973 resultados para Delta C-13
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Alpha resonant states in (13)C tu to 15MeV were excited by the (9)Be ((6)Li,d) (13)C reaction, The data were taken at a bombarding energy of 25.5 MeV employing the sao Paulo-Pelletron-Enge Split Pole facility and the nuclear emulsion technique. The resolution of 50 keV allowed for the separation of the resonant contributions to the known 7/2(-) and (5/2(-)) states near the (9)Be + alpha threshold both associated with an L = 4 transfer. Several narrow alpha resonant states not previously measured were detected, in particular the one at the 3 alpha + n threshold populated by an L = 2 transfer, revealing a (9)Be + alpha component for the 1/2(-) cluster state candidate at this threshold.
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This article describes a solid-state NMR (SSNMR) investigation of the influence of hydration and chemical cross-linking on the molecular dynamics of the constituents of the bovine pericardium (BP) tissues and its relation to the mechanical properties of the tissue. Samples of natural phenetylamine-diepoxide (DE)- and glutaraldehyde (GL)-fixed BP were investigated by (13)C cross-polarization SSNMR to probe the dynamics of the collagen, and the results were correlated to the mechanical properties of the tissues, probed by dynamical mechanical analysis. For samples of natural BP, the NMR results show that the higher the hydration level the more pronounced the molecular dynamics of the collagen backbone and sidechains, decreasing the tissue`s elastic modulus. In contrast, in DE- and GL-treated samples, the collagen molecules are more rigid, and the hydration seems to be less effective in increasing the collagen molecular dynamics and reducing the mechanical strength of the samples. This is mostly attributed to the presence of cross-links between the collagen plates, which renders the collagen mobility less dependent on the water absorption in chemically treated samples. Copyright (C) 2010 John Wiley & Sons, Ltd.
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We have studied the molecular dynamics of one of the major macromolecules in articular cartilage, chondroitin sulfate. Applying (13)C high-resolution magic-angle spinning NMR techniques, the NMR signals of all rigid macromolecules in cartilage can be suppressed, allowing the exclusive detection of the highly mobile chondroitin sulfate. The technique is also used to detect the chondroitin sulfate in artificial tissue-engineered cartilage. The tissue-engineered material that is based on matrix producing chondrocytes cultured in a collagen gel should provide properties as close as possible to those of the natural cartilage. Nuclear relaxation times of the chondroitin sulfate were determined for both tissues. Although T(1) relaxation times are rather similar, the T(2) relaxation in tissue-engineered cartilage is significantly shorter. This suggests that the motions of chondroitin sulfate in data:rat and artificial cartilage different. The nuclear relaxation times of chondroitin sulfate in natural and tissue-engineered cartilage were modeled using a broad distribution function for the motional correlation times. Although the description of the microscopic molecular dynamics of the chondroitin sulfate in natural and artificial cartilage required the identical broad distribution functions for the correlation times of motion, significant differences in the correlation times of motion that are extracted from the model indicate that the artificial tissue does not fully meet the standards of the natural ideal. This could also be confirmed by macroscopic biomechanical elasticity measurements. Nevertheless, these results suggest that NMR is a useful tool for the investigation of the quality of artificially engineered tissue. (C) 2010 Wiley Periodicals, Inc. Biopolymers 93: 520-532, 2010.
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The impact of human activity on the sediments of Todos os Santos Bay in Brazil was evaluated by elemental analysis and (13)C Nuclear Magnetic Resonance ((13)C NMR). This article reports a study of six sediment cores collected at different depths and regions of Todos os Santos Bay. The elemental profiles of cores collected on the eastern side of Frades Island suggest an abrupt change in the sedimentation regime. Auto-regressive Integrated Moving Average (ARIMA) analysis corroborates this result. The range of depths of the cores corresponds to about 50 years ago, coinciding with the implantation of major onshore industrial projects in the region. Principal Component Analysis of the (13)C NMR spectra clearly differentiates sediment samples closer to the Subae estuary, which have high contents of terrestrial organic matter, from those closer to a local oil refinery. The results presented in this article illustrate several important aspects of environmental impact of human activity on this bay. (C) 2011 Elsevier Ltd. All rights reserved.
