Reduction of DDHQ and TCC esters by NaBH4-its specificity in the presence of Alkyl/Aryl esters

DDHQ/TCC esters 3a–f, 7a–g were prepared either by oxidation of spiroketones 1 with DDQ/Image -chloranil or by condensation of acid chloride with DDHQ/TCC. NaBH4 reduction of unsaturated DDHQ 3a–b and TCC 7a–c esters gave the corresponding allylic alcohols in good yield without any observable 1,4-addition products. Reduction of saturated esters 3e, 7d, gave the corresponding alcohols. Alkyl esters 5 and 6, methyl benzoate and phenyl benzoate remained unaffected under these reduction conditions. In the reduction of compound 7e containing both alkyl and TCC esters, TCC ester is selectively reduced. Reduction of TCC mono esters 7f–g gave the lactones. The observed facile reduction has been rationalised.

Representation of thermodynamic properties of ternary systems and its application to the system silver-gold-copper at 1350 K

The article presents a generalized analytical expression for description of the integral excess Gibbs free energy of mixing of a ternary system. Twelve constants of the equation are assessed by the least mean squares regressional analysis of the experimental integral excess data of the constituent binaries; three ternary parameters are evaluated by a regressional analysis based on the partial experimental data of a component of the ternary system. The assessed values of the ternary parameters describe the nature of the ternary interaction in the system. Activities and isoactivities of the components in the Ag-Au-Cu system at 1350 K are calculated and found to be in good agreement with the experimental data. This analytical treatment is particularly useful to ternary systems where the thermodynamic data are available from different sources.

Oxidation of substituted benzylic hydrocarbons and naphthalenes by peroxydisulphate in the presence of metal ions

Oxidations of various substituted benzylic hydrocarbons with peroxydisulphate in the presence of metal ion catalysts like iron, nickel, copper, cobalt, silver and cerium were examined. Among the metal ions copper (II) catalysed reaction gives products in excellent yield, whereas oxidation of naphthalene and substituted naphthalenes gives low to moderate yield of the products with peroxydisulphate- copper (II).

Peristaltic pumping in a circular tube in the presence of an eccentric catheter

The influence of an eccentrically inserted catheter on the peristaltic pumping in a tube is investigated under long wavelength, low Reynolds number assumptions. The radially asymmetric deformation of the wall arising through an eccentrically inserted catheter is taken into consideration by choosing an appropriate bipolar coordinate system. The effect of the position and size of the catheter on pumping characteristics is studied. The best performance of pumping is noticed at a certain position of the catheter. The size of the catheter, when placed eccentrically, alters the pressure signature significantly inside the bolus, unlike the concentric case discussed by Lykoudis and Roos (1971). Further, the maximum pressure rise in one period of the peristaltic wave is observed to decrease with an increase in the eccentricity.

Direction of arrival estimation in the presence of distributed noise sources: Cumulant based approach

In the past few years there have been attempts to develop subspace methods for DoA (direction of arrival) estimation using a fourth?order cumulant which is known to de?emphasize Gaussian background noise. To gauge the relative performance of the cumulant MUSIC (MUltiple SIgnal Classification) (c?MUSIC) and the standard MUSIC, based on the covariance function, an extensive numerical study has been carried out, where a narrow?band signal source has been considered and Gaussian noise sources, which produce a spatially correlated background noise, have been distributed. These simulations indicate that, even though the cumulant approach is capable of de?emphasizing the Gaussian noise, both bias and variance of the DoA estimates are higher than those for MUSIC. To achieve comparable results the cumulant approach requires much larger data, three to ten times that for MUSIC, depending upon the number of sources and how close they are. This is attributed to the fact that in the estimation of the cumulant, an average of a product of four random variables is needed to make an evaluation. Therefore, compared to those in the evaluation of the covariance function, there are more cross terms which do not go to zero unless the data length is very large. It is felt that these cross terms contribute to the large bias and variance observed in c?MUSIC. However, the ability to de?emphasize Gaussian noise, white or colored, is of great significance since the standard MUSIC fails when there is colored background noise. Through simulation it is shown that c?MUSIC does yield good results, but only at the cost of more data.

