Microwave, infrared-microwave double resonance, and theoretical studies of C2H4 center dot center dot center dot H2S complex

In this manuscript, rotational spectra of four new isotopologues of the S-H center dot center dot center dot pi bonded C2H4 center dot center dot center dot H2S complex, i.e., C2D4 center dot center dot center dot H2S, C2D4 center dot center dot center dot D2S, C2D4 center dot center dot center dot HDS, and (CCH4)-C-13 center dot center dot center dot H2S have been reported and analyzed. All isotopologues except C2D4 center dot center dot center dot HDS show a four line pattern whereas a doubling of the transition frequencies was observed for C2D4 center dot center dot center dot HDS. These results together with our previous report on the title complex M. Goswami, P. K. Mandal, D. J. Ramdass, and E. Arunan, Chem. Phys. Lett. 393(1-3), 22-27 (2004)] confirm that both subunits (C2H4 and H2S) are involved in large amplitude motions leading to a splitting of each rotational transition to a quartet. Further, the results also confirm that the motions which are responsible for the observed splittings involve both monomers. Molecular symmetry group analysis, considering the interchange of equivalent H atoms in H2S and C2H4 could explain the observed four line pattern and their intensities in the microwave spectrum. In addition, hydride stretching fundamentals of the complex were measured using coherence-converted population transfer Fourier Transform Microwave-infrared (IR-MW double resonance) experiments in the S-H and C-H stretch regions. Changes in the tunneling splittings upon vibrational excitation are consistent with the isotopic dependence of pure rotational transitions. A complexation shift of 2.7-6.5 cm(-1) has been observed in the two fundamental S-H stretching modes of the H2S monomer in the complex. Vibrational pre-dissociation in the bound S-H stretch has been detected whereas the instrument-limited line-shapes in other S-H and C-H stretches indicate slower pre-dissociation rate. Some local perturbations in the vibrational spectra have been observed. Two combination bands have been observed corresponding to both the S-H stretching fundamentals and what appears to be the intermolecular stretching mode at 55 cm(-1). The tunneling splitting involved in the rotation of C2H4 unit has been deduced to be 1.5 GHz from the IR-MW results. In addition, ab initio barrier heights derived for different motions of the monomers support the experimental results and provide further insight into the motions causing the splitting. (C) 2013 AIP Publishing LLC.

The Modified Selenenyl Amide, M-hydroxy Ebselen, Attenuates Diabetic Nephropathy and Diabetes-Associated Atherosclerosis in ApoE/GPx1 Double Knockout Mice

Seleno-organic glutathione peroxidase (GPx) mimetics, including ebselen (Eb), have been tested in in vitro studies for their ability to scavenge reactive oxygen and nitrogen species, including hydrogen peroxide and peroxynitrite. In this study, we investigated the efficacies of two Eb analogues, m-hydroxy ebselen (ME) and ethanol-ebselen (EtE) and compared these with Eb in cell based assays. We found that ME is superior in attenuating the activation of hydrogen peroxide-induced pro-inflammatory mediators, ERK and P38 in human aortic endothelial cells. Consequently, we investigated the effects of ME in an in vivo model of diabetes, the ApoE/GPx1 double knockout (dKO) mouse. We found that ME attenuates plaque formation in the aorta and lesion deposition within the aortic sinus of diabetic dKO mice. Oxidative stress as assessed by 8-OHdG in urine and nitrotyrosine immunostaining in the aortic sinus and kidney tubules, was reduced by ME in diabetic dKO mice. ME also attenuated diabetes-associated renal injury which included tubulointerstitial fibrosis and glomerulosclerosis. Furthermore, the bioactivity of the pro-fibrotic cytokine transforming growth factor-beta (TGF-beta) as assessed by phospho-Smad2/3 immunostaining was attenuated after treatment with ME. TGF-beta-stimulated increases in collagen I and IV gene expression and protein levels were attenuated by ME in rat kidney tubular cells. However, in contrast to the superior activity of ME in in vitro and cell based assays, ME did not further augment the attenuation of diabetes-associated atherosclerosis and renal injury in our in vivo model when compared with Eb. In conclusion, this study strengthens the notion that bolstering GPx-like activity using synthetic mimetics may be a useful therapeutic strategy in lessening the burden of diabetic complications. However, these studies highlight the importance of in vivo analyses to test the efficacies of novel Eb analogues, as in vitro and cell based assays are only partly predictive of the in vivo situation.

