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.

Raman Spectroscopy of the Charge Transfer Complex (TTF)x C60 Br8

We report Raman studies on powder samples of the charge transfer complex (TTF)(x)C60Br8 at room temperature. The phonons show considerable softening with respect to the frequencies observed in the Raman spectrum of solid C60Br8. The strongest mode at 1464 cm(-1) in C60Br8 is red shifted to a doublet with peaks at 1414 and 1421 cm(-1), implying an average phonon softening Delta omega of -47 cm(-1). A comparison with the phonon softening of the corresponding A(g)(2) mode in alkali-doped C-60 (Delta omega similar to -36 cm(-1) for A(6)C(60), A = K, Rb or Cs) suggests that 8 electrons are transferred per C60Br8 molecule in the charge transfer complex. The mode at 503 cm(-1) in C60Br8 is shifted upwards, similar to that in A(6)C(60) compounds.

Scheduling expression trees with reusable registers on delayed-load architectures

In this paper, we look at the problem of scheduling expression trees with reusable registers on delayed load architectures. Reusable registers come into the picture when the compiler has a data-flow analyzer which is able to estimate the extent of use of the registers. Earlier work considered the same problem without allowing for register variables. Subsequently, Venugopal considered non-reusable registers in the tree. We further extend these efforts to consider a much more general form of the tree. We describe an approximate algorithm for the problem. We formally prove that the code schedule produced by this algorithm will, in the worst case, generate one interlock and use just one more register than that used by the optimal schedule. Spilling is minimized. The approximate algorithm is simple and has linear complexity.

Sliding wear of YTZP ceramic against steel: observations on ceramic transfer and wear transition

Sliding tests were conducted, in air, of YTZP ceramic pins against steel discs at an applied pressure of 15.5 MPa over a speed range of 0.3 to 4.0 ms(-1). Pin wear was not detectable until 2.0 m s(-1), after which a finite but small wear rate was observed at 3.0 m s(-1), accompanied by a red glow at the contacting surface. A transition in wear behaviour and friction (mu) occurred at 4.0 ms(-1), increasing the former by over two orders of magnitude. Both mu and wear behaviour changed with time at 4.0 m s(-1). During initial periods mu was high and wear rate increased steadily with time accompanied by ceramic transfer onto the disc, which increased with time. When disc coverage exceeds a certain threshold value, mu decreased rapidly and the wear rate stabilized at a very high value. Metal transfer was not observed at any speed. High surface temperatures brought about significant adhesion between TZP and steel and this together with enhanced plastic deformation brought about a transition in wear behaviour.

Variation of Cu-O charge-transfer energies in YBa2Cu3O7-x thin films studied by photoemission spectroscopy

It is pointed out that the change in the oxidation state of Cu in YBa2CU3O7-x with increasing x vitiates the trend in the Cu(2p) satellite intensity and hence the Cu-O charge-transfer energy. When Y is partly replaced by Ca, however, the satellite intensity and T(c) decrease with the increase in Ca content or hole concentration, just as in other cuprates.

Direct Evaluation Of Transient Stability Improvement With Static Var Compensators Using A Structure Preserving Energy Function

The ability of Static Var Compensators (SVCs) to rapidly and continuously control reactive power in response to changing system conditions can result in the improvement of system stability and also increase the power transfer in the transmission system. This paper concerns the application of strategically located SVCs to enhance the transient stability limits and the direct evaluation of the effect of these SVCs on transient stability using a Structure Preserving Energy Function (SPEF). The SVC control system can be modelled from the steady- state control characteristic to accurately simulate its effect on transient stability. Treating the SVC as a voltage-dependent reactive power load leads to the derivation of a path-independent SPEF for the SVC. Case studies on a 10-machine test system using multiple SVCs illustrate the effects of SVCs on transient stability and its accurate prediction.

Gas-phase controlled mass transfer in a foam-bed reactor

Gas-phase controlled absorption of ammonia in foams made of solutions of sulphuric acid has been studied experimentally. Effects of gas-phase concentration of ammonia and type of surfactant on the performance of the foam-bed reactor are investigated. Gas-phase controlled absorption from a spherical bubble is anaylzed using the asymptotic value of Sherwood number (Sh = 6.58), for both negligible as well as significant changes in the volume of the bubble. The experimental data are shown to be in good agreement with the single-stage model of the foam-bed reactor using these asymptotic sub-models, as well as the diffusion-in-sphere analysis available in literature. Influence of effective diffusivity on the time dependence of fractional gas absorption has been found to be unimportant for foam columns with large times of contact. The asymptotic sub-models have been compared and use of the rigid-sphere asymptotic sub-model is recommended for foam columns of practical relevence.

Multi-installment load distribution in tree networks with delays

This paper presents a new strategy for load distribution in a single-level tree network equipped with or without front-ends. The load is distributed in more than one installment in an optimal manner to minimize the processing time. This is a deviation and an improvement over earlier studies in which the load distribution is done in only one installment. Recursive equations for the general case, and their closed form solutions for a special case in which the network has identical processors and identical links, are derived. An asymptotic analysis of the network performance with respect to the number of processors and the number of installments is carried out. Discussions of the results in terms of some practical issues like the tradeoff relationship between the number of processors and the number of installments are also presented.

