872 resultados para NMR SHIFT
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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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This essay has investigated the question of an ongoing language shift from Plattdeutsch and German to Spanish among the Mennonites in Paraguay and the role of the school in this process. The aims of the study were to compare the use of languages among the Mennonites in Asuncion and in the Menno colony and to identify the importance that parents give to the languages and to compare this with a school leader perspective. The aim was also to identify factors that influence the language shift and identify the influence that the shift excerpts on Mennonite values and identity. The results are based on my own observations, interviews with Mennonite women and interviews with key informants who have insight into the school policy issues. The outcome may be used as a basis for educational and language planning. There is a need to consciously sit down and re-define the Mennonite identity and to make the community and the school aware of their responsibility in language maintenance.
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Igiogbe cultural heritage has existed since the founding of Bini kingdom without any controversy; however since the Supreme Court decision in Idehen v Idehen the issue of Igiogbe has assumed new dimensions. Igiogbe - the house in which a Benin man lived and died devolves on his first son absolutely; but since the beginning of 20th century litigation as to the real meaning of Igiogbe and who is entitled to inheritance thereof began to increase. Controversies and increase in litigation over Igiogbe has occasioned a shift in the practice, the Bini’s are not conscious of some of these changes, most of them (Bini’s) still claim Igiogbe practices is rigidly adhered to. This study on Igiogbe inheritance in Bini kingdom is therefore carried out with a view to bringing out the changes in Igiogbe cultural practice using legal and anthropological tools to examine the changes. While laying the foundation for the discussion on the main research object the researcher examined the origin and status of customary law in Nigeria. There after I examined Igiogbe inheritance in Bini kingdom. Igiogbe and the issue of first son were critically analyzed with the aid of the research questions bringing out the changes in Igiogbe concept from traditional practice to modern practice. Study shows Igiogbe practice is still relevant in modern Bini kingdom, however, the shift and changes in practice of this cultural milieu has lead me to ask some fundamental questions which I intend to answer in the broader research work in future.
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The Sustainability revolution: A societal paradigm shift – ethos, innovation, governance transformation This paper identifies several key mechanisms that underlie major paradigm shifts. After identifying four such mechanisms, the article focuses on one type of transformation which has a prominent place in the sustainability revolution that the article argues is now taking place. The transformation is piecemeal, incremental, diffuse – in earlier writings referred to as ”organic”. This is a more encompassing notion than grassroots, since the innovation and transformation processes may be launched and developed at multiple levels through diverse mechanisms of discovery and development. Major features of the sustainability revolution are identified and comparisons made to the industrial revolution.
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The photolytic phenanthrene-based precursors for both β-methoxycarbene and β-ethoxycarbene were synthesized with and without a deuterium label attached to the a carbon. The incorporation of this deuterium label allowed distinction between a 1, 2-H shift and a 1, 2-O shift pathway to the respective alkyl vinyl ether, without the influence of a primary kinetic isotope effect. Photolyses of these precursors gave rearrangement products of the expected β-alkoxycarbenes. In the case of β-methoxycarbene, no methyl vinyl ether was observed due to its volatility. However, the appearance of aldehyde peaks in the NMR spectra, from an apparent further rearrangement to acetaldehyde through an enol intermediate, indicated that a 1,2-H shift had occurred. Ethyl vinyl ether was isolated following the photolysis of the β-ethoxycarbene precursor. Quantification of the two pathways showed less than 2% undergoing an ethoxy shift to the ethyl vinyl ether. Yield experiments on this photolysis demonstrated a maximum yield of β-ethoxycarbene as 43%, though this decreased as the experiment continued. Computational work on the β-ethoxycarbene system indicates that the triplet scate is more stable than the singlet. In addition, the activation energy to the 1.2-H shift pathway is remarkably low and is clearly consistent with the observed overwhelming preference for this pathway in the experiment.
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We have examined the effect of the uncharged species of lidocaine (LDC) and etidocaine (EDC) on the acyl chain moiety of egg phosphatidylcholine liposomes. Changes in membrane organization caused by both anesthetics were detected through the use of EPR spin labels (5, 7 and 12 doxyl stearic acid methyl ester) or fluorescence probes (4, 6, 10, 16 pyrene-fatty acids). The disturbance caused by the LA was greater when the probes were inserted in more external positions of the acyl chain and decreased towards the hydrophobic core of the membrane. The results indicate a preferential insertion of LDC at the polar interface of the bilayer and in the first half of the acyl chain, for EDC. Additionally, 2 H NMR spectra of multilamellar liposomes composed by acyl chain-perdeutero DMPC and EPC (1:4 mol%) allowed the determination of the segmental order (S-mol) and dynamics (T-1) of the acyl chain region. In accordance to the fluorescence and EPR results, changes in molecular orientation and dynamics are more prominent if the LA preferential location is more superficial, as for LDC while EDC seems to organize the acyl chain region between carbons 2-8, which is indicative of its positioning. We propose that the preferential location of LDC and EDC inside the bilayers creates a "transient site", which is related to the anesthetic potency since it could modulate the access of these molecules to their binding site(s) in the voltage-gated sodium channel. (C) 2007 Elsevier B.V. All rights reserved.
