Time-Resolved Resonance Raman Spectroscopy: Exploring Reactive Intermediates

The study of reaction mechanisms involves systematic investigations of the correlation between structure, reactivity, and time. The challenge is to be able to observe the chemical changes undergone by reactants as they change into products via one or several intermediates such as electronic excited states (singlet and triplet), radicals, radical ions, carbocations, carbanions, carbenes, nitrenes, nitrinium ions, etc. The vast array of intermediates and timescales means there is no single ``do-it-all'' technique. The simultaneous advances in contemporary time-resolved Raman spectroscopic techniques and computational methods have done much towards visualizing molecular fingerprint snapshots of the reactive intermediates in the microsecond to femtosecond time domain. Raman spectroscopy and its sensitive counterpart resonance Raman spectroscopy have been well proven as means for determining molecular structure, chemical bonding, reactivity, and dynamics of short-lived intermediates in solution phase and are advantageous in comparison to commonly used time-resolved absorption and emission spectroscopy. Today time-resolved Raman spectroscopy is a mature technique; its development owes much to the advent of pulsed tunable lasers, highly efficient spectrometers, and high speed, highly sensitive multichannel detectors able to collect a complete spectrum. This review article will provide a brief chronological development of the experimental setup and demonstrate how experimentalists have conquered numerous challenges to obtain background-free (removing fluorescence), intense, and highly spectrally resolved Raman spectra in the nanosecond to microsecond (ns-mu s) and picosecond (ps) time domains and, perhaps surprisingly, laid the foundations for new techniques such as spatially offset Raman spectroscopy.

The Thermodynamics of Oxygen in Reactive Metals

For some new applications of metals in functional devices, metals of high purity are required. In recent years, many high-purity metals have been produced commercially for use in electronics, but the demand for ultra-high-purity metals is increasing rapidly because of more stringent specifications for materials used in high-performance information devices.

Reactive interdiffusion: deviation from local equilibrium in the Fe-NiTiO3 couple

Deviation from local equilibrium between Fe–Ni alloy and (Fe,Ni)TiO3 solid solution in the reaction–diffusion zone of the Fe–NiTiO3 couple at 1273 K is evaluated by comparing the measured compositions in the zone with experimentally determined equilibrium tie-lines. The deviation is quantified by computing the Gibbs energy change for the reaction, Fe + NiTiO3 → FeTiO3 + Ni, from measured compositions in the zone and activity data available in the literature. Except near the extremities of the zone, the computed Gibbs energy change is constant, 8.2 kJ mol−1 higher than the standard Gibbs energy change for the reaction.

Reactive pulsed laser deposition and characterization of niobium nitride thin films

We present a systematic study to explore the effect of important process variables on the composition and structure of niobium nitride thin films synthesized by Reactive Pulsed Laser Deposition (RPLD) technique through ablation of high purity niobium target in the presence of low pressure nitrogen gas. Secondary Ion Mass Spectrometry has been used in a unique way to study and fix gas pressure, substrate temperature and laser fluence, in order to obtain optimized conditions for one variable in single experimental run. The x-ray diffraction and electron microscopic characterization have been complemented by proton elastic backscattering spectroscopy and x-ray photoelectron spectroscopy to understand the incorporation of oxygen and associated non-stoichiometry in the metal to nitrogen ratio. The present study demonstrates that RPLD can be used for obtaining thin film architectures using non-equilibrium processing. Finally the optimized NbN thin films were characterized for their hardness using nano-indentation technique and found to be similar to 30 GPa at the deposition pressure of 8 Pa. (C) 2011 Elsevier B.V. All rights reserved.

A Novel VSI- and CSI-Fed Active-Reactive Induction Motor Drive with Sinusoidal Voltages and Currents

Till date load-commutated inverter (LCI)-fed synchronous motor drive configuration is popular in high power applications (>10 MW). The leading power factor operation of synchronous motor by excitation control offers this simple and rugged drive structure. On the contrary, LCI-fed induction motor drive is absent as it always draws lagging power factor current. Therefore, complicated commutation circuit is required to switch off thyristors for a current source inverter (CSI)-driven induction motor. It poses the major hindrance to scale up the power rating of CSI-fed induction motor drive. Anew power topology for LCI-fed induction motor drive for medium-voltage drive application is proposed. A new induction machine (active-reactive induction machine) with two sets of three-phase winding is introduced as a drive motor. The proposed power configuration ensures sinusoidal voltage and current at the motor terminals. The total drive power is shared among a thyristor-based LCI, an insulated gate bipolar transistor (IGBT)-based two-level voltage source inverter (VSI), and a three-level VSI. The benefits of SCRs and IGBTs are explored in the proposed drive. Experimental results from a prototype drive verify the basic concepts of the drive.

New static 3-step distance relay

A new static 3-step distance relay based on the principle of multi-input phase comparison is described in the paper. Design principles and typical discriminating and logic circuits are described for the new relaying system. The relaying system uses semiconductor circuits throughout and features high speed and good performance. The comparator model, which effects multi-input phase comparison, has been devised to provide reliable pickup for closein faults, and to achieve an improved polar characteristic in the complex- impedance plane, which fits around only the fault area of a transmission line. Operating time of the relay is less than 1 cycle for unbalanced faults, and less than a halfcycle for 3-phase faults. Protective circuits have also been added to detect power swing and to block tripping for a predetermined number of power-swing cycles. The operating characteristics of the relay, as expressed by accuracy/range charts, are presented.