Variations in the Levels of Aminoacylation and Modified Nucleotide Content Between Total Transfer-RNAS From Chloroplasts and Etioplasts in Cucumber Cotyledons

Total tRNAs isolated from chloroplasts and etioplasts of cucumber cotyledons were compared with respect to amino acid acceptance, isoacceptor distribution and extent of modification. Aminoacylation of the tRNAs with nine different amino acids studied indicated that the relative acceptor activities of chloroplast total tRNAs for four amino acids are significantly higher than etioplast total tRNAs. Two dimensional polyacrylamide gel electrophoresis (2D-PAGE) of chloroplast total tRNAs separated at least 32 spots, while approximately 41 spots were resolved from etioplast total tRNAs. Comparison of the reversed-phase chromatography (RPC-5) profiles of chloroplast and etioplast leucyl-, lysyl-, phenylalanyl-, and valyl-tRNA species showed no qualitative differences in the elution profiles. However, leucyl-, lysyl- and valyl-tRNA species showed quantitative differences in the relative amounts of the isoaccepting species present in chloroplasts and etioplasts. The analysis of modified nucleotides of total tRNAs from the two plastid types indicated that total tRNA from etioplasts was undermodified with respect to ribothymidine, isopentenyladenosine/hydroxy-isopentenyladenosine, 1-methylguanosine and 2-o-methylguanosine. This indicates that illumination may cause de novo synthesis of chloroplast tRNA-modifying enzymes encoded for by nuclear genes leading to the formation of highly modified tRNAs in chloroplasts. Based on these results, we speculate that the observed decrease in levels of aminoacylation, variations in the relative amounts of certain isoacceptors, and differences in the electrophoretic mobilities of some extra tRNA spots in the etioplast total tRNAs as compared to chloroplast total tRNAs could be due to some partially undermodified etioplast tRNAs. Taken together, the data suggested that the light-induced transformation of etioplasts into chloroplasts is accompanied by increases in the relative levels of some functional chloroplast tRNAs by post transcriptional nucleotide modifications.

Non-exponentiality in electron transfer kinetics: Static versus dynamic disorder models

Non-exponential electron transfer kinetics in complex systems are often analyzed in terms of a quenched, static disorder model. In this work we present an alternative analysis in terms of a simple dynamic disorder model where the solvent is characterized by highly non-exponential dynamics. We consider both low and high barrier reactions. For the former, the main result is a simple analytical expression for the survival probability of the reactant. In this case, electron transfer, in the long time, is controlled by the solvent polarization relaxation-in agreement with the analyses of Rips and Jortner and of Nadler and Marcus. The short time dynamics is also non-exponential, but for different reasons. The high barrier reactions, on the other hand, show an interesting dynamic dependence on the electronic coupling element, V-el.

Non-viral ex vivo hepatic gene transfer by in situ lipofection of liver and intraperitoneal transplantation of hepatocytes

Perfusion of liver with plasmid DNA-lipofectin complexes via the portal vein results in efficient accumulation of the vector in hepatocytes. Such hepatocytes, when administered intraperitoneally into a hepatectomized rat, repopulate the liver and express the transgene efficiently. This procedure obviates the need for large-scale hepatocyte culture for ex vivo gene transfer. Further, intraperitoneal transplantation is a simple and cost-effective strategy of introducing genetically modified hepatocytes into liver. Thus, in situ lipofection of liver and intraperitoneal transfer of hepatocytes can be developed into a novel method of non-viral ex vivo gene transfer technique that has applications in the treatment of metabolic disorders of liver and hepatic gene therapy.

Pressure-induced charge transfer in lanthanum nickel ferrate (LaNi0.5Fe0.5O3) and analogies to composition-driven charge transfer in dilanthanum cuprate (La2CuO4): an infrared study

A reversible pressure-induced phase transition in lanthanum nickel ferrate (LaNi0.5Fe0.5O3) manifests itself in the infrared spectrum of the transition metal-oxygen stretching (nu(TM-O)) modes by the emergence of new peaks at pressures greater than similar to 1.4 x 10(9) Pa. Analogies to this transition are made by considering charge transfer in dilanthanum cuprate (La2CuO4) and its modification by partial substitution of copper ions by chromium ions.

Studies on age-hardening characteristics of ceramic particle/matrix interfaces in Al-Cu-SiCp composites using ultra low-load-dynamic microhardness measurements

Ultra low-load-dynamic microhardness testing facilitates the hardness measurements in a very low volume of the material and thus is suited for characterization of the interfaces in MMC's. This paper details the studies on age-hardening behavior of the interfaces in Al-Cu-5SiC(p) composites characterized using this technique. Results of hardness studies have been further substantiated by TEM observations. In the solution-treated condition, hardness is maximum at the particle/matrix interface and decreases with increasing distance from the interface. This could be attributed to the presence of maximum dislocation density at the interface which decreases with increasing distance from the interface. In the case of composites subjected to high temperature aging, hardening at the interface is found to be faster than the bulk matrix and the aging kinetics becomes progressively slower with increasing distance from the interface. This is attributed to the dislocation density gradient at the interface, leading to enhanced nucleation and growth of precipitates at the interface compared to the bulk matrix. TEM observations reveal that the sizes of the precipitates decrease with increasing distance from the interface and thus confirms the retardation in aging kinetics with increasing distance from the interface.

Sulfur transfer reactions of tetrathiomolybdate in water: Synthesis of alkyl disulfides from alkyl halides

Reaction of a number of alkyl halides with tetrathiomolybdate in water as the solvent affords the corresponding disulfides in good yields.