Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(II) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies

Four dinuclear bis(mu-Cl) bridged copper(II) complexes, Cu-2(mu-Cl)(2)(L-X)(2)](ClO4)(2) (L-X = N,N-bis(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H(1), OMe(2), Me(3) and Cl(4)), have been synthesized and characterized by the single crystal X-ray diffraction method. In these complexes, each copper(II) center is penta-coordinated with square-pyramidal geometry. In addition to the tridentate L-X ligand, a chloride ion occupies the last position of the square plane. This chloride ion is also bonded to the neighboring Cu(II) site in its axial position forming an SP-I dinuclear Cu(II) unit that exhibits small intramolecular ferromagnetic interactions and supported by DFT calculations. The complexes 1-3 exhibit methylmonooxygenase (pMMO) behaviour and oxidise 4-tert-butylcatechol (4-TBCH2) with molecular oxygen in MeOH or MeCN to 4-tert-butyl-benzoquinone (4-TBQ), 5-methoxy-4-tert-butyl-benzoquinone (5-MeO-4-TBQ) as the major products along with 6,6'-Bu-t-biphenyl-3,4,3',4'-tetraol and others as minor products. These are further confirmed by ESI- and FAB-mass analyses. A tentative catalytic cycle has been framed based on the mass spectral analysis of the products and DFT calculations on individual intermediates that are energetically feasible.

Mobile agent based TCP attacker identification in MANET using the traffic history (MAITH)

TCP attacks are the major problem faced by Mobile Ad hoc Networks (MANETs) due to its limited network and host resources. Attacker traceback is a promising solution which allows a victim to identify the exact location of the attacker and hence enables the victim to take proper countermeasure near attack origins, for forensics and to discourage attackers from launching the attacks. However, attacker traceback in MANET is a challenging problem due to dynamic network topology, limited network and host resources such as memory, bandwidth and battery life. We introduce a novel method of TCP attacker Identification in MANET using the Traffic History - MAITH. Based on the comprehensive evaluation based on simulations, we showed that MAITH can successfully track down the attacker under diverse mobile multi-hop network environment with low communication, computation, and memory overhead.

A computational study of heat transfer, soot production and transport in an acetylene-air laminar diffusion flame in the field of a line vortex

The present work involves a computational study of soot formation and transport in case of a laminar acetylene diffusion flame perturbed by a co nvecting line vortex. The topology of the soot contours (as in an earlier experimental work [4]) have been investigated. More soot was produced when vortex was introduced from the air si de in comparison to a fuel side vortex. Also the soot topography was more diffused in case of the air side vortex. The computational model was found to be in good agreement with the ex perimental work [4]. The computational simulation enabled a study of the various parameters affecting soot transport. Temperatures were found to be higher in case of air side vortex as compared to a fuel side vortex. In case of the fuel side vortex, abundance of fuel in the vort ex core resulted in stoichiometrically rich combustion in the vortex core, and more discrete so ot topography. Overall soot production too was low. In case of the air side vortex abundan ce of air in the core resulted in higher temperatures and more soot yield. Statistical techniques like probability density fun ction, correlation coefficient and conditional probability function were introduced to explain the transient dependence of soot yield and transport on various parameters like temperature, a cetylene concentration.

A computational study of flame dynamics on soot production and transport for an acetylene-air laminar diffusion flame in the field of a convecting line vortex

The present work involves a computational study of soot formation and transport in case of a laminar acetylene diffusion flame perturbed by a convecting line vortex. The topology of the soot contours (as in an earlier experimental work [4]) have been investigated. More soot was produced when vortex was introduced from the air side in comparison to a fuel side vortex. Also the soot topography was more diffused in case of the air side vortex. The computational model was found to be in good agreement with the experimental work [4]. The computational simulation enabled a study of the various parameters affecting soot transport. Temperatures were found to be higher in case of air side vortex as compared to a fuel side vortex. In case of the fuel side vortex, abundance of fuel in the vort ex core resulted in stoichiometrically rich combustion in the vortex core, and more discrete soot topography. Overall soot production too was low. In case of the air side vortex abundance of air in the core resulted in higher temperatures and more soot yield. Statistical techniques like probability density function, correlation coefficient and conditional probability function were introduced to explain the transient dependence of soot yield and transport on various parameters like temperature, a cetylene concentration.

