83 resultados para Mixed-effect models


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The advent of a new class of high-mobility semiconducting polymers opens up a window to address fundamental issues in electrical transport mechanism such as transport between localized states versus extended state conduction. Here, we investigate the origin of the ultralow degree of disorder (E-a similar to 16 meV) and the ``bandlike'' negative temperature (T) coefficient of the field effect electron mobility: mu(e)(FET) (T) in a high performance (mu(e)(FET) > 2.5 cm(2) V-1 s(-1)) diketopyrrolopyrrole based semiconducting polymer. Models based on the framework of mobility edge with exponential density of states are invoked to explain the trends in transport. The temperature window over which the system demonstrates delocalized transport was tuned by a systematic introduction of disorder at the transport interface. Additionally, the Hall mobility (mu(e)(Hall)) extracted from Hall voltage measurements in these devices was found to be comparable to field effect mobility (mu(e)(FET)) in the high T bandlike regime. Comprehensive studies with different combinations of dielectrics and semiconductors demonstrate the effectiveness of rationale molecular design, which emphasizes uniform-energetic landscape and low reorganization energy.

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The inhibition behavior of colchicine (CC) on the corrosion of mild steel in 0.5 M H2SO4 was evaluated by electrochemical methods such as potentiodynamic polarization and electrochemical impedance spectroscopic measurements. The inhibition efficiency increases with increasing concentration of CC. The potentiodynamic polarization results reveal that CC act as a mixed-type inhibitor by retarding both cathodic and anodic corrosion reactions. Additionally, the synergism was carried out between CC and KI to improve the corrosion inhibition behavior of CC on mild steel. The adsorption of both CC alone and the combined inhibitor (CC + KI) on mild steel surface follows Langmuir adsorption isotherm. The synergism parameter (S (theta) ) was calculated to recognize the existence of synergism between CC and iodide ions. Lastly, an adsorption mechanism of CC molecules with iodide ions is discussed.

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We have employed the highly sensitive electron magnetic resonance technique complimented by magnetization measurements to study the impact of size reduction on the magnetic ordering in nanosized Sm1-x Ca (x) MnO3 (x = 0.35, 0.65 and 0.92). In the bulk form, x = 0.35 sample shows a charge ordering transition at 235 K followed by a mixed magnetic phase, the sample with x = 0.65 exhibits charge order below 275 K and shows an antiferromagnetic insulator phase below 135 K while that with x = 0.92 has a ferromagnetic-cluster glass ground state. Thus, a comparative study of magnetic ground states of bulk and nanoparticles (diameter similar to 25 nm) enables us to investigate size-induced effects on different types of magnetic ordering. It is seen that in the bulk samples the temperature dependences of the EPR parameters are quite different from each other. This difference diminishes for the nanosamples where all the three samples show qualitatively similar behavior. The magnetization measurements corroborate this conclusion.

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Classical models are not successful in describing discharge characteristics of a lead-acid battery when the current density is varied over a wide range. A model is developed in this work to overcome this lacuna by introducing into the standard models two mechanisms that have not been used earlier. Lead sulfate particles nucleate and grow on active materials of electrodes during discharge, resulting in coverage of active area. Increasing rate of discharge builds supersaturation of lead sulfate rapidly, and causes increased extents of nucleation and coverage. Electrodes behave almost like an insulator due to deposition of lead sulfate when active materials are converted to a critical extent, and this can stop discharge process. Influence of this mechanism is also rate dependent. The new model developed is tested against data on polarization behavior, and capacity drawn as a function of current. The model successfully predicts both polarization curves and Peukert behavior. The model is used to predict charge that can be drawn at a current after partial discharge at a different current. Model suggests that altering nucleation behavior can be useful in enhancing capacity available for discharge. (C) 2015 The Electrochemical Society.

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The inhibition performance of ibuprofen triazole (IT) on mild steel (MS) corrosion in 1.0 M HCl and 0.5 M H2SO4 has been investigated by using electrochemical (potentiodynamic polarization and electrochemical impedance spectroscopy), gravimetric, and quantum chemical studies. Electrochemical investigation indicates that IT hampers MS corrosion via adsorption through a mixed inhibition mechanism. The protection ability of IT increases with an increasing concentration of inhibitor and decreases with increasing temperature. The adsorption of IT molecules on MS surface follows the Langmuir adsorption isotherm. Certain quantum chemical parameters were calculated to ascertain the correlation between inhibitive effect and molecular structure of IT.

