113 resultados para Electrostatic Potential Dipole Legendre Induced Dyad Polarization
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The ac conductivity and dielectric behaviors of sodium borovanadate glasses have been studied over wide ranges of composition and frequency. The de activation energies calculated from the complex impedance plots decrease linearly with the Na2O concentration, indicating that ionic conductivity dominates in these glasses. The possible origin of low-temperature departures of conductivity curves (from linearity) of vanadium-rich glasses in log sigma versus 1/T plots is discussed. The ac conductivities have been fitted to the Almond-West type power law expression with use of a single value of s. It is found that in most of the glasses s exhibits a temperature-dependent minimum. The dielectric data are converted into moduli (M*) and are analyzed using the Kohlrausch-William-Watts stretched exponential function, The activation barriers, W, calculated from the temperature-dependent dielectric loss peaks compare well with the activation barriers calculated from the de conductivity plots. The stretching exponent beta is found to be temperature independent and is not likely to be related as in the equation beta = 1 - s, An attempt is made to elucidate the origin of the stretching phenomena. It appears that either a model of the increased contribution of polarization energy (caused by the increased modifier concentration) and hence the increased monopole-induced dipole interactions or a model based on increased intercationic interactions can explain the slowing down of the primitive relaxation in ionically conducting glasses.
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An escape mechanism in a bistable system driven by colored noise of large but finite correlation time (tau) is analyzed. It is shown that the fluctuating potential theory [Phys. Rev. A 38, 3749 (1988)] becomes invalid in a region around the inflection points of the bistable potential, resulting in the underestimation of the mean first passage time at finite tau by this theory. It is shown that transitions at large but finite tau are caused by noise spikes, with edges rising and falling exponentially in a time of O(tau). Simulation of the dynamics of the bistable system driven by noise spikes of the above-mentioned nature clearly reveal the physical mechanism behind the transition.
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Cobalt and iron nanoparticles are doped in carbon nanotube (CNT)/polymer matrix composites and studied for strain and magnetic field sensing properties. Characterization of these samples is done for various volume fractions of each constituent (Co and Fe nanoparticles and CNTs) and also for cases when only either of the metallic components is present. The relation between the magnetic field and polarization-induced strain are exploited. The electronic bandgap change in the CNTs is obtained by a simplified tight-binding formulation in terms of strain and magnetic field. A nonlinear constitutive model of glassy polymer is employed to account for (1) electric bias field dependent softening/hardening (2) CNT orientations as a statistical ensemble and (3) CNT volume fraction. An effective medium theory is then employed where the CNTs and nanoparticles are treated as inclusions. The intensity of the applied magnetic field is read indirectly as the change in resistance of the sample. Very small magnetic fields can be detected using this technique since the resistance is highly sensitive to strain. Its sensitivity due to the CNT volume fraction is also discussed. The advantage of this sensor lies in the fact that it can be molded into desirable shape and can be used in fabrication of embedded sensors where the material can detect external magnetic fields on its own. Besides, the stress-controlled hysteresis of the sample can be used in designing memory devices. These composites have potential for use in magnetic encoders, which are made of a magnetic field sensor and a barcode.
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0.85PbMg(1/3)Nb(2/3)O(3)-0.15PbTiO(3) ferroelectric-relaxor thin films have been deposited on La(0.5)nSr(0.5)CoO(3)/(1 1 1) Pt/TiO(2)/SiO(2)/Si by pulsed laser ablation at various oxygen partial pressures in the range 0.05 to 0.4 Torr. All the films have a rhombohedral perovskite structure. The grain morphology and orientation are drastically affected by the oxygen pressure, studied by x-ray diffraction and scanning electron microscopy. The domain structure investigations by dynamic contact electrostatic force microscopy have revealed that the distribution of polar nanoregions and their dynamics is influenced by the grain morphology, orientation and more importantly, oxygen vacancies. The correlation length extracted from autocorrelation function images has shown that the polarization disorder decreases with oxygen pressure up to 0.3 Torr. The presence of polarized domains and their electric field induced switching is discussed in terms of internal bias field and domain wall pinning. Film deposited at 0.4 Torr presents a curious case with unique triangular grain morphology and large polarization disorder.