Microscopic dynamics of nanoparticle monolayers at air-water interface

We present results of surface mechanical and particle tracking measurements of nanoparticles trapped at the air-water interface as a function of their areal density. We monitor both the surface pressure (II) and isothermal compression modulus (epsilon) as well as the dynamics of nanoparticle clusters, using fluorescence confocal microscopy while they are compressed to very high density near the two dimensional close packing density Phi similar to 0.82. We observe non-monotonic variation in both epsilon and the dynamic heterogeneity, characterized by the dynamical susceptibility chi(4) with Phi, in such high density monolayers. We provide insight into the underlying nature of such transitions in close packed high density nanoparticle monolayers in terms of the morphology and flexibility of these soft colloidal particles.. We discuss the significance our results in the context of related studies on two dimensional granular or colloidal systems. (C) 2013 Elsevier Inc. All rights reserved.

Antioxidant and oxidative stress parameters in brain of Heteropneustes fossilis under air exposure condition; role of mitochondrial electron transport chain

Many fishes are exposed to air in their natural habitat or during their commercial handling. In natural habitat or during commercial handling, the cat fish Heteropneustes fossilis is exposed to air for > 24 h. Data on its oxidative metabolism in the above condition are not available. Oxidative stress (OS) indices (lipid and protein oxidation), toxic reactive oxygen species (ROS: H2O2) generation, antioxidative status (levels of superoxide dismutase, catalase, glutathione peroxidase and reductase, ascorbic acid and nonprotein sulfhydryl) and activities of electron transport chain (ETC) enzymes (complex I-IV) were investigated in brain tissue of H. fossilis under air exposure condition (0, 3, 6, 12 and 18 h at 25 degrees C). Decreased activities of antioxidant (except catalase) and ETC enzymes (except complex II) with increased H2O2 and OS levels were observed in the tissue under water deprivation condition. Positive correlation was observed for complex II activity and non-protein thiol groups with time period of air exposure. The critical time period to induce OS and to reduce most of the studied antioxidant level in brain was found to be 3-6 h air exposure. The data can be useful to minimize the stress generated during commercial handling of the live fishes those exposed to air in general and H. fossilis in particular. (C) 2013 Elsevier Inc. All rights reserved.

Scalar transport in diffusion flame wrapped up by an air and fuel side vortex

The present work involves a computational study of soot (chosen as a scalar which is a primary pollutant source) formation and transport in a laminar acetylene diffusion flame perturbed by a convecting line vortex. The topology of soot contours resulting from flame vortex interactions has been investigated. More soot was produced when vortex was introduced from the air side in comparison to the fuel side. Also, the soot topography was spatially more diffuse in the case of air side vortex. The computational model was found to be in good agreement with the experimental work previously reported in the literature. The computational simulation enabled a study of various parameters like temperature, equivalence ratio and temperature gradient affecting the soot production and transport. Temperatures were found to be higher in the case of air side vortex in contrast to the fuel side one. In case of fuel side vortex, abundance of fuel in the vortex core resulted in fuel-rich combustion zone in the core and a more discrete soot topography. Besides, the overall soot production was observed to be low in the fuel side vortex. However, for the air side vortex, air abundance in the core resulted in higher temperatures and greater soot production. Probability density functions (PDFs) have been introduced to investigate the spatiotemporal variation of soot yield and transport and their dependence on temperature and acetylene concentration from statistical view point. In addition, the effect of flame curvature on soot production is also studied. The regions convex to fuel stream side witnessed thicker soot layer. All numerical simulations have been carried out on Fluent 6.3.26. (C) 2013 Elsevier Ltd. All rights reserved.

