Benefits of Electronic Wiring and Spacers on Lithium Storage in Nanostructured Lithium-Ion Battery Anodes

The demand for high power density lithium-ion batteries (LIBs) for diverse applications ranging from mobile electronics to electric vehicles have resulted in an upsurge in the development of nanostructured electrode materials worldwide. Graphite has been the anode of choice in commercial LiBs. Due to several detrimental electrochemical and environmental issues, efforts are now on to develop alternative non-carbonaceous anodes which are safe, nontoxic and cost effective and at the same time exhibit high lithium storage capacity and rate capability. Titania (TiO2) and tin (Sn) based systems have gained much attention as alternative anode materials. Nanostructuring of TiO2 and SnO2 have resulted in enhancement of structural stability and electrochemical performances. Additionally, electronic wiring of mesoporous materials using carbon also effectively enhanced electronic conductivity of mesoporous electrode materials. We discuss in this article the beneficial influence of structural spacers and electronic wiring in anatase titania (TiO2) and tin dioxide (SnO2).

Influence of GaN underlayer thickness on structural, electrical and optical properties of InN films grown by PAMBE

We present an extensive study on the structural, electrical and optical properties of InN thin films grown on c-Al2O3, GaN(130 nm)/Al2O3, GaN(200 nm)/Al2O3 and GaN(4 mu m)/Al2O3 by using plasma-assisted molecular beam epitaxy. The high resolution X-ray diffraction study reveals better crystalline quality for the film grown on GaN(4 mu m)/Al2O3 as compared to others. The electronic and optical properties seem to be greatly influenced by the structural quality of the films, as can be evidenced from Hall measurement and optical absorption spectroscopy. Kane's k.p model was used to describe the dependence of optical absorption edge of InN films on carrier concentration by considering the non-parabolic dispersion relation for carrier in the conduction band. Room temperature Raman spectra for the InN films grown on GaN show the signature of residual tensile stress in contrast to the compressive stress observed for the films grown directly on c-Al2O3. (C) 2012 Elsevier B.V. All rights reserved.

Tertiary amine-based glutathione peroxidase mimics: some insights into the role of steric and electronic effects on antioxidant activity

In this work, several tertiary amine-based diaryl diselenides were synthesized and evaluated for their glutathione peroxidase (GPx)-like antioxidant activities using hydrogen peroxide, tert-butyl hydroperoxide and cumene hydroperoxide as substrates and thiophenol (PhSH) and glutathione (GSH) as co-substrates. A comparison of the GPx-like activity of 4-methoxy-substituted N,N-dialkylbenzylamine-based diselenides with that of the corresponding 6-methoxy-substituted compounds indicates that the activity highly depends on the position of the methoxy substituent. Although the methoxy group at 4- and 6-position alters the electronic properties of selenium, the substitution at the 6-position provides the required steric protection for some of the key intermediates in the catalytic cycle. A detailed experimental and theoretical investigation reveals that the 6-methoxy substituent prevents the undesired thiol exchange reactions at the selenium centers in the selenenyl sulfide intermediates. The 6-methoxy substituent also prevents the formation of seleninic and selenonic acids. When PhSH is used as the thiol co-substrate, the 4-methoxy-substituted diselenides exhibit GPx-like activity similar to that of the parent compounds as the 4-methoxy substituent does not block the selenium center in the selenenyl sulfide intermediates from thiol exchange reactions. In contrast, the 4-methoxy substituent significantly enhances the GPx-like activity of the diselenides when glutathione (GSH) is used as the co-substrate. (C) 2012 Elsevier Ltd. All rights reserved.

Chiral discrimination and the measurement of enantiomeric excess from a severely overcrowded NMR spectrum

NMR spectroscopic chiral visualization, unambiguous assignment of peaks pertaining to R and S enantiomers and the subsequent measurement of enantiomeric composition demands a highly resolved spectrum. The method fails when the spectrum is severely overcrowded or highly complex, thereby hampering the determination of enantiomeric excess. In order to circumvent such problems we propose the utility of pure shift spectrum obtained by resolving the chemical shift and coupling information in two orthogonal dimensions. The skew projected spectrum yields singlet's at the respective chemical shift positions, permitting the unravelling of the superimposed spectral transitions for each enantiomer and measurement of enantiomeric composition. (C) 2012 Elsevier B. V. All rights reserved.

Dual emissive borane-BODIPY dyads: molecular conformation control over electronic properties and fluorescence response towards fluoride ions

Facile synthesis of two new dimesitylboryl appended BODIPYs is reported. The two dyads have similar fluorescent chromophores but differ in their molecular conformations. They exhibit dual fluorescence, intramolecular energy transfer between boryl and BODIPY chromophores and different fluorescence responses (emission enhancement and quenching) upon fluoride binding.

