornis cultured in a shrimp (Litopenaeus vannamei) pond and to determine the absorption efficiency and the kinetics parameters (Vmax, Ks e Vmax:Ks) of this macroalgae for the nutrients N-NO3-, N-NH4+ and P-PO4-3, aiming at its use as bioremediatory of eutrophicated environments. For this study, two experiments (field and laboratory) were developed. In the field study, the seaweed was examined in relation to the growth and the biomass. In the laboratory experiment, the absorption efficiency of G. cervicornis was measured through the monitoring of the concentration of the three nutrients (N-NO3-, N-NH4+ e P-PO4-3) during 5 hours and the kinetic parameters were determined through the formula of Michaelis-Menten. The results obtained in this study demonstrated that G. cervicornis benefited from the available nutrients in the pond, increasing 52.4% of its biomass value after 30 days of culture. It was evidenced that the variability of the biomass could be explained through the salinity, availability of light (transparency and solid particle in suspension) and concentration of N-NO3- in the environment. In the laboratory experiment, the highest absorption efficiency was found in the treatments with low concentration (5 µmol.L-1), being evidenced a reduction of up to 85,3%, 97,5% and 81,2% of N-NH4+, N-NO3- and P-PO43-, respectively. Regarding the kinetic parameters, G. cervicornis presented better ability in absorbing N-NH4+ in high concentrations (Vmax = 158,5 µmol g-1 dry wt h-1) and P-PO43- in low concentrations (Ks = 5 µmol.L-1 e Vmax:Ks = 10,3). The results of this study show that G. cervicornis could be cultivated in shrimp ponds, presents a good capacity of absorption for the tested nutrients and is a promising candidate for biorremediation in shrimp pond effluent

Contribuição da catodoluminescência para o entendimento da diagênese da formação Jandaíra: áreas do campo de petróleo da fazenda Belém e Lajedo do Rosário

The general objective of this study was to contribute to the understanding of the chemical evolution of fluids that percolate through carbonate rocks of the Jandaíra Formation. The oxidation and reduction conditions in which grains, source and cement were formed was investigated using the cathodoluminescence technique (CL). The study area is located in the west part of the Potiguar Basin (Fazenda Belém field) and Rosário Ledge (Felipe Guerra municipality, State of Rio Grande do Norte, Brazil). The analysis of thin sections of carbonate rocks under CL revealed that grains (allochemical or not) and diagenetic products (micritization, dolomitization, neomorphism and cementation) exhibit since absence of luminescence the various luminescence colors (yellow, orange, red, brown, and blue) in a variety of intensities. As pure calcite shows dark blue luminescence, the occurrence of different luminescence colors in calcite crystals suggest one or more punctual crystal defects such as free electron, free space and impurity. The dyeing of thin sections with alizarin and potassium ferrocyanide revealed the absence of ferrous carbonate in the different lithotypes of Jandaíra Formation. Therefore, the different colors and intensities of CL observed in these rocks are probably caused by the presence of ion activators such as Mn2+ and is not an activator/inhibitor combination. In the same way, the absence of luminescence is very probably caused by the absence of activator ions and not due to the low concentration of inhibitor ions such as Fe2+. The incorporation of Mn2+ in the different members of the Jandaíra Formation must have been controlled by the redox state of the depositional environment and diagenesis. Therefore, it is possible that the luminescent members have been formed (e.g.,ooids) or have been modified (gastropod neomorphism) under reduction conditions in the depositional environments, in subsurface during the burial, or, in the case of Rosario Ledge samples , during the post-burial return to surface conditions. As regards the sudden changes from low to moderate and to strong luminescence, these features should indicate the precipitation of a fluid with chemical fluctuations, which formed the frequent zonations in the block cement of the Rosario Ledge samples. This study suggests that the different intensities and colors of CL should be correlated with the Mn2+ and Fe2+ contents, and stable isotopes of samples to determine the salinity, temperature, pH e Eh conditions during deposition

Efeito da perda de carga e calor no poço injetor no processo de drenagem gravitacional assistido com vapor e solvente