Modeling and analysis of MOS capacitor controlled by independent double gates

This paper, for the first time, explores the charcatersictics of MOS capacitor controlled by independent double gates by numerical simulation and analytical modeling for its possible use in RF circuit design as a varactor. By numerical simulation it is shown how the quasi-static and non-quasi-static characteristics of the first gate capacitance could be tuned by the second gate biases. Effect of body doping and energy quantization are also discussed in this regard. A semi-empirical quasi-static model is also developed by using the existing incomplete Poisson solution of independent double gate transistors. Proposed model, which is valid from accumulation to inversion, is shown to have excellent agreement with numerical simulation for practical bias conditions.

Influence of binder solvent on carbon-layer structure in electrical-double-layer capacitors

Porous activated-carbons with a large surface-area have been the most common materials for electrical-double-layer capacitors (EDLCs). These carbons having a wide pore distribution ranges from micropores to macropores in conjunction with a random pore connection that facilitates the high specific-capacitance values. Pore distribution plays a central role in controlling the capacitance value of EDLCs, since electrolyte distribution inside the active material mainly depends on the pore distribution. This has a direct influence on the distribution of resistance and capacitance values within the electrode. As a result, preparation of electrodes remains a vital issue in realising high-performance EDLCs. Generally, carbon materials along with some binders are dispersed into a solvent and coated onto the current collectors. This study examines the role of binder solvents used for the carbon-ink preparation on the microstructure of the electrodes and the consequent performance of the EDLCs. It is observed that the physical properties of the binder solvent namely its dielectric constant, viscosity and boiling point have important role in determining the pore-size distribution as well as the microstructure of electrodes which influence their specific capacitance values.

Design of double toggle switching mechanisms

Toggle mechanisms are ubiquitous in electrical switches. However, literature for their mechanical design is scarce. This paper defines and classifies the toggle phenomena observed during switching. The concept of double toggle introduced in this paper enables a systematic screening of kinematic structure for the suitability in high performance switches. Seven structural and three kinematic criteria are identified for this purpose. It is also demonstrated that each such feasible kinematic structure lends itself to multiple physical embodiments. Therefore, the theory and procedure presented in this work can be used for design of numerous kinematically distinct mechanisms. One representative mechanical embodiment for a novel double toggle switch, including mass and geometric shape of links has been included in the paper. The switching behavior of the design is validated using Pro/Mechanism (TM). (C) 2013 Elsevier Ltd. All rights reserved.

Glassy dielectric response in Tb2NiMnO6 double perovskite with similarities to a Griffiths phase

Results of frequency-dependent and temperature-dependent dielectric measurements performed on the double-perovskite Tb2NiMnO6 are presented. The real (epsilon(1)(f,T)) and imaginary (epsilon(2)(f,T)) parts of dielectric permittivity show three plateaus suggesting dielectric relaxation originating from the bulk, grain boundaries and the sample-electrode interfaces, respectively. The epsilon(1)(f,T) and epsilon(2)(f,T) are successfully simulated by a RC circuit model. The complex plane of impedance, Z'-Z `', is simulated using a series network with a resistor R and a constant phase element. Through the analysis of epsilon(f,T) using the modified Debye model, two different relaxation time regimes separated by a characteristic temperature, T*, are identified. The temperature variation of R and C corresponding to the bulk and the parameter alpha from modified Debye fit lend support to this hypothesis. Interestingly, the T* compares with the Griffiths temperature for this compound observed in magnetic measurements. Though these results cannot be interpreted as magnetoelectric coupling, the relationship between lattice and magnetism is markedly clear. We assume that the observed features have their origin in the polar nanoregions which originate from the inherent cationic defect structure of double perovskites. Copyright (C) EPLA, 2013

A Gibbs-ensemble based technique for Monte Carlo simulation of electric double layer capacitors (EDLC) at constant voltage

Current methods for molecular simulations of Electric Double Layer Capacitors (EDLC) have both the electrodes and the electrolyte region in a single simulation box. This necessitates simulation of the electrode-electrolyte region interface. Typical capacitors have macroscopic dimensions where the fraction of the molecules at the electrode-electrolyte region interface is very low. Hence, large systems sizes are needed to minimize the electrode-electrolyte region interfacial effects. To overcome these problems, a new technique based on the Gibbs Ensemble is proposed for simulation of an EDLC. In the proposed technique, each electrode is simulated in a separate simulation box. Application of periodic boundary conditions eliminates the interfacial effects. This in addition to the use of constant voltage ensemble allows for a more convenient comparison of simulation results with experimental measurements on typical EDLCs. (C) 2014 AIP Publishing LLC.