Bubble size measurement and error analysis in a gas liquid ejector

Bubble size in a gas liquid ejector has been measured using the image technique and analysed for estimation of Sauter mean diameter. The individual bubble diameter is estimated by considering the two dimensional contour of the ellipse, for the actual three dimensional ellipsoid in the system by equating the volume of the ellipsoid to that of the sphere. It is observed that the bubbles are of oblate and prolate shaped ellipsoid in this air water system. The bubble diameter is calculated based on this concept and the Sauter mean diameter is estimated. The error between these considerations is reported. The bubble size at different locations from the nozzle of the ejector is presented along with their percentage error which is around 18%.

Measurement and correlation of quaternary solubilities of dihydroxybenzene isomers in supercritical carbon dioxide

The equilibrium quaternary solubilities of dihydroxybenzene (resorcinol + pyrocatechol + hydroquinone + SCCO2) isomers were experimentally determined at 308, 318 and 328K over a pressure range of 9.8-15.7 MPa by using a saturation method. The effects of temperature, pressure and the components on each other have been thoroughly investigated. The selectivity of SCCO2 for ternary (resorcinol + pyrocatechol + SCCO2) and quaternary systems was discussed. A new model equation for quaternary solubilities of solids has been developed by accounting for non-idealities by combining the solution model with Wilson activity coefficient model. The model equation has five adjustable parameters and correlates the quaternary solubilities of current data along with two other quaternary data reported in the literature. (C) 2012 Elsevier B.V. All rights reserved.

A method for measurement of planar liquid volume fraction in dense sprays

A methodology for measurement of planar liquid volume fraction in dense sprays using a combination of Planar Laser-Induced Fluorescence (PLIF) and Particle/Droplet Imaging Analysis (PDIA) is presented in this work. The PLIF images are corrected for loss of signal intensity due to laser sheet scattering, absorption and auto-absorption. The key aspect of this work pertains to simultaneously solving the equations involving the corrected PLIF signal and liquid volume fraction. From this, a quantitative estimate of the planar liquid volume fraction is obtained. The corrected PLIF signal and the corrected planar Mie scattering can be also used together to obtain the Sauter Mean Diameter (SMD) distribution by using data from the PDIA technique at a particular location for calibration. This methodology is applied to non-evaporating sprays of diesel and a more viscous pure plant oil at an injection pressure of 1000 bar and a gas pressure of 30 bar in a high pressure chamber. These two fuels are selected since their viscosity values are very different with a consequently very different spray structure. The spatial distribution of liquid volume fraction and SMD is obtained for two fuels. The proposed method is validated by comparing liquid volume fraction obtained by the current method with data from PDIA technique. (C) 2012 Elsevier Inc. All rights reserved.

Measurement of IGBT switching characteristics and loss using coaxial current transformer

Device switching times and switching energy losses are required over a wide range of practical working conditions for successful design of insulated gate bipolar transistor (IGBT) based power converters. This paper presents a cost-effective experimental setup using a co-axial current transformer for measurement of IGBT switching characteristics and switching energy loss. Measurements are carried out on a 50A, 1200V IGBT (SKM50GB123D) for different values of gate resistance, device current and junction temperature. These measurements augment the technical data available in the device datasheet.Short circuit transients are also investigated experimentally under hard switched fault as well as fault under load conditions.

Electronic energy transfer between long-range resonance states of 3-mercaptopropionic acid capped CdTe quantum dots in aqueous media

We demonstrate electronic energy transfer between resonance states of 2 and 2.8 nm CdTe quantum dots in aqueous media using steady-state photoluminescence spectroscopy without using any external linker molecule. With increasing concentration of larger dots, there is subsequent quenching of luminescence in smaller dots accompanied by the enhancement of luminescence in larger dots. Our experimental evidence suggests that there is long-range resonance energy transfer among electronic excitations, specifically from the electronically confined states of the smaller dots to the higher excited states of the larger dots.

Tunability of electronic states in ultrathin gold nanowires

The electronic state in ultrathin gold nanowires is tuned by careful engineering of the device architecture via a chemical methodology. The electrons are localized to an insulating state (showing variable range hopping transport) by simply bringing them close to the substrate, while the insertion of an interlayer leads to a Tomonaga Luttinger liquid state.

Calibration of etched fiber bragg grating sensor arrays for measurement of molecular surface adsorption

Etched Fiber Bragg Grating (EFBG) sensors are attractive from the point of the inherently high multiplexing ability of fiber based sensors. However, the strong dependence of the sensitivity of EFBG sensors on the fiber diameter requires robust methods for calibration when used for distributed sensing in a large array format. Using experimental data and numerical modelling, we show that knowledge of the wavelength shift during the etch process is necessary for high-fidelity calibration of EFBG arrays. However as this approach requires the monitoring of every element of the sensor array during etching, we also proposed and demonstrated a calibration scheme using data from bulk refractometry measurements conducted post-fabrication without needing any information about the etching process. Although this approach is not as precise as the first one, it may be more practical as there is no requirement to monitor each element of the sensor array. We were able to calibrate the response of the sensors to within 3% with the approach using information acquired during etching and to within 5% using the post-fabrication bulk refractometry approach in spite of the sensitivities of the array element differing by more than a factor of 4. These two approaches present a tradeoff between accuracy and practicality.

