113 resultados para Electrostatic Potential Dipole Legendre Induced Dyad Polarization
Resumo:
The polarization of radiation by scattering on an atom embedded in combined external quadrupole electric and uniform magnetic fields is studied theoretically. Limiting cases of scattering under Zeeman effect, and Hanle effect in weak magnetic fields are discussed. The theory is general enough to handle scattering in intermediate magnetic fields (Hanle-Zeeman effect) and for arbitrary orientation of magnetic field. The quadrupolar electric field produces asymmetric line shifts, and causes interesting level-crossing phenomena either in the absence of an ambient magnetic field, or in its presence. It is shown that the quadrupolar electric field produces an additional depolarization in the Q/I profiles and rotation of the plane of polarization in the U/I profile over and above that arising from magnetic field itself. This characteristic may have a diagnostic potential to detect steady-state and time-varying electric fields that surround radiating atoms in solar atmospheric layers. (c) 2007 Elsevier Ltd. All rights reserved.
The dynamics of solvation of an electron in the image potential state by a layer of polar adsorbates
Resumo:
Recently, ultrafast two-photon photoemission has been used to study electron solvation at a two-dimensional metal/polar adsorbate interfaces [A. Miller , Science 297, 1163 (2002)]. The electron is bound to the surface by the image interaction. Earlier we have suggested a theoretical description of the states of the electron interacting with a two-dimensional layer of the polar adsorbate [K. L. Sebastian , J. Chem. Phys. 119, 10350 (2003)]. In this paper we have analyzed the dynamics of electron solvation, assuming a trial wave function for the electron and the solvent polarization and then using the Dirac-Frenkel variational method to determine it. The electron is initially photoexcited to a delocalized state, which has a finite but large size, and causes the polar molecules to reorient. This reorientation acts back on the electron and causes its wave function to shrink, which will cause further reorientation of the polar molecules, and the process continues until the electron gets self-trapped. For reasonable values for the parameters, we are able to obtain fair agreement with the experimental observations. (c) 2005 American Institute of Physics.
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Usually metallicity accompanies ferromagnetism. K2Cr8O16 is one of the less common examples of magnetic materials, exhibiting ferromagnetism in the insulating state. Analyzing the electronic and magnetic properties within first principles electronic structure calculations, we find that the doped electrons due to K induce a charge-ordered and insulating ground state and interestingly also introduce a ferromagnetic coupling between the Cr ions. The primary considerations driving the charge ordering are found to be electrostatic ones with the charge being localized on two Cr atoms that minimize the electrostatic energy. The structural distortion that accompanies the ordering gives rise to a rare example of a charge-order driven ferromagnetic insulator.
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Polymorphic forms of the DNA duplex with long stretches of structural monotony are known. Several alternating purine-pyrimidine sequences have been shown to adopt left-handed Z-conformation. We report a DNA sequence d(CGCGCGATCGAT)n exhibiting alternating right-handed B and left-handed Z helical conformation after every half a turn. Further, this unusual conformation with change in handedness after every six base pairs was induced at physiological superhelical density.
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Compositionally up and downgraded Bi4-x/3Ti3-xVxO12 (x=0.0, 0.012,0.03, 0.06) thin films were grown on Pt coated silicon substrates by pulsed laser deposition technique. Downgraded fabrication showed improved ferroelectric polarization in comparison to upgraded fabrication. Films deposited at 650 and 700 degrees C showed very large remnant polarization (2P(r)) value of 82 mu C cm(-2), which is comparatively large among all bismuth based thin films reported so far. A mechanism based on vanadium enrich seeded layer formation in the downgraded structure is proposed for the improvement. Moreover, frequency independent behavior (100Hz-5kHz) of the graded films ensures its potential application for various microelectronic devices. (c) 2010 American Institute of Physics. [doi :10.1063/1.3431543].
Resumo:
Current-potential relationships are derived for porous electrode systems following a homogeneous model and whenadsorbed intermediates participate in the electrode reaction. Limiting Tafel slopes were deduced and compared with thecorresponding behavior on planar electrode systems. The theoretical results showed doubling of Tafel slopes when theslow-step is a charge-transfer reaction and a nonlogarithmic current-voltage behavior when the slow-step is a chemical reaction.Comparison of the experimental results with theory for the case of oxygen reduction on carbon surfaces in alkalinemedia indicates that a slow chemical reaction following the initial charge-transfer reaction to be the likely rate-controllingstep. Theoretical relationships are utilized to determine the exchange current density and the surface coverage by the adsorbedintermediates during the course of oxygen reduction from alkaline solutions on "carbon." Tafel slope measurementson planar and porous electrodes for the same reaction are suggested as one of the diagnostic criteria for elucidatingthe mechanistic pathways of electrochemical reactions.
