976 resultados para chemical state


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The performance of three different techniques for determining proton rotating frame relaxation rates (T1pH) in charred and uncharred woods is compared. The variable contact time (VCT) experiment is shown to over-estimate T1pH, particularly for the charred samples, due to the presence of slowly cross-polarizing C-13 nuclei. The variable spin (VSL) or delayed contact experiment is shown to overcome these problems; however, care is needed in the analysis to ensure rapidly relaxing components are not overlooked. T1pH is shown to be non-uniform for both charred and uncharred wood samples; a rapidly relaxing component (T1pH = 0.46-1.07 ms) and a slowly relaxing component (T1pH = 3.58-7.49) is detected in each sample. T1pH for each component generally decreases with heating temperature (degree of charring) and the proportion of rapidly relaxing component increases. Direct T1pH determination (via H-1 detection) shows that all samples contain an even faster relaxing component (0.09-0.24 ms) that is virtually undetectable by the indirect (VCT and VSL) techniques. A new method for correcting for T1pH signal losses in spin counting experiments is developed to deal with the rapidly relaxing component detected in the VSL experiment. Implementation of this correction increased the proportion of potential C-13 CPMAS NMR signal that can be accounted for by up to 50% for the charred samples. An even greater proportion of potential signal can be accounted for if the very rapidly relaxing component detected in the direct T1pH determination is included; however, it must be kept in mind that this experiment also detects H-1 pools which may not be involved in H-1-C-13 cross-polarization. (C) 2002 Elsevier Science (USA).

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We conduct a theoretical analysis of steady-state heat transfer problems through mid-crustal vertical cracks with upward throughflow in hydrothermal systems. In particular, we derive analytical solutions for both the far field and near field of the system. In order to investigate the contribution of the forced advection to the total temperature of the system, two concepts, namely the critical Peclet number and the critical permeability of the system, have been presented and discussed in this paper. The analytical solution for the far field of the system indicates that if the pore-fluid pressure gradient in the crust is lithostatic, the critical permeability of the system can be used to determine whether or not the contribution of the forced advection to the total temperature of the system is negligible. Otherwise, the critical Peclet number should be used. For a crust of moderate thickness, the critical permeability is of the order of magnitude of 10(-20) m(2), under which heat conduction is the overwhelming mechanism to transfer heat energy, even though the pore-fluid pressure gradient in the crust is lithostatic. Furthermore, the lower bound analytical solution for the near field of the system demonstrates that the permeable vertical cracks in the middle crust can efficiently transfer heat energy from the lower crust to the upper crust of the Earth. Copyright (C) 2002 John Wiley Sons, Ltd.

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The volatile components of the chin gland secretion of the wild European rabbit, Oryctolagus cuniculus (L.), were investigated with the use of gas chromatography. Studies of the chemical nature of this secretion by previous workers demonstrated that it was important in the maintenance of social structure in this species. This study identified 34 different volatile components that consist primarily of aromatic and aliphatic hydrocarbons. Especially common are a series of alkyl-substituted benzene derivatives that provide most of the compound diversity in the secretion. Samples of chin gland secretion collected from animals at three different geographical locations, separated by more than 100 km, showed significant differences in composition. This work suggests that variation among populations needs to be considered when undertaking semiochemical research. Alternate nonparametric methods are also used for the analysis of chromatographic data.

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In the Leaven of the Ancients, John Walbridge studies the appropriation of non–Peripatetic philosophical ideas by an anti–Aristotelian Islamic philosopher, Shihab al-Din al-Suhrawardi (d. 1191). He proposes a comprehensive explanation of the origin of Suhrawardi's philosophical system, a revival of the “wisdom of the Ancients” and its philosophical affiliations “grounded” in Greek philosophy (p. xiii). Walbridge attempts to uncover the reasons for Suhrawardi's rejection of the prevailing neo–Aristotelian synthesis in Islamic philosophy, Suhrawardi's knowledge and understanding of non–Aristotelian Greek philosophy, the ancient philosophers Suhrawardi was attempting to follow, the relationship between Suhrawardi's specific philosophical teachings (logic, ontology, physics, and metaphysics), and his understanding of non–Aristotelian ancient philosophy and the relationship between Suhrawardi's system and the major Greek philosophers, schools, and traditions—in particular the Presocratics, Plato, and the Stoics (p. 8). Copyright © 2003 Cambridge University Press