Continuity equation based nonquasi-static charge model for independent double gate MOSFET

Using the numerical device simulation we show that the relationship between the surface potentials along the channel in any double gate (DG) MOSFET remains invariant in QS (quasistatic) and NQS (nonquasi-static) condition for the same terminal voltages. This concept along with the recently proposed `piecewise charge linearization' technique is then used to develop the intrinsic NQS charge model for a Independent DG (IDG) MOSFET by solving the governing continuity equation. It is also demonstrated that unlike the usual MOSFET transcapacitances, the inter-gate transcapacitance of a IDG-MOSFET initially increases with the frequency and then saturates, which might find novel analog circuit application. The proposed NQS model shows good agreement with numerical device simulations and appears to be useful for efficient circuit simulation.

Coconut kernel-derived activated carbon as electrode material for electrical double-layer capacitors

Carbonization of milk-free coconut kernel pulp is carried out at low temperatures. The carbon samples are activated using KOH, and electrical double-layer capacitor (EDLC) properties are studied. Among the several samples prepared, activated carbon prepared at 600 A degrees C has a large surface area (1,200 m(2) g(-1)). There is a decrease in surface area with increasing temperature of preparation. Cyclic voltammetry and galvanostatic charge-discharge studies suggest that activated carbons derived from coconut kernel pulp are appropriate materials for EDLC studies in acidic, alkaline, and non-aqueous electrolytes. Specific capacitance of 173 F g(-1) is obtained in 1 M H2SO4 electrolyte for the activated carbon prepared at 600 A degrees C. The supercapacitor properties of activated carbon sample prepared at 600 A degrees C are superior to the samples prepared at higher temperatures.

Heteronuclear proton double quantum-carbon single quantum scalar correlation in solids

A new NMR experiment that exploits the advantages of proton double quantum (DQ) NMR through a proton DQ-carbon single quantum (SQ) correlation experiment in the solid state is proposed. Analogous to the previously proposed 2D H-1 (DQ)-C-13 refocused INEPT experiment (Webber et al., 2010), the correlation between H-1 and C-13 is achieved through scalar coupling evolution, while the double quantum coherence among protons is generated through dipolar couplings. However, the new experiment relies on C-13 transverse coherence for scalar transfer. The new experiment dubbed MAS-J-H-1 (DQ)-C-13-HMQC, is particularly suited for unlabeled molecules and can provide higher sensitivity than its INEPT counterpart. The experiment is applied to four different samples. (C) 2014 Elsevier Inc. All rights reserved.

Effect of Rayleigh numbers on the evolution of double-diffusive salt fingers

This is a transient two-dimensional numerical study of double-diffusive salt fingers in a two-layer heat-salt system for a wide range of initial density stability ratio (R-rho 0) and thermal Rayleigh numbers (Ra-T similar to 10(3) - 10(11)). Salt fingers have been studied for several decades now, but several perplexing features of this rich and complex system remain unexplained. The work in question studies this problem and shows the morphological variation in fingers from low to high thermal Rayleigh numbers, which have been missed by the previous investigators. Considerable variations in convective structures and evolution pattern were observed in the range of Ra-T used in the simulation. Evolution of salt fingers was studied by monitoring the finger structures, kinetic energy, vertical profiles, velocity fields, and transient variation of R-rho(t). The results show that large scale convection that limits the finger length was observed only at high Rayleigh numbers. The transition from nonlinear to linear convection occurs at about Ra-T similar to 10(8). Contrary to the popular notion, R-rho(t) first decrease during diffusion before the onset time and then increase when convection begins at the interface. Decrease in R-rho(t) is substantial at low Ra-T and it decreases even below unity resulting in overturning of the system. Interestingly, all the finger system passes through the same state before the onset of convection irrespective of Rayleigh number and density stability ratio of the system. (C) 2014 AIP Publishing LLC.