Photolysis of arene chromium tricarbonyl complexes in presence of amine-boranes: Observation of sigma-borane complexes in solution

Activation of the B-H sigma-bond of amine-boranes on the chromium(0) center of arene chromium tricarbonyl complexes (eta(6)-arene) Cr(CO)(3) (arene = fluorobenzene, 1a; benzene, 1b and mesitylene, 1c) has been studied. Photolysis of 1b in presence of ammonia-borane (H3N center dot BH3, AB) and tert-butylamine-borane ((BuH2N)-Bu-t center dot BH3, TBAB) resulted in H-2 evolution and precipitation of a BNHx polymer. On the other hand, photolysis in the presence of trimethylamine-borane (Me3N center dot BH3, TMAB) resulted in the formation of a sigma-borane complex (2) along with Cr(CO)(5)(eta(1)-HBH2 center dot NMe3) (3). The sigma-borane complexes (eta(6)-arene) Cr-( CO)(2)(eta(1)-HBH2 center dot NMe3) (arene = fluorobenzene, 2a; benzene, 2b and mesitylene, 2c) were characterized in solution by H-1, B-11, and C-13 NMR spectroscopy. Electron withdrawing substituents on the arene ring provide the more stable sigma-borane moiety in this series of complexes. (C) 2011 Elsevier B.V. All rights reserved.

Representation of thermodynamic properties of quaternary systems using interaction parameters

Integral excess free energy of a quaternary system has been expressed in terms of the MacLaurin infinite series. The series is subjected to appropriate boundary conditions and each of the derivatives correlated to the corresponding interaction coefficients. The derivation of the partial functions involves extensive summation of various infinite series pertaining to the first order and quaternary parameters to remove any truncational error. The thermodynamic consistency of the derived partials has been established based on the Gibbs-Duhem relations. The equations are used to interpret the thermodynamic properties of the Fe-Cr-Ni-N system.

The actor-critic algorithm as multi-time-scale stochastic approximation

The actor-critic algorithm of Barto and others for simulation-based optimization of Markov decision processes is cast as a two time Scale stochastic approximation. Convergence analysis, approximation issues and an example are studied.

Distributed intrusion detection in the presence of correlated sensor readings: Signal-space and communication-complexity view-point

The problem of sensor-network-based distributed intrusion detection in the presence of clutter is considered. It is argued that sensing is best regarded as a local phenomenon in that only sensors in the immediate vicinity of an intruder are triggered. In such a setting, lack of knowledge of intruder location gives rise to correlated sensor readings. A signal-space view-point is introduced in which the noise-free sensor readings associated to intruder and clutter appear as surfaces f(s) and f(g) and the problem reduces to one of determining in distributed fashion, whether the current noisy sensor reading is best classified as intruder or clutter. Two approaches to distributed detection are pursued. In the first, a decision surface separating f(s) and f(g) is identified using Neyman-Pearson criteria. Thereafter, the individual sensor nodes interactively exchange bits to determine whether the sensor readings are on one side or the other of the decision surface. Bounds on the number of bits needed to be exchanged are derived, based on communication-complexity (CC) theory. A lower bound derived for the two-party average case CC of general functions is compared against the performance of a greedy algorithm. Extensions to the multi-party case is straightforward and is briefly discussed. The average case CC of the relevant greaterthan (CT) function is characterized within two bits. Under the second approach, each sensor node broadcasts a single bit arising from appropriate two-level quantization of its own sensor reading, keeping in mind the fusion rule to be subsequently applied at a local fusion center. The optimality of a threshold test as a quantization rule is proved under simplifying assumptions. Finally, results from a QualNet simulation of the algorithms are presented that include intruder tracking using a naive polynomial-regression algorithm. 2010 Elsevier B.V. All rights reserved.

Synthesis of workspaces of planar manipulators with arbitrary topology using shape representation and simulated annealing

This paper presents a general methodology for the synthesis of the external boundary of the workspaces of a planar manipulator with arbitrary topology. Both the desired workspace and the manipulator workspaces are identified by their boundaries and are treated as simple closed polygons. The paper introduces the concept of best match configuration and shows that the corresponding transformation can be obtained by using the concept of shape normalization available in image processing literature. Introduction of the concept of shape in workspace synthesis allows highly accurate synthesis with fewer numbers of design variables. This paper uses a new global property based vector representation for the shape of the workspaces which is computationally efficient because six out of the seven elements of this vector are obtained as a by-product of the shape normalization procedure. The synthesis of workspaces is formulated as an optimization problem where the distance between the shape vector of the desired workspace and that of the workspace of the manipulator at hand are minimized by changing the dimensional parameters of the manipulator. In view of the irregular nature of the error manifold, the statistical optimization procedure of simulated annealing has been used. A number of worked-out examples illustrate the generality and efficiency of the present method. (C) 1998 Elsevier Science Ltd. All rights reserved.