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A unified treatment of polarization relaxation, dielectric dispersion and solvation dynamics in a dense, dipolar liquid is presented. It is shown that the information of solvent polarization relaxation that is obtained by macroscopic dielectric dispersion experiments is not sufficient to understand dynamics of solvation of a newly created ion or dipole. In solvation, a significant contribution comes from intermediate wave vector processes which depend critically on the short range (nearest‐neighbor) spatial and orientational order that are present in a dense, dipolar liquid. An analytic expression is obtained for the time dependent solvation energy that depends, in addition to the translational and rotational diffusion coefficients of the liquid, on the ratio of solute–solvent molecular sizes and on the microscopic structure of the polar liquid. Mean spherical approximation (MSA) theory is used to obtain numerical results for polarization relaxation, for wave vector and frequency dependent dielectric function and for time dependent solvation energy. We find that in the absence of translational contribution, the solvation of an ion is, in general, nonexponential. In this case, the short time decay is dominated by the longitudinal relaxation time but the long time decay is dominated by much slower large wave vector processes involving nearest‐neighbor molecules. The presence of a significant translational contribution drastically alters the decay behavior. Now, the long‐time behavior is given by the longitudinal relaxation time constant and the short time dynamics is controlled by the large wave vector processes. Thus, although the continuum model itself is conceptually wrong, a continuum model like result is recovered in the presence of a sizeable translational contribution. The continuum model result is also recovered in the limit of large solute to solvent size ratio. In the opposite limit of small solute size, the decay is markedly nonexponential (if the translational contribution is not very large) and a complete breakdown of the continuum model takes place. The significance of these results is discussed.
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Abrin is a type II ribosome-inactivating protein comprising of two subunits, A and B. Of the two, the A-subunit harbours the RNA-N-glycosidase activity and the B subunit is a galactose specific lectin that enables the entry of the protein inside the cell. Abrin inhibits protein synthesis and has been reported to induce apoptosis in several cell types. Based on these observations abrin is considered to have potential for the construction of immunotoxin in cell targeted therapy. Preliminary data from our laboratory however showed that although abrin inhibited the protein synthesis in all cell types, the mode of cell death varied. The aim of the present study was therefore to understand different death pathways induced by abrin in different cells. We used the human B cell line, U266B1 and compared it with the earlier studied T cell line Jurkat, for abrin-mediated inhibition of protein translation as well as cell death. While abrin triggered programmed apoptosis in Jurkat cells in a caspase-dependent manner, it induced programmed necrosis in U266B1 cells in a caspase-independent manner, even when there was reactive oxygen species production and loss of mitochondrial membrane potential. The data revealed that abrin-mediated necrosis involves lysosomal membrane permeabilization and release of cathepsins from the lysosomes. Importantly, the choice of abrin-mediated death pathway in the cells appears to depend on which of the two events occurs first: lysosomal membrane permeabilization or loss of mitochondrial membrane potential that decides cell death by necrosis or apoptosis. (C) 2010 Elsevier Ltd. All rights reserved.
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Potential transients are obtained by using “Padé approximants” (an accurate approximation procedure valid globally — not just perturbatively) for all amplitudes of concentration polarization and current densities. This is done for several mechanistic schemes under constant current conditions. We invert the non-linear current-potential relationship in the form (using the Lagrange or the Ramanujan method) of power series appropriate to the two extremes, namely near reversible and near irreversible. Transforming both into the Pad́e expressions, we construct the potential-time profile by retaining whichever is the more accurate of the two. The effectiveness of this method is demonstrated through illustrations which include couplings of homogeneous chemical reactions to the electron-transfer step.
Molecular expression for dielectric friction on a rotating dipole: Reduction to the continuum theory
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Recently we presented a microscopic expression for dielectric friction on a rotating dipole. This expression has a rather curious structure, involving the contributions of the transverse polarization modes of the solvent and also of the molecular length scale processes. It is shown here that under proper limiting conditions, this expression reduces exactly to the classical continuum model expression of Nee and Zwanzig [J. Chem. Phys. 52, 6353 (1970)]. The derivation requires the use of the asymptotic form of the orientation‐dependent total pair correlation function, the neglect of the contributions of translational modes of the solvent, and also the use of the limit that the size of the solvent molecules goes to zero. Thus, the derivation can be important in understanding the validity of the continuum model and can also help in explaining the results of a recent computer simulation study of dielectric relaxation in a Brownian dipolar lattice.