Growth mechanism of the Nb(X)Si-2 and [Nb(X)](5)Si-3 phases by reactive diffusion in Nb (X = Ti, Mo, or Zr)-Si systems

The effects of Mo, Ti, and Zr on the diffusion and growth of the Nb(X)Si-2 and Nb(X)(5)Si-3 phases in an Nb(X)-Si system are analyzed. The integrated diffusion coefficients are determined from diffusion couple experiments and compared with the data previously calculated in a binary Nb-Si system. The growth rates of both phases are affected by the addition of Mo and Zr, whereas the addition of Ti has no effect. The atomic mechanism of diffusion is also discussed based on the crystal structure and the possible changes in the defect concentrations due to alloying. Finally, the growth mechanism of the phases is discussed on the basis of a physico-chemical approach. (C) 2011 Elsevier Ltd. All rights reserved.

Saccharomyces cerevisiae NineTeen Complex (NTC)-associated Factor Bud31/Ycr063w Assembles on Precatalytic Spliceosomes and Improves First and Second Step Pre-mRNA Splicing Efficiency

Pre-mRNA splicing occurs in spliceosomes whose assembly and activation are critical for splice site selection and catalysis. The highly conserved NineTeen complex protein complex stabilizes various snRNA and protein interactions early in the spliceosome assembly pathway. Among several NineTeen complex-associated proteins is the nonessential protein Bud31/Ycr063w, which is also a component of the Cef1p subcomplex. A role for Bud31 in pre-mRNA splicing is implicated by virtue of its association with splicing factors, but its specific functions and spliceosome interactions are uncharacterized. Here, using in vitro splicing assays with extracts from a strain lacking Bud31, we illustrate its role in efficient progression to the first catalytic step and its requirement for the second catalytic step in reactions at higher temperatures. Immunoprecipitation of functional epitope-tagged Bud31 from in vitro reactions showed that its earliest association is with precatalytic B complex and that the interaction continues in catalytically active complexes with stably bound U2, U5, and U6 small nuclear ribonucleoproteins. In complementary experiments, wherein precatalytic spliceosomes are selected from splicing reactions, we detect the occurrence of Bud31. Cross-linking of proteins to pre-mRNAs with a site-specific 4-thio uridine residue at the -3 position of exon 1 was tested in reactions with WT and bud31 null extracts. The data suggest an altered interaction between a similar to 25-kDa protein and this exonic residue of pre-mRNAs in the arrested bud31 null spliceosomes. These results demonstrate the early spliceosomal association of Bud31 and provide plausible functions for this factor in stabilizing protein interactions with the pre-mRNA.

Improved algorithm for optimum reactive power allocation

An improvised algorithm is presented for optimal VAr allocation in a large power system using a linear programming technique. The proposed method requires less computer memory than those algorithms currently available.

Comparison of Optimum Reactive Power Schedule with Different Objectives Using LP Technique

Three algorithms for reactive power optimization are proposed in this paper with three different objective functions. The objectives in the proposed algorithm are to minimize the sum of the squares of the voltage deviations of the load buses, minimization of sum of squares of voltage stability L-indices of load buses (:3L2) algorithm, and also the objective of system real power loss (Ploss) minimization. The approach adopted is an iterative scheme with successive power flow analysis using decoupled technique and solution of the linear programming problem using upper bound optimization technique. Results obtained with all these objectives are compared. The analysis of these objective functions are presented to illustrate their advantages. It is observed comparing different objective functions it is possible to identify critical On Load Tap Changers (OLTCs) that should be made manual to avoid possible voltage instability due to their operation based on voltage improvement criteria under heavy load conditions. These algorithms have been tested under simulated conditions on few test systems. The results obtained on practical systems of 24-node equivalent EHV Indian power network, and for a 205 bus EHV system are presented for illustration purposes.

Fuzzy Expert Approach with Curtailed Controllers for Improved Reactive Power Dispatch

This paper addresses the problem of curtailing the number of control actions using fuzzy expert approach for voltage/reactive power dispatch. It presents an approach using fuzzy set theory for reactive power control with the purpose of improving the voltage profile of a power system. To minimize the voltage deviations from pre-desired values of all the load buses, using the sensitivities with respect to reactive power control variables form the basis of the proposed Fuzzy Logic Control (FLC). Control variables considered are switchable VAR compensators, On Load Tap Changing (OLTC) transformers and generator excitations. Voltage deviations and controlling variables are translated into fuzzy set notations to formulate the relation between voltage deviations and controlling ability of controlling devices. The developed fuzzy system is tested on a few simulated practical Indian power systems and modified IEEE-30 bus system. The performance of the fuzzy system is compared with conventional optimization technique and results obtained are encouraging. Results obtained for a modified IEEE-30 bus test system and a 205-node equivalent EHV system a part of Indian southern grid are presented for illustration purposes. The proposed fuzzy-expert technique is found suitable for on-line applications in energy control centre as the solution is obtained fast with significant speedups with few number of controllers.