The onset of oscillatory Marangoni convection in a two-layer system of conducting fluid in the presence of a uniform magnetic field

A combination of numerical and analytical techniques is used to analyse the effect of magnetic field and encapsulated layer on the onset of oscillatory Marangoni instability in a two layer system. Oscillatory Marangoni instability is possible for a deformed free surface only when the system is heated from above. It is observed that the existence of a second layer has a positive effect on Marangoni overstability with magnetic field whereas it has an opposite effect without magnetic field.

Throughput performance of distributed applications in switched networks in presence of end-system bottlenecks

The steady state throughput performance of distributed applications deployed in switched networks in presence of end-system bottlenecks is studied in this paper. The effect of various limitations at an end-system is modelled as an equivalent transmission capacity limitation. A class of distributed applications is characterised by a static traffic distribution matrix that determines the communication between various components of the application. It is found that uniqueness of steady state throughputs depends only on the traffic distribution matrix and that some applications (e.g., broadcast applications) can yield non-unique values for the steady state component throughputs. For a given switch capacity, with traffic distribution that yield fair unique throughputs, the trade-off between the end-system capacity and the number of application components is brought out. With a proposed distributed rate control, it has been illustrated that it is possible to have unique solution for certain traffic distributions which is otherwise impossible. Also, by proper selection of rate control parameters, various throughput performance objectives can be realised.

On Training and Training Voids for Receive Antenna Subset Selection in Time-Varying Channels

Antenna selection (AS) provides most of the benefits of multiple-antenna systems at drastically reduced hardware costs. In receive AS, the receiver connects a dynamically selected subset of N available antennas to the L available RF chains. The "best" subset to be used for data reception is determined by means of channel estimates acquired using training sequences. Due to the nature of AS, the channel estimates at different antennas are obtained from different transmissions of the pilot sequence, and are, thus, outdated by different amounts in a time-varying channel. We show that a linear weighting of the estimates is optimum for the subset selection process, where the weights are related to the temporal correlation of the channel variations. When L is not an integer divisor of N, we highlight a new issue of "training voids", in which the last pilot transmission is not fully exploited by the receiver. We present a "void-filling" method for fully exploiting these voids, which essentially provides more accurate training for some antennas, and derive the optimal subset selection rule for any void-filling method. We also derive new closed-form equations for the performance of receive AS with optimal subset selection.

BER Analysis of Uplink OFDMA in the Presence of Carrier Frequency and Timing Offsets on Rician Fading Channels

In uplink orthogonal frequency division multiple access (OFDMA), carrier frequency offsets (CFO) and/or timing offsets (TO) of other users with respect to a desired user can cause significant multiuser interference (MUI). In this paper, we derive an analytical bit error rate (BER) expression that quantify the degradation in BER due to the combined effect of both CFOs and TOs in uplink OFDMA on Rician fading channels. Such an analytical BER derivation for uplink OFDMA with CFOs and TOs on Rician fading channels has not been reported so far. For the case of non-zero CFOs/TOs, we obtain an approximate BER expression involving a single integral. Analytical and simulation BER results are shown to match very well.

Training and Voids in Receive Antenna Subset Selection in Time-Varying Channels

Receive antenna selection (AS) provides many benefits of multiple-antenna systems at drastically reduced hardware costs. In it, the receiver connects a dynamically selected subset of N available antennas to the L available RF chains. Due to the nature of AS, the channel estimates at different antennas, which are required to determine the best subset for data reception, are obtained from different transmissions of the pilot sequence. Consequently, they are outdated by different amounts in a time-varying channel. We show that a linear weighting of the estimates is necessary and optimum for the subset selection process, where the weights are related to the temporal correlation of the channel variations. When L is not an integer divisor of N , we highlight a new issue of ``training voids'', in which the last pilot transmission is not fully exploited by the receiver. We then present new ``void-filling'' methods that exploit these voids and greatly improve the performance of AS. The optimal subset selection rules with void-filling, in which different antennas turn out to have different numbers of estimates, are also explicitly characterized. Closed-form equations for the symbol error probability with and without void-filling are also developed.