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We have grown Ga deficient GaN epitaxial films on (0001) sapphire substrate by plasma-assisted molecular beam epitaxy and report the experimental evidence of room temperature ferromagnetic behavior. The observed yellow emission peak in room temperature photoluminescence spectra and the peak positioning at 300 cm(-1) in Raman spectra confirms the existence of Ga vacancies. The x-ray photoelectron spectroscopic measurements further confirmed the formation of Ga vacancies; since the N/Ga is found to be >1. The ferromagnetism is believed to originate from the polarization of the unpaired 2p electrons of N surrounding the Ga vacancy. (C) 2011 American Institute of Physics. [doi:10.1063/1.3654151]
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Niobium-modified lead zirconate stannate titanate antiferroelectric thin films with the chemical composition of (Pb0.99Nb0.02)(Zr0.57Sn0.38Ti0.05)0.98O3 were deposited by pulsed excimer laser ablation technique on Pt-coated Si substrates. Field-induced phase transition from antiferroelectric to ferroelectric properties was studied at different fields as a function of temperature. The field forced ferroelectric phase transition was elucidated by the presence of double-polarization hysteresis and double-butterfly characteristics from polarization versus applied electric field and capacitance and voltage measurements, respectively. The measured forward and reverse switching fields were 25 kV/cm and 77 kV/cm, respectively. The measured dielectric constant and dissipation factor were 540 and 0.001 at 100 kHz, respectively, at room temperature.
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Three-component ferroelectric superlattices consisting of alternating layers of SrTiO3, BaTiO3, and CaTiO3 (SBC) with variable interlayer thickness were fabricated on Pt(111)/TiO2/SiO2/Si (100) substrates by pulsed laser deposition. The presence of satellite reflections in x-ray-diffraction analysis and a periodic concentration of Sr, Ba, and Ca throughout the film in depth profile of secondary ion mass spectrometry analysis confirm the fabrication of superlattice structures. The Pr (remnant polarization) and Ps (saturation polarization) of SBC superlattice with 16.4-nm individual layer thickness (SBC16.4) were found to be around 4.96 and 34 μC/cm2, respectively. The dependence of polarization on individual layer thickness and lattice strain were studied in order to investigate the size dependence of the dielectric properties. The dielectric constant of these superlattices was found to be much higher than the individual component layers present in the superlattice configuration. The relatively higher tunability ( ∼ 55%) obtained around 300 K indicates that the superlattice is a potential electrically tunable material for microwave applications at room temperature. The enhanced dielectric properties were thus discussed in terms of the interfacial strain driven polar region due to high lattice mismatch and electrostatic coupling due to polarization mismatch between individual layers.
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Abstract | A growing interest in the research of chalcogenide glasses can be currently witnessed, which to a large extent is caused by newly opened fields of applications for these materials. Applications in the field of micro- and opto-electronics, xerography and lithography, acousto-optic and memory switching devices and detectors for medical imaging seem to be most remarkable. Accordingly, photo induced phenomena in chalcogenide glasses are attracting much interest. These phenomena can be found both in uniform thin films as well as multilayered films. Among amorphous multilayers, chalcogenide multilayers are attractive because of the potential it has for tailoring the optical properties. I will be presenting some basic idea of photoinduced effects followed by the diffusion mechanisms of Se, Sb and Bi in to As2S3 films.
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We report high pressure Raman studies on single crystals of metallic LaB6 upto a pressure of 16.$ GPa. Raman spectra shows three lines at 680 cm(-1) (T-2g), 1120 cm(-1) (E-g) and 1258 cm(-1) (A(1g)), associated with the internal modes of B-6 molecule. The T-2g mode shows an asymmetric Fano line shape, arising from the interference between the phonon line and the electronic continuum. The line is fitted with I(omega) = I-0(q + epsilon(2))/(I + epsilon(2)) where epsilon = (omega - omega(0))/Gamma, omega(0) is the phonon frequency renormalised due to electron-phonon self energy corrections, Tis the width parameter proportional to the square of the matrix element of the electron-phonon interaction potential. The parameter a signifies the strength of interference. Most interestingly our pressure data for the T-2g mode shows a significant change in the slope of the mode frequency with pressure d omega(0)/dP and Gamma at 9.5 GPa. This clearly indicates that LaB6 undergoes a subtle phase transition at 9.5 GPa within the metallic phase.