Traffic engineered NoC for streaming applications

Streaming applications demand hard bandwidth and throughput guarantees in a multiprocessor environment amidst resource competing processes. We present a Label Switching based Network-on-Chip (LS-NoC) motivated by throughput guarantees offered by bandwidth reservation. Label switching is a packet relaying technique in which individual packets carry route information in the form of labels. A centralized LS-NoC Management framework engineers traffic into Quality of Service (QoS) guaranteed routes. LS-NoC caters to the requirements of streaming applications where communication channels are fixed over the lifetime of the application. The proposed NoC framework inherently supports heterogeneous and ad hoc system-on-chips. The LS-NoC can be used in conjunction with conventional best effort NoC as a QoS guaranteed communication network or as a replacement to the conventional NoC. A multicast, broadcast capable label switched router for the LS-NoC has been designed. A 5 port, 256 bit data bus, 4 bit label router occupies 0.431 mm(2) in 130 nm and delivers peak bandwidth of 80 Gbits/s per link at 312.5 MHz. Bandwidth and latency guarantees of LS-NoC have been demonstrated on traffic from example streaming applications and on constant and variable bit rate traffic patterns. LS-NoC was found to have a competitive AreaxPower/Throughput figure of merit with state-of-the-art NoCs providing QoS. Circuit switching with link sharing abilities and support for asynchronous operation make LS-NoC a desirable choice for QoS servicing in chip multiprocessors. (C) 2013 Elsevier B.V. All rights reserved.

Experimental studies on air-assisted impinging jet atomization

In the present study, a novel air-assisted impinging jet atomization is demonstrated. A configuration in which a gas jet is directed on to the impinging point of two liquid jets is used to improve the atomization. The effect of liquid properties such as viscosity and surface tension, angle between liquid jets and gas injection orifice diameter on spray characteristics has been experimentally studied. Backlit imaging and particle/droplet imaging and analysis techniques are utilized to characterize the sprays. The experimental results indicate that the effect of liquid viscosity is significant on the liquid sheet break up formed by the impinging jets. However, surface tension does not affect the spray structure significantly in this mode of atomization. At low liquid jet velocity, the prompt mode of atomization is observed where as atomization occurs in classical mode at higher liquid jet velocity. Results showed that variation in the angle between liquid jets do not affect the breakup phenomenon significantly. The spray angle is computed by finding the angle between the lines joining the impinging point and spray edge at an axial distance of 15 mm downstream of the impinging point from the ensemble-averaged data over 100 spray images. It was observed that effect of liquid jets impinging angle on the spray angle is higher at higher liquid velocity. Higher viscosity liquids exhibit lower spray angles. Droplet size measurements indicate a radial variation in the spray. An overall Sauter Mean Diameter (SMD) value is obtained by combining the droplet statistics at all radial locations at a fixed axial location. A very interesting trend is that the SMD is constant beyond a critical Gas to Liquid Ratio (GLR) and momentum ratio for a large variation in liquid viscosity and surface tension. This observation has important ramifications for fuel flexible systems. (C) 2013 Elsevier Ltd. All rights reserved.

Rack Level Modeling of Air Flow Through Perforated Tile in a Data Center

Effective air flow distribution through perforated tiles is required to efficiently cool servers in a raised floor data center. We present detailed computational fluid dynamics (CFD) modeling of air flow through a perforated tile and its entrance to the adjacent server rack. The realistic geometrical details of the perforated tile, as well as of the rack are included in the model. Generally, models for air flow through perforated tiles specify a step pressure loss across the tile surface, or porous jump model based on the tile porosity. An improvement to this includes a momentum source specification above the tile to simulate the acceleration of the air flow through the pores, or body force model. In both of these models, geometrical details of tile such as pore locations and shapes are not included. More details increase the grid size as well as the computational time. However, the grid refinement can be controlled to achieve balance between the accuracy and computational time. We compared the results from CFD using geometrical resolution with the porous jump and body force model solution as well as with the measured flow field using particle image velocimetry (PIV) experiments. We observe that including tile geometrical details gives better results as compared to elimination of tile geometrical details and specifying physical models across and above the tile surface. A modification to the body force model is also suggested and improved results were achieved.

The problem of clear air turbulence: Changing perspectives in the understanding of the phenomenon

Due to rapid improvements in on-board instrumentation and atmospheric observation systems, in most cases, aircraft are able to steer clear of regions of adverse weather. However, they still encounter unexpected bumpy flight conditions in regions away from storms and clouds. This is the phenomenon of clear air turbulence (CAT), which has been a challenge to our understanding as well as efforts at prediction. While most of such cases result in mild discomfort, a few cases can be violent leading to serious injuries to passengers and damage to the aircraft. The underlying physical mechanisms have been sought to be explained in terms of fluid dynamic instabilities and waves in the atmosphere. The main mechanisms which have been proposed are: (i) Kelvin-Helmholtz instability of shear layers, (ii) waves generated from flow over mountains, (iii) inertia-gravity waves from clouds and other sources, (iv) spontaneous imbalance theory and (v) horizontal vortex tubes. This has also undergone a change over the years. We present an overview of the mechanisms proposed and their implications for prediction.

