Excited state structure and dynamics of p-benzoquinone and bromanil from time-resolved resonance Raman spectra and simulation

p-Benzoquinone and its halogen substituted derivatives are known to have differing reactivities in the triplet excited state. While bromanil catalyzes the reduction of octaethylporphyrin most efficiently among the halogenated p-benzoquinones, the reaction does not take place in presence of the unsubstituted p-benzoquinone (T. Nakano and Y. Mori, Bull. Chem. Soc. Jpn., 67, 2627 (1994)). Understanding of such differences requires a detailed knowledge of the triplet state structures, normal mode compositions and excited state dynamics. In this paper, we apply a recently presented scheme (M. Puranik, S. Umapathy, J. G. Snijders, and J. Chandrasekhar, J. Chem, Phys., 115, 6106 (2001)) that combines parameters from experiment and computation in a wave packet dynamics simulation to the triplet states of p-benzoquinone and bromanil. The absorption and resonance Raman spectra of both the molecules have been simulated. The normal mode compositions and mode specific excited state displacements have been presented and compared. Time-dependent evolution of the absorption and Raman overlaps for all the observed modes has been discussed in detail. In p-benzoquinone, the initial dynamics is along the C=C stretching and C-H bending modes whereas in bromanil nearly equal displacements are observed along all the stretching coordinates.

Sandwich propellant combustion: Modeling and experimental comparison

This paper reports reacting fluid dynamics calculations for an ammonium percholrate binder sandwich and extracts experimentally observed features including surface profiles and maximum regression rates as a function of pressure and binder thickness. These studies have been carried out by solving the two-dimensional unsteady Navier-Stokes equations with energy and species conservation equations and a kinetic model of three reaction steps (ammonium perchlorate decomposition flame, primary diffusion flame, and final diffusion flame) in the gas phase. The unsteady two-dimensional conduction equation is solved in the condensed phase. The regressing surface is unsteady and two dimensional. Computations have been carried out for a binder thickness range of 25-125 mum and a pressure range of 1.4 to 6.9 MPa. Good comparisons at several levels of detail are used to demonstrate the need for condensed-phase two-dimensional unsteady conduction and three-step gas-phase reactions. The choice of kinetic and thermodynamic parameters is crucial to good comparison with experiments. The choice of activation energy parameters for ammonium percholrate combustion has been made with stability of combustion in addition to experimentally determined values reported in literature. The choice of gas-phase parameters for the diffusion flames are made considering that (a) primary diffusion flame affects the low-pressure behavior and (b) final diffusion flame affects high-pressure behavior. The predictions include the low-pressure deflagration limit of the sandwich apart from others noted above. Finally, this study demonstrates the possibility of making meaningful comparisons with experimental observations on sandwich propellant combustion.

Multi-Mode Phonon-Controlled Field Emission from Carbon Nanotubes: Modeling and Experiments

The main idea proposed in this paper is that in a vertically aligned array of short carbon nanotubes (CNTs) grown on a metal substrate, we consider a frequency dependent electric field, so that the mode-specific propagation of phonons, in correspondence with the strained band structure and the dispersion curves, take place. We perform theoretical calculations to validate this idea with a view of optimizing the field emission behavior of the CNT array. This is the first approach of its kind, and is in contrast to the the conventional approach where a DC bias voltage is applied in order to observe field emission. A first set of experimental results presented in this paper gives a clear indication that phonon-assisted control of field emission current in CNT based thin film diode is possible.

Experimental evidence for interplay of dynamic heterogeneity and finite-size effect in glassy polymers

Despite two decades of extensive research, direct experimental evidence of a dynamical length scale determining the glass transition of confined polymers has yet to emerge. Using a recently established experimental technique of interface micro-rheology we provide evidence of finite-size effect truncating the growth of a quantity proportional to a dynamical length scale in confined glassy polymers, on cooling towards the glass transition temperature. We show how the interplay of variation of polymer film thickness and this temperature-dependent growing dynamical length scale determines the glass transition temperature, which in our case of 2-3nm thick films, is reduced significantly as compared to their bulk values.

A PPCA based non-parametric modeling and retrieval of PD signal buried in excessive noise

The problem of on-line recognition and retrieval of relatively weak industrial signals such as partial discharges (PD), buried in excessive noise, has been addressed in this paper. The major bottleneck being the recognition and suppression of stochastic pulsive interference (PI) due to the overlapping broad band frequency spectrum of PI and PD pulses. Therefore, on-line, onsite, PD measurement is hardly possible in conventional frequency based DSP techniques. The observed PD signal is modeled as a linear combination of systematic and random components employing probabilistic principal component analysis (PPCA) and the pdf of the underlying stochastic process is obtained. The PD/PI pulses are assumed as the mean of the process and modeled instituting non-parametric methods, based on smooth FIR filters, and a maximum aposteriori probability (MAP) procedure employed therein, to estimate the filter coefficients. The classification of the pulses is undertaken using a simple PCA classifier. The methods proposed by the authors were found to be effective in automatic retrieval of PD pulses completely rejecting PI.