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In situ electrochemical polymerization of aniline in a Langmuir trough under applied surface pressure assists in the preferential orientation of polyaniline (PANI) in planar polaronic structure. Exfoliated graphene oxide (EGO) spread on water surface is used to bring anilinium cations present in the subphase to air-water interface through electrostatic interactions. Subsequent electrochemical polymerization of aniline under applied surface pressure in the Schaefer mode results in EGO/PANT composite with PANT in planar polaronic form. The orientation of PANI is confirmed by electrochemical and Raman spectroscopic studies. This technique opens up possibilities of 2-D polymerization at the air-water interface. Electrochemical sensing of hydrogen peroxide is used to differentiate the activity of planar and coiled forms of PANI toward electrocatalytic reactions.
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Acetaminophen is a widely prescribed drug used to relieve pain and fever; however, it is a leading cause of drug-induced liver injury and a burden on public healthcare. In this study, hepatotoxicity in mice post oral dosing of acetaminophen was investigated using liver and sera samples with Fourier Transform Infrared microspectroscopy. The infrared spectra of acetaminophen treated livers in BALB/ mice show decrease in glycogen, increase in amounts of cholesteryl esters and DNA respectively. Rescue experiments using L-methionine demonstrate that depletion in glycogen and increase in DNA are abrogated with pre-treatment, but not post-treatment, with L-methionine. This indicates that changes in glycogen and DNA are more sensitive to the rapid depletion of glutathione. Importantly, analysis of sera identified lowering of glycogen and increase in DNA and chlolesteryl esters earlier than increase in alanine aminotransferase, which is routinely used to diagnose liver damage. In addition, these changes are also observed in C57BL/6 and Nos2(-/-) mice. There is no difference in the kinetics of expression of these three molecules in both strains of mice, the extent of damage is similar and corroborated with ALT and histological analysis. Quantification of cytokines in sera showed increase upon APAP treatment. Although the levels of Tnf alpha and Ifn gamma in sera are not significantly affected, Nos2(-/-) mice display lower Il6 but higher Il10 levels during this acute model of hepatotoxicity. Overall, this study reinforces the growing potential of Fourier Transform Infrared microspectroscopy as a fast, highly sensitive and label-free technique for non-invasive diagnosis of liver damage. The combination of Fourier Transform Infrared microspectroscopy and cytokine analysis is a powerful tool to identify multiple biomarkers, understand differential host responses and evaluate therapeutic regimens during liver damage and, possibly, other diseases.
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S100A2, an EF hand calcium-binding protein, is a potential biomarker in several cancers and is also a TGF-beta (transforming growth factor-beta)-regulated gene in melanoma and lung cancer cells. However, the mechanism of S100A2 regulation by TGF-beta and its significance in cancer progression remains largely unknown. In the present study we report the mechanism of S100A2 regulation by TGF-beta and its possible role in TGF-beta-mediated tumour promotion. Characterization of the S100A2 promoter revealed an AP-1 (activator protein-1) element at positions -1161 to -1151 as being the most critical factor for the TGF-beta 1 response. Chromatin immunoprecipitation and electrophoretic mobility-shift assays confirmed the functional binding of the AP-1 complex, predominantly JunB, to the S100A2 promoter in response to TGF-beta 1 in HaCaT keratinocytes. JunB overexpression markedly stimulated the S100A2 promoter which was blocked by the dominant-negative JunB and MEK1 MAPK (mitogen-activated protein kinase)/ERK (extracellular-signal-regulated kinase) kinase 1] inhibitor, PD98059. Intriguingly, despite the presence of a putative SMAD-binding element, S100A2 regulation by TGF-beta 1 was found to be SMAD3 independent. Interestingly, p53 protein and TGF-beta 1 show synergistic regulation of the S100A2 promoter. Finally, knockdown of S100A2 expression compromised TGF-beta 1-induced cell migration and invasion of Hep3B cells. Together our findings highlight an important link between the TGF-beta 1-induced MAPK and p53 signalling pathways in the regulation of S100A2 expression and pro-tumorigenic actions.
