Theory of electron transfer processes via chemisorbed intermediates: Part II. Current-potential characteristics

Current-potential characteristics are obtained numerically for a lone-adsorbate-mediated anodic charge transfer at the electrode-solution interface. An increase in the overpotential leads to the appearance of maxima in the anodic current-potential plots instead of the extended activationless region (i.e. a saturation current at large positive overpotentials) predicted by the direct heterogeneous outer-sphere anodic charge transfer process. A detailed analysis of the dependence of current-potential profiles and other kinetic parameters on various system parameters is also presented.

Embedded Thin Film Resistors on BCB by Low-Cost PWB Compatible Electroless Plating by Direct Foil Lamination Transfer Processes

Benzocyclobutene (BCB) has been proposed as a board level dielectric for advanced system-on-package (SOP) module primarily due to its attractive low-loss (for RF application) and thin film (for high density wiring) properties. Realization of embedded resistors on low loss benzocyclobutene (dielectric loss ~0.0008 at > 40 GHz) has been explored in this study. Two approaches, viz, foil transfer and electroless plating have been attempted for deposition of thin film resistors on benzocyclobutene (BCB). Ni-P alloys were plated using conventional electroless plating, and NiCr and NiCrAlSi foils were used for the foil transfer process. This paper reports NiP and NiWP electroless plated embedded resistors on BCB dielectric for the first time in the literature

Probing Ultrafast Photoinduced Electron Transfer to TiO2 from CdS Nanocrystals of Varying Crystallographic Phase Content

The photoinduced electron transfer processes in a nanoheterostructured semiconductor assembly are complex and depend on various parameters Of the constituents of the assembly. We present here the ultrafast electron transfer characteristics of an assembly comprised of a Wide band semiconductor, titanium dioxide (TiO2), attached to light-harvesting cadmium sulfide (CdS) nanotrystals of varying crystallographic phase content. Quantitative analysis of Synchrotron high-resolution X-ray. diffraction data of CdS nanocrystals precisely reveals the presence of both wurtzite and zinc blende phases in varying amounts. The,estimated content of crystal phases is observed to be strongly dependent on an important synthesis parameter, viz., the ratio of the two solvents. The biphasit nature of CdS influences directly the shape of the nanocrystal at long reaction times as well as the transfer of the photoexcited electrons from the CdS to TiO2 as obtained from transient absorption spectroscopy. A higher amount of zinc blende Phase is observed to be beneficial for fast electron transfer across the CdS-TiO2 interface. The electron transfer rate constant differs by one order of magnitude between the CdS nanocryStals and varies linearly with the fraction of the phases.

Thermochemical and kinetic studies on the effects of cobalt salicylate on the oxidative degradation of polystyrene

The effect of cobalt salicylate on the oxidative degradation and ignition of polystyrene has been studied. It was found that cobalt salicylate sensitizes both the degradation and ignition of polystyrene by facilitating electron-transfer processes in the propagation step. From thermochemical and kinetic studies it was found that the cobalt ion, owing to its ability to exist in variable valence states, promotes electron transfer in the propagation step of polymer degradation, increasing the rate of propagation and consequently the overall rate. Using solid-phase thermal ignition theory, an attempt has been made to explain the sensitization of ignition by the cobalt ion.

Kinetics and mechanism for dye degradation with ionic Pd-substituted ceria

The degradation of the dye, Orange G, was carried out in the presence of H2O2 and Pd-substituted/impregnated CeO2. The effects of pH, initial dye concentration, initial H2O2 concentration, temperature, catalyst loading, and Pd content in the catalyst on the degradation of the dye were investigated. Eight to twelve percent degradation of the dye was obtained in 1 h when the reaction was carried out in the presence of CeO2 or H2O2 or Pd-substituted/impregnated CeO2 while 17% and 97% degradation was obtained when H2O2 was used with Pd-impregnated CeO2 and Pd-substituted CeO2, respectively. This difference clearly indicated that the ionic substitution of Pd played a key role in the degradation of the dye. A mechanism for the reaction was proposed based upon the catalyst structure and the electron transfer processes that take place in the metal ion substituted system in a reducible oxide. The reaction was found to follow first order kinetics and the influence of all the parameters on the degradation kinetics was compared using the rate constants. (c) 2011 Elsevier B.V. All rights reserved.