Nowadays, most of the hydrocarbon reserves in the world are in the form of heavy oil, ultra - heavy or bitumen. For the extraction and production of this resource is required to implement new technologies. One of the promising processes for the recovery of this oil is the Expanding Solvent Steam Assisted Gravity Drainage (ES-SAGD) which uses two parallel horizontal wells, where the injection well is situated vertically above the production well. The completion of the process occurs upon injection of a hydrocarbon additive at low concentration in conjunction with steam. The steam adds heat to reduce the viscosity of the oil and solvent aids in reducing the interfacial tension between oil/ solvent. The main force acting in this process is the gravitational and the heat transfer takes place by conduction, convection and latent heat of steam. In this study was used the discretized wellbore model, where the well is discretized in the same way that the reservoir and each section of the well treated as a block of grid, with interblock connection with the reservoir. This study aims to analyze the influence of the pressure drop and heat along the injection well in the ES-SAGD process. The model used for the study is a homogeneous reservoir, semi synthetic with characteristics of the Brazilian Northeast and numerical simulations were performed using the STARS thermal simulator from CMG (Computer Modelling Group). The operational parameters analyzed were: percentage of solvent injected, the flow of steam injection, vertical distance between the wells and steam quality. All of them were significant in oil recovery factor positively influencing this. The results showed that, for all cases analyzed, the model considers the pressure drop has cumulative production of oil below its respective model that disregards such loss. This difference is more pronounced the lower the value of the flow of steam injection

Resposta imune-humoral de búfalos (Bubalus bubalis) contra Anaplasma marginale (Theiler, 1910)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Resposta de mudas de goiabeira a aplicação de fósforo

Phosphorus is a nutrient that most limits plant growth because of its importance in nutrition and low concentration in tropical soils. The present study aimed to evaluate the response of guava to application of phosphorus. For this, the experiment was conducted in a greenhouse at UNESP, Jaboticabal Campus, with guava plants (cv. Paluma) from herbaceous plants cultivated in plastic bags (2.8 dm(-3)), filled with Alfissol (P = 2 mg dm(-3)), between November 2007 and April 2008. The treatments consisted of five doses of phosphorus (0, 100, 200, 300 and 400 mg dm(-3)) in the form of triple superphosphate (44% P(2)O(5)), arranged in a randomized block design with four replications. After 100 days of transplantation evaluated the phosphorus content in soil, dry weight of shoot and root phosphorus and zinc in the shoot. The highest production of dry weight guava was a dose of 257 g dm(-3) of phosphorus and was associated with P content in soil and leaf 110 mg dm(-3) and 2,3 g kg(-1).

Resposta de mudas de goiabeira à aplicação de zinco

O subsolo, normalmente utilizado para produção de mudas de frutíferas, apresenta baixa concentração de zinco e, assim, existe grande probabilidade de resposta à aplicação deste micronutriente. Considerando a falta de informações sobre o assunto, procurou-se avaliar o efeito da aplicação de zinco ao substrato de produção das mudas de goiabeira e acompanhar os efeitos no desenvolvimento, na produção de matéria seca e no estado nutricional das plantas. O delineamento experimental foi em blocos ao acaso, com cinco tratamentos e cinco repetições. As doses de zinco, na forma de sulfato de zinco, foram: 0; 2; 4; 6 e 8 mg dm-3 de Zn. No plantio, as mudas receberam doses de N, P, K e B de 300; 100; 150 e 0,5 mg dm-3, respectivamente. O experimento foi conduzido em viveiro telado, em vasos com 2,8 dm³ de substrato de um Argissolo Vermelho-Amarelo. Após 135 dias do plantio, avaliaram-se: a altura, a área foliar e a matéria seca da parte aérea e das raízes, bem como os teores de macronutrientes e de Zn. As mudas de goiabeira responderam positivamente à aplicação de zinco. O maior desenvolvimento das mudas esteve associado à dose de 2 mg dm-3 de Zn. Doses iguais ou superiores a 4 mg dm-3 causaram redução significativa no desenvolvimento e no acúmulo de macronutrientes nas mudas de goiabeira.

Liberação de micronutrientes de uma escória aplicada em um Argissolo Vermelho-Amarelo cultivado com mudas de goiabeira (Psidium guajava L.)