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Evaluating the hazard potential of the Makran subduction zone requires understanding the previous records of the large earthquakes and tsunamis. We address this problem by searching for earthquake and tectonic proxies along the Makran Coast and linking those observations with the available constraints on historical seismicity and the tell-tale characteristics of sea floor morphology. The earthquake of Mw 8.1 of 1945 and the consequent tsunami that originated on the eastern part of the Makran are the only historically known hazardous events in this region. The seismic status of the western part of the subduction zone outside the rupture area of the 1945 earthquake remains an enigma. The near-shore shallow stratigraphy of the central part of Makran near Chabahar shows evidence of seismically induced liquefaction that we attribute to the distant effects of the 1945 earthquake. The coastal sites further westward around Jask are remarkable for the absence of liquefaction features, at least at the shallow level. Although a negative evidence, this possibly implies that the western part of Makran Coast region may not have been impacted by near-field large earthquakes in the recent past-a fact also supported by the analysis of historical data. On the other hand, the elevated marine terraces on the western Makran and their uplift rates are indicative of comparable degree of long-term tectonic activity, at least around Chabahar. The offshore data suggest occurrences of recently active submarine slumps on the eastern part of the Makran, reflective of shaking events, owing to the great 1945 earthquake. The ocean floor morphologic features on the western segment, on the contrary, are much subdued and the prograding delta lobes on the shelf edge also remain intact. The coast on the western Makran, in general, shows indications of progradation and uplift. The various lines of evidence thus suggest that although the western segment is potentially seismogenic, large earthquakes have not occurred there in the recent past, at least during the last 600 years. The recurrence period of earthquakes may range up to 1,000 years or more, an assessment based on the age of the youngest dated coastal ridge. The long elapsed time points to the fact that the western segment may have accumulated sufficient slip to produce a major earthquake.
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The synthesis, hydrogelation, and aggregation-induced emission switching of the phenylenedivinylene bis-N-octyl pyridinium salt is described. Hydrogelation occurs as a consequence of pi-stacking, van der Waals, and electrostatic interactions that lead to a high gel melting temperature and significant mechanical properties at a very low weight percentage of the gelator. A morphology transition from fiber-to-coil-to-tube was observed depending on the concentration of the gelator. Variation in the added salt type, salt concentrations, or temperature profoundly influenced the order of aggregation of the gelator molecules in aqueous solution. Formation of a novel chromophore assembly in this way leads to an aggregation-induced switch of the emission colors. The emission color switches from sky blue to white to orange depending upon the extent of aggregation through mere addition of external inorganic salts. Remarkably, the salt effect on the assembly of such cationic phenylenedivinylenes in water follow the behavior predicted from the well-known Hofmeister effects. Mechanistic insights for these aggregation processes were obtained through the counterion exchange studies. The aggregation-induced emission switching that leads to a room-temperature white-light emission from a single chromophore in a single solvent (water) is highly promising for optoelectronic applications.
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We present a detailed study on the behavior of vinylcyclopropanes as masked donor acceptor system toward the stereoselective synthesis of Z-alkylidenetetrahydrofurans. Results of bromenium catalyzed indirect activation of C-C bond of vinylcyclopropanes and concomitant cyclization to alkylidenetetrahydrofuran and other heterocycles have been discussed. The stereoselective formation of the Z-isomer is strongly controlled by the extent of destabilization of one of the gauche conformers of the vinylcyclopropane. The ring-opening/cyclization step was found to be stereospecific as in the case of DA cyclopropanes. The activation of the C-C bond leads to a tight-carbocation intermediate, which is evident from the complete retention of the stereochemistry. The retention of configuration has been established by a necessary control experiment that rules out the possibility of a double inversion pathway. The present results serve as direct stereochemical evidence in support of a tight ion-pair intermediate versus the controversial S(N)2 pathway. A 2D potential energy scan has been carried out at B3LYP/6-31G(d) level theory to obtain the relative energies of the conformers. The Z-selectivity observed has been explained on the basis of the relative population of the conformers and modeling the intermediate and transition state involved in the reaction at M06-2x/6-31+G(d) level. Energy profile for the cyclization step was modeled considering various possible pathways through which cyclization can happen. The methodology has been successfully demonstrated on vinylcyclobutanes as well.