Rapid Synthesis of Ultrahigh Adsorption Capacity Zirconia by a Solution Combustion Technique

Tetragonal ZrO2 was synthesized by the solution combustion technique using glycine as the fuel. The compound was characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and BET surface area analysis. The ability of this compound to adsorb dyes was investigated, and the compound had a higher adsorption capacity than commercially activated carbon. Infrared spectroscopic observations were used to determine the various interactions and the groups responsible for the adsorption activity of the compound. The effects of the initial concentration of the dye, temperature, adsorbent concentration, and pH of the solution were studied. The kinetics of adsorption was described as a first-order process, and the relative magnitudes of internal and external mass transfer processes were determined. The equilibrium adsorption was also determined and modeled by a composite Langmuir-Freundlich isotherm.

Turbulent free convection above a heated plate inclined at a small angle to the horizontal Journal

An investigation has been made of the structure of the motion above a heated plate inclined at a small angle (about 10°) to the horizontal. The turbulence is considered in terms of the similarities to and differences from the motion above an exactly horizontal surface. One effect of inclination is, of course, that there is also a mean motion. Accurate data on the mean temperature field and the intensity of the temperature fluctuations have been obtained with platinum resistance thermometers, the signals being processed electronically. More approximate information on the velocity field has been obtained with quartz fibre anemometers. These results have been supplemented qualitatively by simultaneous observations of the temperature and velocity fluctuations and also by smoke experiments. The principal features of the flow inferred from these observations are as follows. The heat transfer and the mean temperature field are not much altered by the inclination, though small, not very systematic, variations may result from the complexities of the velocity field. This supports the view that the mean temperature field is largely governed by the large-scale motions. The temperature fluctuations show a systematic variation with distance from the lower edge and resemble those above a horizontal plate when this distance is large. The largescale motions of the turbulence start close to the lower edge, but the smaller eddies do not attain full intensity until the air has moved some distance up the plate. The mean velocity receives a sizable contribution from a ‘through-flow’ between the side-walls. Superimposed on this are developments that show that the momentum transfer processes are complex and certainly not capable of representation by any simple theory such as an eddy viscosity. On the lower part of the plate there is surprisingly large acceleration, but further up the mixing action of the small eddies has a decelerating effect.

Two-channel Kondo physics in odd impurity chains

We study odd-membered chains of spin-1/2 impurities, with each end connected to its own metallic lead. For antiferromagnetic exchange coupling, universal two-channel Kondo (2CK) physics is shown to arise at low energies. Two overscreening mechanisms are found to occur depending on coupling strength, with distinct signatures in physical properties. For strong interimpurity coupling, a residual chain spin-1/2 moment experiences a renormalized effective coupling to the leads, while in the weak-coupling regime, Kondo coupling is mediated via incipient single-channel Kondo singlet formation. We also investigate models in which the leads are tunnel-coupled to the impurity chain, permitting variable dot filling under applied gate voltages. Effective low-energy models for each regime of filling are derived, and for even fillings where the chain ground state is a spin singlet, an orbital 2CK effect is found to be operative. Provided mirror symmetry is preserved, 2CK physics is shown to be wholly robust to variable dot filling; in particular, the single-particle spectrum at the Fermi level, and hence the low-temperature zero-bias conductance, is always pinned to half-unitarity. We derive a Friedel-Luttinger sum rule and from it show that, in contrast to a Fermi liquid, the Luttinger integral is nonzero and determined solely by the ``excess'' dot charge as controlled by gate voltage. The relevance of the work to real quantum dot devices, where interlead charge-transfer processes fatal to 2CK physics are present, is also discussed. Physical arguments and numerical renormalization-group techniques are used to obtain a detailed understanding of these problems.

The June 2010 Nicobar Earthquake: Fault Reactivation on the Subducting Oceanic Plate

The similar to 1300-km-long rupture zone of the 2004 Andaman-Sumatra megathrust earthquake continues to generate a mix of thrust, normal, and strike-slip faulting events. The 12 June 2010 M(w) 7.5 event on the subducting plate is the most recent large earthquake on the Nicobar segment. The left-lateral faulting mechanism of this event is unusual for the outer-rise region, considering the stress transfer processes that follow great underthrusting earthquakes. Another earthquake (M(w) 7.2) with a similar mechanism occurred very close to this event on 24 July 2005. These earthquakes and most of their aftershocks on the subducting plate were generated by left-lateral strike-slip faulting on north-northeast-south-southwest oriented near-vertical faults, in response to north-northwest-south-southeast directed compression. Pre-2004 earthquake faulting mechanisms on the subducting oceanic plate are consistent with this pattern. Post-2004, left-lateral faulting on the subducting oceanic plate clusters between 5 degrees N and 9 degrees N, where the 90 degrees E ridge impinges the trench axis. Our study observes that the subducting plate off the Sumatra and Nicobar segments behaves similarly to a chip of the India-Australia plate, deforming in response to a generally northwest-southeast oriented compression, an aspect that must be factored into the plate deformation models.