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Objective: The present study is to evaluate the antiulcer effect of hydroalcoholic (70%) extract of Terminalia chebula fruit. Materials and methods: Aspirin, ethanol and cold restraint stress-induced ulcer methods in rats were used for the study. The effects of the extract on gastric secretions, pH, total and free acidity using pylorus ligated methods were also evaluated. Results: Animals pretreated with doses of 200 and 500 mg/kg hydroalcoholic extract showed significant reduction in lesion index, total affected area and percentage of lesion in comparison with control group (P < 0.05 and P < 0.01) in the aspirin, ethanol and cold restraint stress-induced ulcer models. Similarly extracts increased mucus production in aspirin and ethanol-induced ulcer models. At doses of 200 and 500 mg/kg of T. chebula extract showed antisecretory activity in pylorus ligated model, which lead to a reduction in the gastric juice volume, free acidity, total acidity, and significantly increased gastric pH. Discussion and conclusion: These findings indicate that hydroalcoholic extract of the fruit T. chebula displays potential antiulcerogenic activity. This activity thus lends pharmacological credence to the suggested use of the plant as a natural remedy in the treatment or management of ulcer.
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A complete cDNA encoding a novel hybrid Pro-rich protein (HyPRP) was identified by differentially screening 3x10(4) recombinant plaques of a Cuscuta reflexa cytokinin-induced haustorial cDNA library constructed in lambda gt10. The nucleotide (nt) sequence consists of: (i) a 424-bp 5'-non coding region having five start codons (ATGs) and three upstream open reading frames (uORFs); (ii) an ORF of 987 bp with coding potential for a 329-amino-acid (aa) protein of M(r), 35203 with a hydrophobic N-terminal region including a stretch of nine consecutive Phe followed by a Pro-rich sequence and a Cys-rich hydrophobic C terminus; and (iii) a 178-bp 3'-UTR (untranslated region). Comparison of the predicted aa sequence with the NBRF and SWISSPROT databases and with a recent report of an embryo-specific protein of maize [Jose-Estanyol et al., Plant Cell 4 (1992) 413-423] showed it to be similar to the class of HyPRPs encoded by genes preferentially expressed in young tomato fruits, maize embryos and in vitro-cultured carrot embryos. Northern analysis revealed an approx. 1.8-kb mRNA of this gene expressed in the subapical region of the C. reflexa vine which exhibited maximum sensitivity to cytokinin in haustorial induction.
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A computerized non-linear-least-squares regression procedure to analyse the galvanostatic current-potential data for kinetically hindered reactions on porous gas-diffusion electrodes is reported. The simulated data fit well with the corresponding measured values. The analytical estimates of electrode-kinetic parameters and uncompensated resistance are found to be in good agreement with their respective values obtained from Tafel plots and the current-interrupter method. The procedure circumvents the need to collect the data in the limiting-current region where the polarization values are usually prone to errors. The polarization data for two typical cases, namely, methanol oxidation on a carbon-supported platinum-tin electrode and oxygen reduction on a Nafion-coated platinized carbon electrode, are successfully analysed.
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Photoluminescence and Raman scattering experiments have been carried out on single crystals of C70 up to 31 GPa to investigate the effect of pressure on the optical band gap, vibrational modes and stability of the molecule. The photoluminescence band shifts to lower energies and the pressure dependence of the band maxima yields the hydrostatic deformation potential to be 2.15 eV. The slope changes in the pressure dependence of peak positions and linewidths of the Raman modes associated with the intramolecular vibrations at 1 GPa mark the known face-centred cubic-->rhombohedral orientational ordering transition. The reversible amorphization in C70 at P > 20 GPa has been compared with the irreversible amorphization in C60 at P > 22 GPa in terms of carbon-carbon distance between the neighbouring molecules at the threshold transition pressures, in conjunction with the interplay between the intermolecular and intramolecular interactions.
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A cDNA clone isolated by differentially screening a cytokinin-induced haustorial cDNA library of Cuscuta reflexa was sequenced and identified as the gene coding for cytochrome b(5), based on the similarity of the deduced amino-acid sequence with that of the cauliflower (60% identity) and tobacco (78% identity) proteins. The 5'-UTR is unusually long (720 bp) and contains 14 potential start codons (ATG) and 10 short ORFs.