146 resultados para ESPECTROSCOPIA C-13 NMR


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Although many studies have shown that soil solution chemistry can be a reliable indicator of biogeochemical cycling in forest ecosystems, the effects of litter manipulations on the fluxes of dissolved elements in gravitational soil solutions have rarely been investigated. We estimated the fluxes of NH4-N, NO3-N, K, Ca, Mg, Na, Cl, dissolved organic nitrogen (DON) and dissolved organic carbon (DOC) over the first two years after re-planting Eucalyptus trees in the coastal area of Congo. Two treatments were replicated in two blocks after clear-cutting 7-year-old stands: in treatment R, all the litter above the mineral soil was removed before planting, and in a double slash (DS) treatment, the amount of harvest residues was doubled. The soil solutions were sampled down to a depth of 4 m and the water fluxes were estimated using the Hydrus 1D model parameterized from soil moisture measurements in 4 plots. Isotopic and spectroscopic analytical techniques were used to assess the changes in dissolved organic matter (DOM) properties throughout the transfer in the soil. The first year after planting, the fluxes of NH4-N, K, Ca, Mg, Na, Cl and DOC in the topsoil of the DS treatment were 2-5 times higher than in R, which showed that litter was a major source of dissolved nutrients. Nutrient fluxes in gravitational solutions decreased sharply in the second year after planting, irrespective of the soil depth, as a result of intense nutrient uptake by Eucalyptus trees. Losses of dissolved nutrients were noticeably low in these Eucalyptus plantations despite a low cation exchange capacity, a coarse soil texture and large amounts of harvest residues left on-site at the clear cut in the DS treatment. All together, these results clarified the strong effect of litter manipulation observed on eucalypt growth in Congolese sandy soils. DOM fluxes, as well as changes in delta C-13, C:N and aromaticity of DOM throughout the soil profile showed that the organic compounds produced in the litter layer were mainly consumed by microorganisms or retained in the topsoil. Below a depth of 15 cm, most of the DOC and the DON originated from the first 2 cm of the soil and the exchanges between soil solutions and soil organic matter were low. (C) 2014 Elsevier B.V. All rights reserved.

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In this work we compute the one-nucleon-induced nonmesonic hypernuclear decay rates of He-5(Lambda), C-12(Lambda) and C-13(Lambda) using a formalism based on the independent particle shell model in terms of laboratory coordinates. To ascertain the correctness and precision of the method, these results are compared with those obtained using a formalism in terms of center-of-mass coordinates, which has been previously reported in the literature. The formalism in terms of laboratory coordinates will be useful in the shell-model approach to two-nucleon-induced transitions.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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

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The aim of this study was to use proximate chemical composition, macro and trace elements, fatty acid profile and stable isotopes as traceability tools to assess geographic origin and seasonality of croaker (Micropogonicts fumieri). Croaker from Parnaiba contained higher ash in July and lower fat content than croaker from Santos. In contrast, croaker from Santos had statistically higher proportion of 16:1n-9+16:1n-7, 20:1n-11, 20:1n-9, MUFA and n-3/n-6 ratio than croaker from Parnaiba. Concerning seasonality, croaker caught in July had significantly higher amounts of 14:0, 15:0, 16:1n-9+16:1n-7 and saturated fatty acids than fish caught in December. Concerning elements, significant differences were also detected between seasons for Cl, Ca, Fe, Sr and S, whereas differences between geographic origins were only observed with K. delta C-13 and delta N-15 were statistically different between geographic origins, whereas differences between seasons were only detected in delta N-15 ratio of croaker from Santos. Fatty acids, minerals and stable isotope are effective methods to trace geographic origin and seasonality of croaker. Nonetheless, further investigation is still required with larger samples of croaker to enable the implementation of fatty acids, elements or stable isotope as authenticity tools by food control agencies. (C) 2014 Elsevier Ltd. All rights reserved.

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

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The purpose of this study was to evaluate the effect of self-adhesive and self-etching resin cements on the bond strength of nonmetallic posts in different root regions. Sixty single-rooted human teeth were decoronated, endodontically treated, post-space prepared, and divided into six groups. Glass-fiber (GF) posts (Exacto, Angelus) and fiber-reinforced composite (FRC) posts (EverStick, StickTeck) were cemented with self-adhesive resin cement (Breeze) (SA) (Pentral Clinical) and self-etching resin cement (Panavia-F) (SE) (Kuraray). Six 1-mm-thick rods were obtained from the cervical (C), middle (M), and apical (A) regions of the roots. The specimens were then subjected to microtensile testing in a special machine (BISCO; Schaumburg, IL, USA) at a crosshead speed of 0.5 mm/min. Microtensile bond strength data were analyzed with two-way ANOVA and Tukey's tests. Means (and SD) of the MPa were: GF/SA/C: 14.32 (2.84), GF/SA/M: 10.69 (2.72), GF/SA/A: 6.77 (2.17), GF/SE/C: 11.56 (4.13), GF/SE/M: 6.49 (2.54), GF/SE/A: 3.60 (1.29), FRC/SA/C: 16.89 (2.66), FRC/SA/M: 13.18 (2.19), FRC/SA/A: 8.45 (1.77), FRC/SE/C: 13.69 (3.26), FRC/SE/M: 9.58 (2.23), FRC/SE/A: 5.62 (2.12). The difference among the regions was statistically significant for all groups (p < 0.05). The self-adhesive resin cement showed better results than the self-etching resin cement when compared to each post (p < 0.05). No statistically significant differences in bond strengths of the resin cements when comparable to each post (p > 0.05). The bond strength values were significantly affected by the resin cement and the highest values were found for self-adhesive resin cement.

