985 resultados para Electrochemical determination
Resumo:
The role of Chlamydia trachomatis HtrA (CtHtrA) for the growth and pathogenesis of this organism is presented. Inhibition of CtHtrA led to loss of infectious progeny in Chlamydia, particularly during heat stress or recovery from penicillin persistence. Isolation of CtHtrA inhibitor resistant mutants identified positive selection for mutants in fatty acid related pathways. Importantly, HtrA inhibition was effective against clinical isolates of C. trachomatis. Thus the findings combined indicate that CtHtrA is an important chlamydial growth factor that has the potential to be targeted for the development of anti-chlamydial drugs in the future.
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The crystallization of amorphous semiconductors is a strongly exothermic process. Once initiated the release of latent heat can be sufficient to drive a self-sustaining crystallization front through the material in a manner that has been described as explosive. Here, we perform a quantitative in situ study of explosive crystallization in amorphous germanium using dynamic transmission electron microscopy. Direct observations of the speed of the explosive crystallization front as it evolves along a laser-imprinted temperature gradient are used to experimentally determine the complete interface response function (i.e., the temperature-dependent front propagation speed) for this process, which reaches a peak of 16 m/s. Fitting to the Frenkel-Wilson kinetic law demonstrates that the diffusivity of the material locally/immediately in advance of the explosive crystallization front is inconsistent with those of a liquid phase. This result suggests a modification to the liquid-mediated mechanism commonly used to describe this process that replaces the phase change at the leading amorphous-liquid interface with a change in bonding character (from covalent to metallic) occurring in the hot amorphous material.
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The standard curve-fitting methods, Casagrande's log t method and Taylor's root t method, for the determination of the coefficient of consolidation use the later part of the consolidation curve and are influenced by secondary compression effects. Literature shows that secondary compression is concurrent with primary consolidation and that its effect is to decrease the value of the coefficient of consolidation. If the early part of the time-compression data is used, the values obtained will be less influenced by secondary compression effects. A method that uses the early part of the log t plot is proposed in this technical note. As the influence of secondary compression is reduced, the value obtained by this method is greater than that yielded by both the standard methods. The permeability values computed from C-v (obtained from the proposed method) rue more in agreement with the measured values than the standard methods showing that the effects of secondary compression are minimized. Time-compression data for a shorter duration is sufficient for the determination of C-v if the coefficient of secondary compression is not required.
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Electrochemical capacitors are electrochemical devices with fast and highly reversible charge-storage and discharge capabilities. The devices are attractive for energy storage particularly in applications involving high-power requirements. Electrochemical capacitors employ two electrodes and an aqueous or a non-aqueous electrolyte, either in liquid or solid form; the latter provides the advantages of compactness, reliability, freedom from leakage of any liquid component and a large operating potential-window. One of the classes of solid electrolytes used in capacitors is polymer-based and they generally consist of dry solid-polymer electrolytes or gel-polymer electrolyte or composite-polymer electrolytes. Dry solid-polymer electrolytes suffer from poor ionic-conductivity values, between 10(-8) and 10(-7) S cm(-1) under ambient conditions, but are safer than gel-polymer electrolytes that exhibit high conductivity of ca. 10(-3) S cm(-1) under ambient conditions. The aforesaid polymer-based electrolytes have the advantages of a wide potential window of ca. 4 V and hence can provide high energy-density. Gel-polymer electrolytes are generally prepared using organic solvents that are environmentally malignant. Hence, replacement of organic solvents with water in gel-polymer electrolytes is desirable which also minimizes the device cost substantially. The water containing gel-polymer electrolytes, called hydrogel-polymer electrolytes, are, however, limited by a low operating potential-window of only about 1.23 V. This article reviews salient features of electrochemical capacitors employing hydrogel-polymer electrolytes.
Resumo:
Pt ions-CeO2 interaction in Ce1-xPtxO2-delta (x=0.02) has been studied for the first time by electrochemical method combined with x-ray diffraction and x-ray photoelectron spectroscopy. Working electrodes made of CeO2 and Ce0.98Pt0.02O2-delta mixed with 30% carbon are treated electrochemically between 0.0-1.2 V in potentiostatic (chronoamperometry) and potentiodynamic (cyclic voltametry) mode with reference to saturated calomel electrode. Reversible oxidation of Pt-0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y=0.35) after applying 1.2 V, which is not reversible; Ce0.98Pt0.02O2-delta reaches a steady state with Pt2+:Pt4+ in the ratio of 0.60:0.40 and Ce4+:Ce3+ in the ratio of 0.55:0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V, which is reversible. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2-delta forms a stable electrode for oxidation of H2O to O-2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction in Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt-0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple.
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A series of bimetallic acetylacetonate (acac) complexes, AlxCr1-x(acac)(3), 0 <= x <= 1, have been synthesized for application as precursors for the CVD Of Substituted oxides, such as (AlxCr1-x)(2)O-3. Detailed thermal analysis has been carried out on these complexes, which are solids that begin subliming at low temperatures, followed by melting, and evaporation from the melt. By applying the Langmuir equation to differential thermogravimetry data, the vapour pressure of these complexes is estimated. From these vapour pressure data, the distinctly different enthalpies of sublimation and evaporation are calculated, using the Clausius-Clapeyron equation. Such a determination of both the enthalpies of sublimation and evaporation of complexes, which sublime and melt congruently, does not appear to have been reported in the literature to date.