Performance modeling and architecture exploration of network processors

This paper proposes a Petri net model for a commercial network processor (Intel iXP architecture) which is a multithreaded multiprocessor architecture. We consider and model three different applications viz., IPv4 forwarding, network address translation, and IP security running on IXP 2400/2850. A salient feature of the Petri net model is its ability to model the application, architecture and their interaction in great detail. The model is validated using the Intel proprietary tool (SDK 3.51 for IXP architecture) over a range of configurations. We conduct a detailed performance evaluation, identify the bottleneck resource, and propose a few architectural extensions and evaluate them in detail.

A Long Memory Process Based Parametric Modeling and Recognition of PD Signal

We address the problem of recognition and retrieval of relatively weak industrial signal such as Partial Discharges (PD) buried in excessive noise. The major bottleneck being the recognition and suppression of stochastic pulsive interference (PI) which has similar time-frequency characteristics as PD pulse. Therefore conventional frequency based DSP techniques are not useful in retrieving PD pulses. We employ statistical signal modeling based on combination of long-memory process and probabilistic principal component analysis (PPCA). An parametric analysis of the signal is exercised for extracting the features of desired pules. We incorporate a wavelet based bootstrap method for obtaining the noise training vectors from observed data. The procedure adopted in this work is completely different from the research work reported in the literature, which is generally based on deserved signal frequency and noise frequency.

Premixed flame response to equivalence ratio fluctuations: Comparison between reduced order modeling and detailed computations

Combustion instability events in lean premixed combustion systems can cause spatio-temporal variations in unburnt mixture fuel/air ratio. This provides a driving mechanism for heat-release oscillations when they interact with the flame. Several Reduced Order Modelling (ROM) approaches to predict the characteristics of these oscillations have been developed in the past. The present paper compares results for flame describing function characteristics determined from a ROM approach based on the level-set method, with corresponding results from detailed, fully compressible reacting flow computations for the same two dimensional slot flame configuration. The comparison between these results is seen to be sensitive to small geometric differences in the shape of the nominally steady flame used in the two computations. When the results are corrected to account for these differences, describing function magnitudes are well predicted for frequencies lesser than and greater than a lower and upper cutoff respectively due to amplification of flame surface wrinkling by the convective Darrieus-Landau (DL) instability. However, good agreement in describing function phase predictions is seen as the ROM captures the transit time of wrinkles through the flame correctly. Also, good agreement is seen for both magnitude and phase of the flame response, for large forcing amplitudes, at frequencies where the DL instability has a minimal influence. Thus, the present ROM can predict flame response as long as the DL instability, caused by gas expansion at the flame front, does not significantly alter flame front perturbation amplitudes as they traverse the flame. (C) 2012 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Functional characterization, homology modeling and docking studies of beta-glucosidase responsible for bioactivation of cyanogenic hydroxynitrile glucosides from Leucaena leucocephala (subabul)

Glycosyl hydrolase family 1 beta-glucosidases are important enzymes that serve many diverse functions in plants including defense, whereby hydrolyzing the defensive compounds such as hydroxynitrile glucosides. A hydroxynitrile glucoside cleaving beta-glucosidase gene (Llbglu1) was isolated from Leucaena leucocephala, cloned into pET-28a (+) and expressed in E. coli BL21 (DE3) cells. The recombinant enzyme was purified by Ni-NTA affinity chromatography. The optimal temperature and pH for this beta-glucosidase were found to be 45 A degrees C and 4.8, respectively. The purified Llbglu1 enzyme hydrolyzed the synthetic glycosides, pNPGlucoside (pNPGlc) and pNPGalactoside (pNPGal). Also, the enzyme hydrolyzed amygdalin, a hydroxynitrile glycoside and a few of the tested flavonoid and isoflavonoid glucosides. The kinetic parameters K (m) and V (max) were found to be 38.59 mu M and 0.8237 mu M/mg/min for pNPGlc, whereas for pNPGal the values were observed as 1845 mu M and 0.1037 mu M/mg/min. In the present study, a three dimensional (3D) model of the Llbglu1 was built by MODELLER software to find out the substrate binding sites and the quality of the model was examined using the program PROCHEK. Docking studies indicated that conserved active site residues are Glu 199, Glu 413, His 153, Asn 198, Val 270, Asn 340, and Trp 462. Docking of rhodiocyanoside A with the modeled Llbglu1 resulted in a binding with free energy change (Delta G) of -5.52 kcal/mol on which basis rhodiocyanoside A could be considered as a potential substrate.

Evaluation of dynamic voltage and frequency scaling for stream programs

Dynamic Voltage and Frequency Scaling (DVFS) offers a huge potential for designing trade-offs involving energy, power, temperature and performance of computing systems. In this paper, we evaluate three different DVFS schemes - our enhancement of a Petri net performance model based DVFS method for sequential programs to stream programs, a simple profile based Linear Scaling method, and an existing hardware based DVFS method for multithreaded applications - using multithreaded stream applications, in a full system Chip Multiprocessor (CMP) simulator. From our evaluation, we find that the software based methods achieve significant Energy/Throughput2(ET−2) improvements. The hardware based scheme degrades performance heavily and suffers ET−2 loss. Our results indicate that the simple profile based scheme achieves the benefits of the complex Petri net based scheme for stream programs, and present a strong case for the need for independent voltage/frequency control for different cores of CMPs, which is lacking in most of the state-of-the-art CMPs. This is in contrast to the conclusions of a recent evaluation of per-core DVFS schemes for multithreaded applications for CMPs.