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Structural characterization by NMR spectroscopy and DFT calculations was performed for two dimeric naptho-gamma-pyrones, the polyketides Aurasperone A and Fonsecinone A. Experimental data ((13)C NMR chemical shifts and interatomic geometries) were found to be in reasonable agreement with theoretical ones, obtained at B3LYP level for three different basis sets (6-31G/6-31G(d)/6-31G(d,p)). Additionally, the dipolar moments calculation allowed explaining the different solubility for these molecules. The (13)C NMR theoretical chemical shifts were calculated with the GIAO method and the solvent effects were taken into account by means of the PCM approximation. In this work, the DFT/GIAO methodology shows to be a reliable tool in the assignment of experimental NMR chemical shifts of similar molecules. (C) 2008 Wiley Periodicals, Inc. Int J Quantum Chem 108: 2408-2416, 2008.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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This study proposed the use of the stable isotope technique to track the type of food utilized by pacu Piaractus mesopotamicus larvae during their development, and to identify the moment when the larvae start using nutrients from the dry diet by retaining its carbon and nitrogen atoms in their body tissues. Five-day-old pacu larvae at the onset of exogenous feeding were fed Artemia nauplii or formulated diet exclusively; nauplii+formulated diet during the entire period; or were weaned from nauplii to a dry diet after 3, 6 or 12 days after the first feeding. delta(13)C and delta(15)N values for Artemia nauplii were -15.1 parts per thousand and 4.7 parts per thousand, respectively, and -25.0 parts per thousand and 7.4 parts per thousand for the dry diet. The initial isotopic composition of the larval tissue was -20.2 parts per thousand and 9.5 parts per thousand for delta(13)C and delta(15)N respectively. Later, at the end of a 42-day feeding period, larvae fed Artemia nauplii alone reached values of -12.7 parts per thousand and 7.0 parts per thousand for delta(13)C and delta(15)N respectively. Larvae that received the formulated diet alone showed values of -22.7 parts per thousand for delta(13)C and 9.6 parts per thousand for delta(15)N. The stable isotope technique was precise, and the time at which the larvae utilized Artemia nauplii, and later dry diet as a food source could be clearly defined.

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Compararam-se a espectroscopia de ultra-som (US) e os métodos tradicionais (MT) utilizados para a determinação de características físico-químicas do leite e estimaram-se as correlações entre esses métodos e suas acurácias. As características densidade, extrato seco desengordurado (ESD), teor de proteínas e teor de gordura foram determinadas em 65 amostras de leite cru por ambos os métodos. As densidades médias determinadas pelo US e pelos MT não diferiram entre si (P=0,14), e a correlação encontrada entre os dois métodos para a determinação da densidade não foi significativa (P= 0,08). Os teores médios de ESD, proteína e gordura encontrados pelo US e pelos MT foram diferentes (P=0,04, P<0,0001 e P<0,0001, respectivamente), as correlações entre os dois métodos utilizados para a análise dessas características foram positivas e significativas (r=0,0109, r=0,0007, r= <0,0001, respectivamente) e as acurácias dos métodos para essas determinações foram de 0,160, 0,062 e 0,145, respectivamente. Foi determinada a equação de regressão linear, que associa o teor de gordura obtido no método de espectroscopia de ultra-som ao do método butirométrico, que apresentou coeficiente de determinação de 0,5936.

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Chromatographic fractionation of the methanolic extract from the leaves of Miconia cabucu Hoehne (Melastomataceae) afforded the first example of a C-6-C-6 linked flavone dimer, 5-hydroxy-4',7-dimethoxyflavone-(6-C-6)-5-hydroxy-3 4',7-trimethoxyflavone as well as the known compounds, quercetin- 3-O-alpha-L- rhamnopyranosyl-(2 -> 1)-O-beta-D-xylopyranoside, quercetin-3-O-alpha-L-rhamnopyranoside, myricetin-3-O-alpha-L-rhamnopyranoside, quercetin-3-O-beta-D-glucopyranoside, kaempferol -3-O-beta-D-(6-coumaroyl) -glucopyranoside and gallic acid. Their chemical identities were established by application of NMR spectroscopic methods including 2D-NMR, as well as UV and ESI-MS analyses. (c) 2007 Elsevier Ltd. All rights reserved.

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Crotamine is one of four major components of the venom of the South American rattlesnake Crotalus durissus terrificus. Similar to its counterparts in the family of the myotoxins, it induces myonecrosis of skeletal muscle cells. This paper describes a new NMR structure determination of crotamine in aqueous solution at pH 5.8 and 20 degrees C, using standard homonuclear (1)H NMR spectroscopy at 900 MHz and the automated structure calculation software ATNOS/CANDID/DYANA. The automatic NOESY spectral analysis included the identification of a most likely combination of the six cysteines into three disulfide bonds, i.e. Cys4-Cys36, Cys11-Cys30 and Cys18-Cys37; thereby a generally applicable new computational protocol is introduced to determine unknown disulfide bond connectivities in globular proteins. A previous NMR structure determination was thus confirmed and the structure refined. Crotamine contains an alpha-helix with residues 1-7 and a two-stranded anti-parallel beta-sheet with residues 9-13 and 34-38 as the only regular secondary structures. These are connected with each other and the remainder of the polypeptide chain by the three disulfide bonds, which also form part of a central hydrophobic core. A single conformation was observed, with Pro13 and Pro21 in the trans and Pro20 in the cis-form. The global fold and the cysteine-pairing pattern of crotamine are similar to the beta-defensin fold, although the two proteins have low sequence homology, and display different biological activities. (c) 2005 Elsevier Ltd. All rights reserved.

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Pós-graduação em Biofísica Molecular - IBILCE