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To correlate the Raman frequencies of the amide I and III bands to beta-turn structures, three peptides shown to contain beta-turn structure by x-ray diffraction and NMR were examined. The compounds examined were tertiary (formula: see text). The amide I band of these compounds is seen at 1,668, 1,665, and 1,677 cm-1, and the amide III band appears at 1,267, 1,265, and 1,286 cm-1, respectively. Thus, it is concluded that the amide I band for type III beta-turn structure appears in the range between 1,665 and 1,677 cm-1 and the amide III band between 1,265 and 1,286 cm-1.
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The nucleataon growth model of electrochemical phase formation is analysed for the hnear potential sweep input Apart from deducing diagnostic criteria and method~ of estimating model parameters, the predictions of the nucleation growth model are compared and contrasted with those of a sample adsorption model A dastlnCtlOn is made possible between adsorption and phase transition, which seems useful for understanding the nature of ECPF phenomena, especially underpotentlal deposition (UPD).
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The mechanical properties of arterial walls have long been recognized to play an essential role in the development and progression of cardiovascular disease (CVD). Early detection of variations in the elastic modulus of arteries would help in monitoring patients at high cardiovascular risk stratifying them according to risk. An in vivo, non-invasive, high resolution MR-phase-contrast based method for the estimation of the time-dependent elastic modulus of healthy arteries was developed, validated in vitro by means of a thin walled silicon rubber tube integrated into an existing MR-compatible flow simulator and used on healthy volunteers. A comparison of the elastic modulus of the silicon tube measured from the MRI-based technique with direct measurements confirmed the method's capability. The repeatability of the method was assessed. Viscoelastic and inertial effects characterizing the dynamic response of arteries in vivo emerged from the comparison of the pressure waveform and the area variation curve over a period. For all the volunteers who took part in the study the elastic modulus was found to be in the range 50-250 kPa, to increase during the rising part of the cycle, and to decrease with decreasing pressure during the downstroke of systole and subsequent diastole.
Resumo:
The use of two liquid crystals as solvents in the determination of molecular structure has been demonstrated for systems which do not provide structural information from studies in a single solvent owing to the fact that the spectra are deceptively simple, with the result that all the spectral parameters cannot be derived with reasonable precision. The specific system studied was 2-(p-bromophenyl)-4,6-dichloropyrimidine, for which relative inter-proton discances have been determined from the proton NMR spectra in two nematic solvents.
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Power calculation and sample size determination are critical in designing environmental monitoring programs. The traditional approach based on comparing the mean values may become statistically inappropriate and even invalid when substantial proportions of the response values are below the detection limits or censored because strong distributional assumptions have to be made on the censored observations when implementing the traditional procedures. In this paper, we propose a quantile methodology that is robust to outliers and can also handle data with a substantial proportion of below-detection-limit observations without the need of imputing the censored values. As a demonstration, we applied the methods to a nutrient monitoring project, which is a part of the Perth Long-Term Ocean Outlet Monitoring Program. In this example, the sample size required by our quantile methodology is, in fact, smaller than that by the traditional t-test, illustrating the merit of our method.
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A two-state Ising model has been applied to the two-dimensional condensation of tymine at the mercury-water interface. The model predicts a quadratic dependence of the transition potential on temperature and on the logarithm of the adsorbate concentration. Both predictions have been confirmed experimentally.
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An experimental investigation by two-dimensional photoelastic technique is carried out to study the stress distribution and to determine the stress-intensity factors for arbitrarily oriented cracks in thin cylindrical shells subjected to torsion. A new method is employed to evaluate the pure and mixed-mode SIF's.
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The structure of the capsular polysaccharide (CPS) recovered from D46, an extensively antibiotic resistant ST25 Acinetobacter baumannii clinical isolate, was elucidated. The structure was resolved on the basis of NMR spectroscopy and chemical analyses, and was found to contain a branched neutral pentasaccharide with a backbone composed of GalpNAc and Galp residues, all d configured, and a d-Glcp side group. The KL14 gene cluster found in the D46 genome includes genes for four glycosyltransferases but no modules for synthesis of complex sugars, and this is consistent with the structure of K14. The K14 structure and KL14 sequence clarify the relationship between the structure and K locus sequence for A. nosocomialis isolate LUH5541. The identity of the first sugar of the K14 repeat unit (K unit), and the functions of the four encoded glycosyltransferases and Wzy polymerase were predicted.
Resumo:
Stallard (1998, Biometrics 54, 279-294) recently used Bayesian decision theory for sample-size determination in phase II trials. His design maximizes the expected financial gains in the development of a new treatment. However, it results in a very high probability (0.65) of recommending an ineffective treatment for phase III testing. On the other hand, the expected gain using his design is more than 10 times that of a design that tightly controls the false positive error (Thall and Simon, 1994, Biometrics 50, 337-349). Stallard's design maximizes the expected gain per phase II trial, but it does not maximize the rate of gain or total gain for a fixed length of time because the rate of gain depends on the proportion: of treatments forwarding to the phase III study. We suggest maximizing the rate of gain, and the resulting optimal one-stage design becomes twice as efficient as Stallard's one-stage design. Furthermore, the new design has a probability of only 0.12 of passing an ineffective treatment to phase III study.