Simultaneous measurement of mechanical and electrical contact resistances during nanoindentation of NiTi shape memory alloys

The nanoindentation technique can be employed in shape memory alloys (SMAs) to discern the transformation temperatures as well as to characterize their mechanical behavior. In this paper, we use it with simultaneous measurements of the mechanical and the electrical contact resistances (ECR) at room temperature to probe two SMAs: austenite (RTA) and martensite (RTM). Two different types of indenter tips - Berkovich and spherical - are employed to examine the SMAs' indentation responses as a function of the representative strain, epsilon(R). In Berkovich indentation, because of the sharp nature of the tip, and in consequence the high levels of strain imposed, discerning the two SMAs on the basis of the indentation response alone is difficult. In the case of the spherical tip, epsilon(R) is systematically varied and its effect on the depth recovery ratio, eta(d), is examined. Results indicate that RTA has higher eta(d) than RTM, but the difference decreases with increasing epsilon(R) such that eta(d) values for both the alloys would be similar in the fully plastic regime. The experimental trends in eta(d) vs. epsilon(R) for both the alloys could be described well with a eta(d) proportional to (epsilon(R))(-1) type equation, which is developed on the basis of a phenomenological model. This fit, in turn, directs us to the maximum epsilon(R), below which plasticity underneath the indenter would not mask the differences in the two SMAs. It was demonstrated that the ECR measurements complement the mechanical measurements in demarcating the reverse transformation from martensite to austenite during unloading of RTA, wherein a marked increase in the voltage was noted. A correlation between recovery due to reverse transformation during unloading and increase in voltage (and hence the electrical resistance) was found. (C) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

SARAS: a precision system for measurement of the cosmic radio background and signatures from the epoch of reionization

SARAS is a correlation spectrometer purpose designed for precision measurements of the cosmic radio background and faint features in the sky spectrum at long wavelengths that arise from redshifted 21-cm from gas in the reionization epoch. SARAS operates in the octave band 87.5-175 MHz. We present herein the system design arguing for a complex correlation spectrometer concept. The SARAS design concept provides a differential measurement between the antenna temperature and that of an internal reference termination, with measurements in switched system states allowing for cancellation of additive contaminants from a large part of the signal flow path including the digital spectrometer. A switched noise injection scheme provides absolute spectral calibration. Additionally, we argue for an electrically small frequency-independent antenna over an absorber ground. Various critical design features that aid in avoidance of systematics and in providing calibration products for the parametrization of other unavoidable systematics are described and the rationale discussed. The signal flow and processing is analyzed and the response to noise temperatures of the antenna, reference termination and amplifiers is computed. Multi-path propagation arising from internal reflections are considered in the analysis, which includes a harmonic series of internal reflections. We opine that the SARAS design concept is advantageous for precision measurement of the absolute cosmic radio background spectrum; therefore, the design features and analysis methods presented here are expected to serve as a basis for implementations tailored to measurements of a multiplicity of features in the background sky at long wavelengths, which may arise from events in the dark ages and subsequent reionization era.

Redox regulation of protein tyrosine phosphatase 1B (PTP1B): Importance of steric and electronic effects on the unusual cyclization of the sulfenic acid intermediate to a sulfenyl amide

The redox regulation of protein tyrosine phosphatase 1B (PTP1B) via the unusual transformation of its sulfenic acid (PTP1B-SOH) to a cyclic sulfenyl amide intermediate is studied by using small molecule chemical models. These studies suggest that the sulfenic acids derived from the H2O2-mediated reactions o-amido thiophenols do not efficiently cyclize to sulfenyl amides and the sulfenic acids produced in situ can be trapped by using methyl iodide. Theoretical calculations suggest that the most stable conformer of such sulfenic acids are stabilized by n(O) -> sigma* (S-OH) orbital interactions, which force the -OH group to adopt a position trans to the S center dot center dot center dot O interaction, leading to an almost linear arrangement of the O center dot center dot center dot S-O moiety and this may be the reason for the slow cyclization of such sulfenic acids to their corresponding sulfenyl amides. On the other hand, additional substituents at the 6-position of o-amido phenylsulfenic acids that can induce steric environment and alter the electronic properties around the sulfenic acid moiety by S center dot center dot center dot N or S center dot center dot center dot O nonbonded interactions destabilize the sulfenic acids by inducing strain in the molecule. This may lead to efficient the cyclization of such sulfenic acids. This model study suggests that the amino acid residues in the close proximity of the sulfenic acid moiety in PTP1B may play an important role in the cyclization of PTP1B-SOH to produce the corresponding sulfenyl amide.