Os micronutrientes são importantes na nutrição das plantas, especialmente em solos tropicais com baixa concentração devido ao intemperismo. Como fonte alternativa de micronutrientes, tem-se a escória, resíduo da indústria de produção de ferro-gusa e aço. Assim, objetivou-se avaliar a escória como fonte de micronutrientes para mudas de goiabeira. O delineamento experimental foi em blocos ao acaso, com cinco repetições. As doses de escória foram aplicadas objetivando elevar em meia, uma vez, uma vez e meia, duas vezes e duas vezes e meia a saturação por bases do solo igual a 70%, correspondendo a 1,68; 3,36; 5,04; 6,72 e 8,40 g por vaso, além da testemunha sem aplicação. Após 90 dias de incubação da escória com o Argissolo Vermelho-Amarelo, cultivaram-se mudas de goiabeira (cv. Paluma) por 110 dias em vasos com 2,8 dm-3 de substrato, em viveiro telado, em Taquaritinga-SP, no período de outubro de 2000 a abril de 2001. A escória promoveu um efeito favorável na reação do solo e na disponibilidades de Zn, Cu, Mn e B do solo. Houve efeitos quadráticos nas concentrações de Zn, Cu e Mn do solo, que, por sua vez, estiveram associadas às doses de escória superiores a 5,8; 6,3 e 7,5 g por vaso, respectivamente, enquanto, para o B, esse efeito foi linear. A saturação por bases do solo, entre 51 e 55%, resultou em maior disponibilidade dos micronutrientes Zn, Cu e Mn no solo, ao passo que, para o B, esse valor foi de 65%. da mesma forma que ocorreu no solo, a aplicação da escória apresentou efeitos quadráticos nos teores de Zn, Cu e Mn da parte aérea e das raízes das mudas de goiabeira, enquanto, para o B, esse efeito foi linear. Concluiu-se, portanto, que a escória se comportou como material corretivo da acidez e como fonte de micronutrientes.

Efeitos da aplicação de zinco no desenvolvimento, no estado nutricional e na produção de matéria seca de mudas de maracujazeiro

Sabe-se que os solos das regiões tropicais, devido ao intemperismo, apresentam baixas concentrações de micronutrientes, especialmente zinco. Desse modo, objetivou-se avaliar a aplicação de zinco ao substrato de produção de mudas de maracujazeiro, acompanhando seus efeitos no desenvolvimento, no estado nutricional e na produção de matéria seca das plantas. O delineamento experimental foi em blocos ao acaso, com cinco tratamentos e quatro repetições. As doses de zinco, na forma de sulfato de zinco, foram: 0; 2; 4; 6 e 8 mg de Zn dm-3 de solo. As mudas receberam doses de N, P, K e B de 300; 450; 150 e 0,5 mg dm-3, respectivamente, sendo o N e o K parcelados em três vezes (15; 30 e 45 dias após a semeadura). O experimento foi conduzido em condições de casa de vegetação, em vasos com 2 dm³ de substrato de um Latossolo Vermelho distrófico. Após 70 dias do plantio, avaliaram-se: o diâmetro do caule, a altura, a área foliar e a matéria seca da parte aérea e das raízes, bem como os teores de macro e micronutrientes. As mudas de maracujazeiro responderam positivamente à aplicação de zinco. O maior desenvolvimento das mudas esteve associado à dose de 5 mg de Zn dm-3.

Characterization of condensed tannins from native legumes of the Brazilian northeastern semi-arid

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

Reciclagem de material asfáltico fresado utilizando solventes e microemulsões

With the increase of asphalt milling services was also a significant increase in recycling services pavements. The techniques used today are basically physical processes in which the milled material is incorporated into new asphalt mixtures or executed on site, with the addition of virgin asphalt and rejuvenating agent. In this paper seeks to analyze the efficiency of extraction of CAP (Petroleum Asphalt Cement) mixtures from asphalt milling, using commercial solvents and microemulsions. The solvents were evaluated for their ability to solubilize asphalt using an extractor reflux-type apparatus. Pseudoternary diagrams were developed for the preparation of microemulsion O/W surfactant using a low-cost coconut oil saponified (OCS). Microemulsions were used to extract the CAP of asphalt through physicochemical process cold. Analysis was performed concentration of CAP in solution by spectroscopy. The data provided in the analysis of concentration by the absorbance of the solution as the basis for calculating the percentage of extraction and the mass flow of the CAP in the solution. The results showed that microemulsions prepared with low concentration of kerosene and butanol/OCS binary has high extraction power of CAP and its efficiency was higher than pure kerosene, reaching 95% rate of extraction

Correção da acidez e mobilidade de íons em Latossolo com aplicação superficial de escória, lama cal, lodos de esgoto e calcário

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