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We show that quantum feedback control can be used as a quantum-error-correction process for errors induced by a weak continuous measurement. In particular, when the error model is restricted to one, perfectly measured, error channel per physical qubit, quantum feedback can act to perfectly protect a stabilizer codespace. Using the stabilizer formalism we derive an explicit scheme, involving feedback and an additional constant Hamiltonian, to protect an (n-1)-qubit logical state encoded in n physical qubits. This works for both Poisson (jump) and white-noise (diffusion) measurement processes. Universal quantum computation is also possible in this scheme. As an example, we show that detected-spontaneous emission error correction with a driving Hamiltonian can greatly reduce the amount of redundancy required to protect a state from that which has been previously postulated [e.g., Alber , Phys. Rev. Lett. 86, 4402 (2001)].

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N,N,N,N-Tetramethylammonium dicyanamide (Me(4)NDCA) has been examined via differential scanning calorimetry (DSC), thermogravimetric analysis, conductivity, single crystal X-ray diffraction and H-1 nuclear magnetic resonance (NMR) analyses, and was found to be highly conductive in the solid state (sigma = 10(-3) S cm(-2) at 420 K) and to also exhibit unusual plastic crystal behaviour. To investigate the correlation between such behaviour and the occurrence of molecular rotations in the crystal, H-1 NMR second moment measurements are compared with calculated values predicted from the crystal structure. While DSC analysis indicates a number of solid-solid transitions at ambient temperatures, subsequent H-1 NMR analysis of the Me4N+ cation shows that a variety of rotational motions become active at low (

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Andrew Tooke's 1691 English translation of Samuel Pufendorf's De officio hominis et civis, published as The Whole Duty of Man According to the Law of Nature, brought Pufendorf's manual fo statist natural law into English politics at a moment of temporary equilibrium in the unfinished contest between Crown and Parliament for the rights and powers of sovereignty. Drawing on the authors' re-edition of The Whole Duty of Man, this article describes and analyses a telling instance of how--by translation--the core political terms and concepts of the German natural jurist's 'absolutist' formulary were reshaped for reception in the different political culture of late seventeenth-century England.

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Direct and simultaneous observation of root growth and plant water uptake is difficult because soils are opaque. X-ray imaging techniques such as projection radiography or Computer Tomography (CT) offer a partial alternative to such limitations. Nevertheless, there is a trade-off between resolution, large field-of-view and 3-dimensionality: With the current state of the technology, it is possible to have any two. In this study, we used X-ray transmission through thin-slab systems to monitor transient saturation fields that develop around roots as plants grow. Although restricted to 2-dimensions, this approach offers a large field-of-view together with high spatial and dynamic resolutions. To illustrate the potential of this technology, we grew peas in 1 cm thick containers filled with soil and imaged them at regular intervals. The dynamics of both the root growth and the water content field that developed around the roots could be conveniently monitored. Compared to other techniques such as X-ray CT, our system is relatively inexpensive and easy to implement. It can potentially be applied to study many agronomic problems, such as issues related to the impact of soil constraints (physical, chemical or biological) on root development.

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The extent of mixing in blends of poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) (27% HV) and poly(vinyl acetate) (PVAc) has been measured using a number of different techniques, principally solid-state NMR. Differential scanning calorimetry DSC measurements indicated effective mixing of the polymer chains on a scale of several nanometres. The results of H-1 T-1 and H-1 T-1rho. measurements confirm intimate mixing of the chains. A change on blending in the H-1 T-1rho, and the H-1 NMR line width of the signal from the protons of PVAc was consistent with an increase in the amplitude and frequency of motion of this component. The PVAc chains reside within the inter-lamellar space, as confirmed by spin diffusion measurements after H-1 T-1rho preparation. (C) 2003 Society of Chemical Industry.