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Nanocrystalline Mn0.4Zn0.6SmxGdyFe2-(x+y)O4 (x = y = 0.01, 0.02, 0.03, 0.04 and 0.05) were synthesized by combustion route. The detailed structural studies were carried out through X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM). The results confirms the formation of mixed spine phase with cubic structure due to the distortion created with co-dopants substitution at Fe site in Mn-Zn ferrite lattice. Further, the crystallite size increases with an increase of Sm3+-Gd3+ ions concentration while lattice parameter and lattice strain decreases. Furthermore, the effect of Sm-Gd co-doping in Mn-Zn ferrite on the room temperature electrical (dielectric studies) studies were carried out in the wide frequency range 1 GHz-5 GHz. The magnetic studies were carried out using vibrating sample magnetometer (VSM) under applied magnetic field of 1.5T and also room temperature electron paramagnetic resonance (EPR) spectra's were recorded. From the results of dielectric studies, it shows that the real and imaginary part of permittivities are increasing with variation of Gd3+ and Sm3+ concentration. The magnetic studies reveal the decrease of remnant, saturation magnetization and coercivity with increasing of Sm3+-Gd3+ ion concentration. The g-value, peak-to-peak line width and spin concentration evaluated from EPR spectra correlated with cations occupancy. The electromagnetic properties clearly indicate that these materials are the good candidates which are useful at L and C band frequency. (C) 2015 Elsevier B.V. All rights reserved.

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Nonprotein amino acids are being extensively used in the design of synthetic peptides to create new structure mimics. In this study we report the effect of methylene group insertions in a heptapeptide Boc-Ala(1)-Leu(2)-Aib(3)-Xxx(4)-Ala(5)-Leu(6)-Aib(7)-OMe which nicely folds into a mixed 3(10)-/-helical structure when Xxx= Ala. Analogs of this peptide have been made and studied by replacing central Xxx(4) residue with Glycine (-residue), -Alanine (-la), -aminobutyric acid (Gaba), and epsilon-aminocaproic acid (epsilon-Aca). NMR and circular dichroism were used to study the solution structure of these peptides. Crystals of the peptides containing alanine, -la, and Gaba reveal that increasing the number of central methylene (-CH2-) groups introduces local perturbations even as the helical structure is retained. (c) 2015 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 104: 720-732, 2015.

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Hitherto, electron transfer (ET) between redox proteins has been deemed to occur via donor-acceptor binding, and diffusible reactive species are considered as deleterious side-products in such systems. Herein, ET from cytochrome P450 reductase (CPR, an animal membrane flavoprotein) and horseradish peroxidase (HRP, a plant hemoprotein) to cytochrome c (Cyt c, a soluble animal hemoprotein) was probed under diverse conditions, using standard assays. ET in the CPR-Cyt c system was critically inhibited by cyanide and sub-equivalent levels of polar one-electron cyclers like copper ions, vitamin C/Trolox and superoxide dismutase. In the presence of lipids, inhibition was also afforded by amphipathic molecules vitamin E, palmitoyl-vitamin C and the membrane hemoprotein, cytochrome b(5). Such nonspecific inhibition (by diverse agents in both aqueous and lipid phases) indicated that electron transfer/relay was effected by small diffusible agents, whose lifetimes are shortened by the diverse radical scavengers. When CPR was retained in a dialysis membrane and Cyt c presented outside in free solution, ET was still observed. Further, HRP (taken at nM levels) catalyzed oxidation of a phenolic substrate was significantly inhibited upon the incorporation of sub-nM levels of Cyt c. The findings imply that CPR-Cyt c or HRP-Cyt c binding is not crucial for ET. Further, fundamental quantitative arguments (based on diffusion/collision) challenge the erstwhile protein-protein binding-assisted ET hypothesis. It is proven beyond reasonable doubt that mobile and diffusible electron carriers (ions and radicals) serve as ``redox-relay agents'' in the biological ET models/setup studied.