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The literature widely recognizes that shift workers have more health complaints than the general population. The objective of this study was to describe the prevalence of sleep complaints and verify the polysomnographic (PSG) variables of shift workers in two Brazilian nuclear power plants. We carried out a subjective evaluation with a sleep questionnaire. Based on these results, the interviewees that reported sleep-related complaints were referred for polysomnographic evaluation. of the 327 volunteers initially evaluated by the sleep questionnaire, 113 (35%) reported sleep complaints; they were significantly older, had higher body mass index (BMI), and worked more years on shifts than those without sleep complaints. of these 113, 90 met criteria for various sleep disorders: 30 (9%) showed obstructive sleep apnea (OSA), 18 (5.5%) showed limb movement, and 42 (13%) evidenced both sleep problems and had a significantly higher proportion of sleep stage 1 and arousals compared with the 23 shift workers that had no indices of sleep problems. The present study found that 90 (27.5%) of the evaluated participants met the PSG criteria of some type of clinical sleep disorder. This high proportion should be investigated for associations with other aspects of work, such as working hours, working schedule, years performing shift work, and access to health services. Due to the strong association between sleep disorders and the incidence of fatigue and sleepiness, the evaluation of the sleep patterns and complaints of shift workers is essential and should be considered to be one of the basic strategies of industry to prevent accidents.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
Physical properties of pectin-high amylose starch mixtures cross-linked with sodium trimetaphosphate
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Quantum mechanics calculations at the ab initio HF/3-21G* level were carried out with Nuclear Magnetic Resonance (NMR) measurements to characterize citric acid and lithium interactions. The results indicate the formation of a tridentate organometallic compound with one lithium and one citric acid molecule and a tridentate and bidentate compound of two lithium atoms and one citric acid molecule. The results are in agreement with the experimental and theoretical data. (C) 1999 Elsevier B.V. B.V. All rights reserved.
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Shift work (SW) can affect worker health and productivity. Working at night, workers often accumulate fatigue and are less productive. In Brazil, laws have been drafted aiming to reduce night work and rotating shift hours. In order to slash costs, companies have been looking for new arrangements to improve productivity under these conditions. The purpose of this study was to examine management changes and their outcomes in a large glass factory located in an industrial region of Brazil. The results show that the management, seeking equal productivity among shifts, focused its efforts mainly on distributing employee expertise. The arrangement resulted in 12 different groups that combine to serve three fixed shifts. A same shift can be served by more than one group, and the members of a same group share days off on different days. There was no statistically significant productivity difference among the three shifts. The on-site examination showed that part of the production was held by the workers and transferred to the next shift in order for them to be able to meet the management's performance rate requirements. The finding shows how a Brazilian cultural trait (resistance without conflict) is used to drive coping in SW.
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Low molecular weight fractions of polyisoprene extracted from Ficus elastica Herb. ex Hornem. were studied by C-13-NMR. The identification of 2-3 trans terminal units at the end of the polymer chain needed the acquisition of more than 17 000 transients. (C) 2000 Elsevier B.V. Ltd. All rights reserved.
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Electrical conductivity and H-1 Nuclear Magnetic Resonance (NMR) techniques were used to investigate the ion-exchanged layered lead-niobate perovskite HPb2Nb3O10. nH(2)O, over the temperature range 90-350 K. Compounds were synthesized by the sol-gel method and calcinated at 650 degreesC. Analysis of the NMR data gives activation energies for the proton motion in the range 0.14-0.40 eV, which are dependent on the water content. The frequency and temperature dependencies of the proton spin-lattice relaxation times show that the character of the motion of the: water molecules is essentially two-dimensional, reflecting the layered structure of the material. The H-1 line-narrowing transition and the single spin-lattice relaxation rate maximum, observed in the hydrated compounds, are consistent with a Grotthuss-like mechanism for the proton diffusion. (C) 2000 Elsevier B.V. B.V. All rights reserved.