Collective behavior with heterogeneous controllers

In this paper, we study the collective motion of individually controlled planar particles when they are coupled through heterogeneous controller gains. Two types of collective formations, synchronization and balancing, are described and analyzed under the influence of these heterogeneous controller gains. These formations are characterized by the motion of the centroid of the group of particles. In synchronized formation, the particles and their centroid move in a common direction, while in balanced formation the movement of particles possess a fixed location of the centroid. We show that, by selecting suitable controller gains, these formations can be controlled significantly to obtain not only a desired direction of motion but also a desired location of the centroid. We present the results for N-particles in synchronized formation, while in balanced formation our analysis is confined to two and three particles.

Generalized model predictive static programming and its application to 3D impact angle constrained guidance of air-to-surface missiles

A new `generalized model predictive static programming (G-MPSP)' technique is presented in this paper in the continuous time framework for rapidly solving a class of finite-horizon nonlinear optimal control problems with hard terminal constraints. A key feature of the technique is backward propagation of a small-dimensional weight matrix dynamics, using which the control history gets updated. This feature, as well as the fact that it leads to a static optimization problem, are the reasons for its high computational efficiency. It has been shown that under Euler integration, it is equivalent to the existing model predictive static programming technique, which operates on a discrete-time approximation of the problem. Performance of the proposed technique is demonstrated by solving a challenging three-dimensional impact angle constrained missile guidance problem. The problem demands that the missile must meet constraints on both azimuth and elevation angles in addition to achieving near zero miss distance, while minimizing the lateral acceleration demand throughout its flight path. Both stationary and maneuvering ground targets are considered in the simulation studies. Effectiveness of the proposed guidance has been verified by considering first order autopilot lag as well as various target maneuvers.

Modulation of redox regulatory molecules and electron transport chain activity in muscle of air breathing fish Heteropneustes fossilis under air exposure stress

Responses of redox regulatory system to long-term survival (> 18 h) of the catfish Heteropneustes fossilis in air are not yet understood. Lipid and protein oxidation level, oxidant (H2O2) generation, antioxidative status (levels of superoxide dismutase, catalase, glutathione peroxidase and reductase, ascorbic acid and non-protein sulfhydryl) and activities of respiratory complexes (I, II, III and IV) in mitochondria were investigated in muscle of H. fossilis under air exposure condition (0, 3, 6, 12 and 18 h at 25 A degrees C). The increased levels of both H2O2 and tissue oxidation were observed due to the decreased activities of antioxidant enzymes in muscle under water deprivation condition. However, ascorbic acid and non-protein thiol groups were the highest at 18 h air exposure time. A linear increase in complex II activity with air exposure time and an increase up to 12 h followed by a decrease in activity of complex I at 18 h were observed. Negative correlation was observed for complex III and V activity with exposure time. Critical time to modulate the above parameters was found to be 3 h air exposure. Dehydration induced oxidative stress due to modulation of electron transport chain and redox metabolizing enzymes in muscle of H. fossilis was clearly observed. Possible contribution of redox regulatory system in muscle tissue of the fish for long-term survival in air is elucidated. Results of the present study may be useful to understand the redox metabolism in muscle of fishes those are exposed to air in general and air breathing fishes in particular.

Numerical and experimental investigation and optimization of an open wheeled race car cooling air duct

In this study the cooling performance due to air flow and aerodynamics of the Formula Student open wheeled race car has been investigated and optimized with the help of CFD simulations and experimental validation. The race car in context previously suffered from overheating problems. Flow analysis was carried out based on the detailed race car 3D model (NITK Racing 2012 formula student race car). Wind tunnel experiments were carried out on the same. The results obtained from the computer simulations are compared with experimental results obtained from wind tunnel testing of the full car. Through this study it was possible to locate the problem areas and hence choose the best configuration for the cooling duct. The CFD analysis helped in calculating the mass flow rate, pressure and velocity distribution for different velocities of the car which is then used to determine the heat dissipated by the radiator. Area of flow separation could be visualized and made sure smooth airflow into the radiator core area. This significantly increased the cooling performance of the car with reduction in drag.