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Combined fluid inclusion (FI) microthermometry, Raman spectroscopy, X-ray diffraction, C-O-H isotopes and oxygen fugacities of granulites from central Ribeira Fold Belt, SE Brazil, provided the following results: i) Magnetite-Hematite fO(2) estimates range from 10(-11.5) bar (QFM + 1) to 10(-18.3) bar (QFM - 1) for the temperature range of 896 degrees C-656 degrees C, implying fO(2) decrease from metamorphic peak temperatures to retrograde conditions; ii) 5 main types of fluid inclusions were observed: a) CO(2) and CO(2)-N(2) (0-11 mol%) high to medium density (1.01-0.59 g/cm(3)) FI; b) CO(2) and CO(2)-N(2) (0-36 mol%) low density (0.19-0.29 g/cm(3)) FI; c) CO(2) (94-95 mol%)-N(2) (3 mol%)-CH(4) (2-3 mol%)-H(2)O (water phi(v) (25 degrees C) = 0.1) FI; d) low-salinity H(2)O-CO(2) FI; and e) late low-salinity H(2)O FI; iii) Raman analyses evidence two graphite types in khondalites: an early highly ordered graphite (T similar to 450 degrees C) overgrown by a disordered kind (T similar to 330 degrees C); iv) delta(18)O quartz results of 10.3-10.7 parts per thousand, imply high-temperature CO(2) delta(18)O values of 14.4-14.8 parts per thousand, suggesting the involvement of a metamorphic fluid, whereas lower temperature biotite delta(18)O and delta D results of 7.5-8.5 parts per thousand and -54 to -67 parts per thousand respectively imply H(2)O delta(18)O values of 10-11 parts per thousand and delta D(H2O) of -23 to -36 parts per thousand suggesting delta(18)O depletion and increasing fluid/rock ratio from metamorphic peak to retrograde conditions. Isotopic results are compatible with low-temperature H(2)O influx and fO(2) decrease that promoted graphite deposition in retrograde granulites, simultaneous with low density CO(2), CO(2)-N(2) and CO(2)-N(2)-CH(4)-H(2)O fluid inclusions at T = 450-330 degrees C. Graphite delta(13)C results of -10.9 to -11.4 parts per thousand imply CO(2) delta(13)C values of -0.8 to -1.3 parts per thousand suggesting decarbonation of Cambrian marine carbonates with small admixture of lighter biogenic or mantle derived fluids. Based on these results, it is suggested that metamorphic fluids from the central segment of Ribeira Fold Belt evolved to CO(2)-N(2) fluids during granulitic metamorphism at high fO(2), followed by rapid pressure drop at T similar to 400-450 degrees C during late exhumation that caused fO(2) reduction induced by temperature decrease and water influx, turning carbonic fluids into CO(2)-H(2)O (depleting biotite delta(18)O and delta D values), and progressively into H(2)O. When fO(2) decreased substantially by mixture of carbonic and aqueous fluids, graphite deposited forming khondalites. (C) 2010 Elsevier Ltd. All rights reserved.
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Acetaldehyde is an environmentally widespread genotoxic aldehyde present in tobacco smoke, vehicle exhaust and several food products. Endogenously, acetaldehyde is produced by the metabolic oxidation of ethanol by hepatic NAD-dependent alcohol dehydrogenase and during threonine catabolism. The formation of DNA adducts has been regarded as a critical factor in the mechanisms of acetaldehyde mutagenicity and carcinogenesis. Acetaldehyde reacts with 2`-deoxyguanosine in DNA to form primarily N(2)-ethylidene-2`-deoxyguanosine. The subsequent reaction of N(2)-ethylidenedGuo with another molecule of acetaldehyde gives rise to 1,N(2)-propano-2`-deoxyguanosine (1,N(2)-propanodGuo), an adduct also found as a product of the crotonaldehyde reaction with dGuo. However, adducts resulting from the reaction of more than one molecule of acetaldehyde in vivo are still controversial. In this study, the unequivocal formation of 1,N(2)-propanodGuo by acetaldehyde was assessed in human cells via treatment with [(13)C(2)]-acetaldehyde. Detection of labeled 1,N(2)-propanodGuo was performed by HPLC/MS/MS. Upon acetaldehyde exposure (703 mu M), increased levels of both 1,N(2)-etheno-2`-deoxyguanosine (1,N(2)-epsilon dGuo), which is produced from alpha,beta-unsaturated aldehydes formed during the lipid peroxidation process, and 1,N(2)-propanodGuo were observed. The unequivocal formation of 1,N(2)-propanodGuo in cells exposed to this aldehyde can be used to elucidate the mechanisms associated with acetaldehyde exposure and cancer risk.
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The complete assignment of the (1)H and (13)C NMR spectra of the diastereomeric pairs of some alpha-arylsulfinyl-substituted N-methoxy-N-methylpropionamides with the substituents methoxy, methyl, chloro, nitro is reported. Copyright (C) 2008 John Wiley & Sons, Ltd.