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In this study we demonstrate a new in-fermenter chemical extraction procedure that degrades the cell wall of Escherichia coli and releases inclusion bodies (IBs) into the fermentation medium. We then prove that cross-flow microfiltration can be used to remove 91% of soluble contaminants from the released IBs. The extraction protocol, based on a combination of Triton X-100, EDTA, and intracellular T7 lysozyme, effectively released most of the intracellular soluble content without solubilising the IBs. Cross-flow microfiltration using a 0.2 mum ceramic membrane successfully recovered the granulocyte macrophagecolony stimulating factor (GM-CSF) IBs with removal of 91% of the soluble contaminants and virtually no loss of IBs to the permeate. The filtration efficiency, in terms of both flux and transmission, was significantly enhanced by infermenter Benzonase(R) digestion of nucleic acids following chemical extraction. Both the extraction and filtration methods exerted their efficacy directly on a crude fermentation broth, eliminating the need for cell recovery and re-suspension in buffer. The processes demonstrated here can all be performed using just a fermenter and a single cross-flow filtration unit, demonstrating a high level of process intensification. Furthermore, there is considerable scope to also use the microfiltration system to subsequently solubilise the IBs, to separate the denatured protein from cell debris, and to refold the protein using diafiltration. In this way refolded protein can potentially be obtained, in a relatively pure state, using only two unit operations. (C) 2004 Wiley Periodicals Inc.

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Novel cyclopropyl containing fatty acids are good substrates for P450(BM3) catalysed hydroxylation and analysis of their oxidation products indicates the presence of a radical intermediate (maximum rebound rate 2.6x10(10) s(-1)) and the absence of any cationic intermediate.

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This paper measured the variations in performance of small municipalities in the State of Sao Paulo, Brazil, regarding the technical efficiency in the use of public funds in public primary health care actions concerning the funding profile, in a scenario of fiscal federalism. Technical efficiency is one of the parameters of evaluation of public sector performance and was measured by means of Data Envelopment Analysis (DEA). The correlation analysis of DEA score was used to verify possible associations between technical efficiency and the funding profile of expenses with health care. The results showed that 6.41% of the municipalities were considered efficient. They also showed that the level of municipality dependence to inter-governmental general purpose grants and the national health funding specific purpose grants have negative correlation with efficiency scores.

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This article presents a proposal of a systemic model composed for the micro and small companies (MSE) of the region of Ribeiro Preto and the agents which influenced their environment. The proposed model was based on Stafford Beer`s (Diagnosing the system for organizations. Chichester, Wiley, 1985) systemic methodologies VSM (Viable System Model) and on Werner Ulrich`s (1983) CSH (Critical Systems Heuristics). The VSM is a model for the diagnosis of the structure of an organization and of its flows of information through the application of the cybernetics concepts (Narvarte, In El Modelo del Sistema Viable-MSV: experiencias de su aplicacin en Chile. Proyecto Cerebro Colectivo del IAS, Santiago, 2001). On the other hand, CSH focus on the context of the social group applied to the systemic vision as a counterpoint to the organizational management view considered by the VSM. MSE of Ribeiro Preto and Sertozinho had been analyzed as organizations inserted in systems that relate and integrate with other systems concerning the public administration, entities of representation and promotion agencies. The research questions: which are the bonds of interaction among the subsystems in this process and who are the agents involved? The systemic approach not only diagnosed a social group, formed by MSE of Ribeiro Preto and Sertozinho, public authorities and support entities, but could also delineate answers that aimed the clarification of obscure questions generating financial assistance to the formularization of efficient actions for the development of this system.

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The high speciFIcity of alpha-conotoxins for different neuronal nicotinic acetylcholine receptors makes them important probes for dissecting receptor subtype selectivity. New sequences continue to expand the diversity and utility of the pool of available alpha-conotoxins. Their identification and characterization depend on a suite of techniques with increasing emphasis on mass spectrometry and microscale chromatography, which have benefited from recent advances in resolution and capability. Rigorous physicochemical analysis together with synthetic peptide chemistry is a prerequisite for detailed conformational analysis and to provide sufficient quantities of alpha-conotoxins for activity assessment and structure-activity relationship studies.

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Although prosimians are greatly olfaction-oriented, little is known about the specifics of how they use scent to communicate. In this preliminary study we attempted to delineate intra- and interspecific differences among the anogenital gland secretions of two lemur species (Lemur catta and Propithecus verreauxi coquereli) using gas chromatography-mass spectrometry (GC-MS). The results indicate that the two species are discernible through scent. Furthermore, we were able to identify reproductive status using this technique. The anogenital secretions of the different sexes in L. catta, though perhaps not P. v. coquereli, are chemically distinguishable. Given this information, it appears that at least some lemur species can use scent marks to determine species, sex, and reproductive status. (C) 2004 Wiley-Liss, Inc.