Magnetization-steps in Y2CoMnO6 double perovskite: The role of antisite disorder

Antisite disorder is observed to have significant impact on the magnetic properties of the double perovskite Y2CoMnO6 which has been recently identified as a multiferroic. A paramagnetic-ferromagnetic phase transition occurs in this material at T-c approximate to 75 K. At 2K, it displays a strong ferromagnetic hysteresis with a significant coercive field of H-c approximate to 15 kOe. Sharp steps are observed in the hysteresis curves recorded below 8K. In the temperature range 2K <= T <= 5K, the hysteresis loops are anomalous as the virgin curve lies outside the main loop. The field-cooling conditions as well as the rate of field-sweep are found to influence the steps. Quantitative analysis of the neutron diffraction data shows that at room temperature, Y2CoMnO6 consists of 62% of monoclinic P2(1)/n with nearly 70% antisite disorder and 38% Pnma. The bond valence sums indicate the presence of other valence states for Co and Mn which arise from disorder. We explain the origin of steps by using a model for pinning of magnetization at the antiphase boundaries created by antisite disorder. The steps in magnetization closely resemble the martensitic transformations found in intermetallics and display first-order characteristics as revealed in the Arrott's plots. (C) 2014 AIP Publishing LLC.

A Short-Channel Common Double-Gate MOSFET Model Adapted to Gate Oxide Thickness Asymmetry

Existing compact models for common double-gate (CDG) MOSFETs are based on the fundamental assumption of having symmetric gate oxide thickness. In this paper, we demonstrate that using the unique quasi-linear relationship between the surface potentials, it is possible to develop compact model for CDG-MOSFETs without such approximation while preserving the mathematical complexity at the same level of the existing models. In the proposed model, the surface potential relationship is used to include the drain-induced barrier lowering, channel length modulation, velocity saturation, and quantum mechanical effect in the long-channel model and good agreement is observed with the technology computer aided design simulation results.

Observation of magnetically hard grain boundaries in double-perovskite Sr2FeMoO6

Unusual low-temperature magneto-resistance (MR) of ferromagnetic Sr2FeMoO6 polycrystals has been attributed to magnetically hard grain boundaries which act as spin valves. We detected the different magnetic hysteresis curves for the grains and the grain boundaries of polycrystalline Sr2FeMoO6 by utilizing the different probing depths of the different detection modes of x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD), namely, the total electron yield (TEY) mode (probing depth similar to 5 nm) and the total fluorescence yield (TFY) mode (probing depth similar to 100 nm). At 20 K, the magnetic coercivity detected in the TEY mode (H-c,H- TEY) was several times larger than that in the TFY mode (H-c,H- TFY), indicating harder ferromagnetism of the grain boundaries than that of the grains. At room temperature, the grain boundary magnetism became soft and H-c,H- TEY and H-c,H- TFY were nearly the same. From the line-shape analysis of the XAS and XMCD spectra, we found that in the grain boundary region the ferromagnetic component is dominated by Fe2+ or well-screened signals, while the non-magnetic component is dominated by Fe3+ or poorly screened signals. Copyright (C) EPLA, 2014

Enhancing the photocatalytic efficiency of sprayed ZnO thin films through double doping (Sn plus F) and annealing under different ambiences

Doubly (Sn + F) doped zinc oxide (ZnO:Sn:F) thin films were deposited onto glass substrates using a simplified spray pyrolysis technique. The deposited films were annealed at 400 degrees C under two different ambiences (air and vacuum) for 2 h. The photocatalytic activity of these films was assessed through photocatalytic decolorization kinetics of Methylene Blue (MB) dye and the decolorization efficiency of the annealed films was compared with that of their as-deposited counterpart. The photocatalytic studies reveal that the ZnO:Sn:F films annealed under vacuum environment exhibits better photocatalytic efficiency when compared with both air annealed and as-deposited films. The SEM and TEM images depict that the surface of each of the films has an overlayer comprising of nanobars formed on a bottom layer, having spherical grains. The studies show that the diameter of the nanobars plays crucial role in enhancing the photocatalytic activity of the ZnO:Sn:F films. The structural, optical and electrical studies substantiate the discussions on the photocatalytic ability of the deposited films. (C) 2014 Elsevier B.V. All rights reserved.