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In this paper, we show that the steady-state free precession sequence can be used to acquire (13)C high-resolution nuclear magnetic resonance spectra and applied to qualitative analysis. The analysis of brucine sample using this sequence with 60 degrees flip angle and time interval between pulses equal to 300 ms (acquisition time, 299.7 ms; recycle delay, 300 ms) resulted in spectrum with twofold enhancement in signal-to-noise ratio, when compared to standard (13)C sequence. This gain was better when a much shorter time interval between pulses (100 ms) was applied. The result obtained was more than fivefold enhancement in signal-to-noise ratio, equivalent to more than 20-fold reduction in total data recording time. However, this short time interval between pulses produces a spectrum with severe phase and truncation anomalies. We demonstrated that these anomalies can be minimized by applying an appropriate apodization function and plotting the spectrum in the magnitude mode.
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Print No. 69
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print No 68
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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The Bura do Itapira pua carbonatite is located in southern Brazil and belongs to the Cretaceous Ponta Grossa alkaline-carbonatitic province related to the opening of the South Atlantic. The carbonatite complex is emplaced in Proterozoic granites and is mainly composed of plutonic magnesio- to ferrocarbonatite, with smaller amounts of subvolcanic magnesiocarbonatite. Hydrothermal alteration of the carbonatite has led to the formation of quartz, apatite, fluorite, rue earth fluorocarbonates, barite and sulfides in variable proportions. Trace element data, delta(13)C and delta(18)O are presented here, with the aim of better understanding the geochemical nature of hydrothermal alteration related to rare earth elements (REE) mineralization. The non-overprinted plutonic carbonatite shows the lowest REE contents, and its primitive carbon and oxygen stable isotopic composition places it in the field of primary igneous carbonatites. Two types of hydrothermally overprinted plutonic carbonatites can be distinguished based on secondary minerals and geochemical composition. Type I contains mainly quartz, rare earth fluorocarbonates and apatite as hydrothermal secondary minerals, and has steep chondrite normalized REE patterns, with Sigma(REE+Y) of up to 3 wt.% (i.e., two orders of magnitude higher than in fresh plutonic samples). In contrast, the Type II overprint contains apatite, fluorite and barite as dominant hydrothermal minerals, and is characterized by heavy REE enrichment relative to the fresh samples, with flat chondrite normalized REE patterns. Carbon and oxygen stable isotope ratios of Types I and II are elevated (delta(18)O + 8 to + 12 parts per thousand; delta(13)C - 6 to - 2 parts per thousand) relative to the fresh samples. Hydrothermally overprinted carbonatites exposed to weathering show even higher delta(18)O values (delta(18)O 13 to 25 parts per thousand) but no additional REE enrichment. The subvolcanic carbonatite has anomalously high delta(13)C of up to + 1 parts per thousand, which suggests crustal contamination through interaction with carbonate-bearing metasediments. (C) 1999 Elsevier B.V. B.V. All rights reserved.
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Mesembryanthemum crystallinum L. (Aizoaceae) is a facultative annual halophyte and a C-3-photosynthesis/crassulacean acid metabolism intermediate species currently used as a model plant in stress physiology. Both salinity and high light irradiance stress are known to induce CAM in this species. The present study was performed to provide a diagnosis of alterations at the photosystem 11 level during salinity and irradiance stress. Plants were subjected for up to 13 days to either 0.4M NaCl salinity or high irradiance of 1000 mu mol m(-2) s(-1), as well as to both stress factors combined (LLSA = low light plus salt; HLCO = high light of 1000 mu mol m(-2)s(-1), no salt; HLSA = high light plus salt). A control of LLCO = low light of 200 mu mol m(-2) s(-1), no salt was used. Parameters of chlorophyll a fluorescence of photosystem 11 (PSII) were measured with a pulse amplitude modulated fluorometer. HLCO and LLSA conditions induced a weak degree of CAM with day/night changes of malate levels (Delta malate) of similar to 12 mM in the course of the experiment, while HLSA induced stronger CAM of Delta malate similar to 20mM. Effective quantum yield of PSII, Delta F/F'(m), was only slightly affected by LLSA, somewhat reduced during the course of the experiment by HLCO and clearly reduced by HLSA. Potential quantum efficiency of PSII, F-v/F-m, at predawn times was not affected by any of the conditions, always remaining at >= 0.8, showing that there was no acute photoinhibition. During the course of the days HL alone (HLCO) also did not elicit photoinhibition; salt alone (LLSA) caused acute photoinhibition which was amplified by the combination of the two stresses (HLSA). Non-photochemical, NPQ, quenching remained low (< 0.5) under LLCO, LLSA and HLCO and increased during the course of the experiment under HLSA to 1-2. Maximum apparent photosynthetic electron transport rates, ETRmax, declined during the daily courses and were reduced by LLSA and to a similar extent by HLSA. It is concluded that A crystallinum expresses effective stress tolerance mechanisms but photosynthetic capacity is reduced by the synergistic effects of salinity and tight irradiance stress combined. (c) 2006 Elsevier GmbH. All rights reserved.