Tuning the parameters to establish Quenching and enhancement regimes in hybrid Gold nanoparticles and CdSe Quantum dots monolayer

The multi-component nanomaterials combine the individual properties and give rise to emergent phenomenon. Optical excitations in such hybrid nonmaterial's ( for example Exciton in semiconductor quantum dots and Plasmon in Metal nanomaterials) undergo strong weak electromagnetic coupling. Such exciton-plasmon interactions allow design of absorption and emission properties, control of nanoscale energy-transfer processes, and creation of new excitations in the strong coupling regime.This Exciton plasmon interaction in hybrid nanomaterial can lead to both enhancement in the emission as well as quenching. In this work we prepared close-packed hybrid monolayer of thiol capped CdSe and gold nanoparticles. They exhibit both the Quenching and enhancements the in PL emission.The systematic variance of PL from such hybrid nanomaterials monolayer is studied by tuning the Number ratio of Gold per Quantum dots, the surface density of QDs and the spectral overlap of emission spectrum of QD and absorption spectrum of Gold nanoparticles. Role of Localized surface Plasmon which not only leads to quenching but strong enhancements as well, is explored.

Triarylborane-Appended New Triad and Tetrad: Chromogenic and Fluorogenic Anion Recognition

Facile synthesis of triad 3 and tetrad 4 incorporating -B(Mes)(2) (Mes = mesityl (2,4,6-trimethylphenyl)), boron dipyrromethene (BODIPY), and triphenylamine is reported. Introduction of two dissimilar acceptors (triarylborane and BODIPY) on a single donor resulted in two distinct intramolecular charge transfer processes (amine-to-borane and amine-to-BODIPY). The absorption and emission properties of the new triad and tetrad are highly dependent on individual building units. The nature of electronic communication among the individual fluorophore units has been comprehensively investigated and compared with building units. Compounds 3 and 4 showed chromogenic and fluorogenic responses for small anions such as fluoride and cyanide.

Organic white-light emitting materials

Full-color emissive organic materials have attracted significant attention in recent years as key components in display and lighting devices based on OLEDs. An ideal white-light emitter demands simultaneous emission of red, green and blue with nearly similar distribution of intensities covering the entire region of visible spectra. However, the design of such white-light emitters is not straightforward. Mixing several emitters is seldom successful owing to the negative effects of intermolecular interactions and energy transfer processes. Nonetheless, these fundamental questions have been addressed in recent times by several research groups of vastly different expertise leading to a considerable progress in the field of organic white-light emitters. The designs cover a large area of the chemistry ranging from frustrated energy transfer to simple protonation or from designed self-assembly to simple mixing of materials. In this review, the concepts and rational approaches underlying the design of white-light emissive organic materials are described. (C) 2014 Elsevier Ltd. All rights reserved.

Electron transfer amongst flavo- and hemo-proteins: diffusible species effect the relay processes, not protein-protein binding

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.

Flow and heat transfer in a stagnation-point flow over a stretching sheet with a magnetic field

The flow and heat transfer problem in the boundary layer induced by a continuous moving surface is important in many manufacturing processes in industry such as the boundary layer along material handling conveyers, the aerodynamic extrusion of plastic sheet, the cooling of an infinite metalic plate in a cooling bath (which may also be electrolyte). Glass blowing, continuous casting and spinning of fibres also involve the flow due to a stretching surface. Sakiadis [1] was the first to study the flow induced by a semi-infinite moving wall in an ambient fluid. On the other hand, Crane [2] first studied the flow over a linearly stretching sheet in an ambient fluid. Subsequently, Crane [3] also investigated the corresponding heat transfer problem. Since then several authors [4-8] have studied various aspects of this problem such as the effects of mass transfer, variable wall temperature, constant heat flux, magnetic field etc. Recently, Andersson [9] has obtained an exact solution of the Navier-Stokes equations for the MHD flow over a linearly stretching sheet in an ambient fluid. Also Chiam [10] has studied the heat transfer with variable thermal conductivity on a stretching sheet when the velocities of the sheet and the free stream are equal.