An electron rich porous extended framework as a heterogeneous catalyst for Diels-Alder reactions

An electron rich porous metal-organic framework (MOF) has been synthesized, which acts as an effective heterogeneous catalyst for Diels-Alder reactions through encapsulation of the reactants in confined nano-channels of the framework.

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.

Analytical solutions for movement of cold water thermal front in a heterogeneous geothermal reservoir

In the present study an analytical model has been presented to describe the transient temperature distribution and advancement of the thermal front generated due to the reinjection of heat depleted water in a heterogeneous geothermal reservoir. One dimensional heat transport equation in porous media with advection and longitudinal heat conduction has been solved analytically using Laplace transform technique in a semi infinite medium. The heterogeneity of the porous medium is expressed by the spatial variation of the flow velocity and the longitudinal effective thermal conductivity of the medium. A simpler solution is also derived afterwards neglecting the longitudinal conduction depending on the situation where the contribution to the transient heat transport phenomenon in the porous media is negligible. Solution for a homogeneous aquifer with constant values of the rock and fluid parameters is also derived with an aim to compare the results with that of the heterogeneous one. The effect of some of the parameters involved, on the transient heat transport phenomenon is assessed by observing the variation of the results with different magnitudes of those parameters. Results prove the heterogeneity of the medium, the flow velocity and the longitudinal conductivity to have great influence and porosity to have negligible effect on the transient temperature distribution. (C) 2013 Elsevier Inc. All rights reserved.

Minimizing total weighted tardiness on heterogeneous batch processors with incompatible job families

In this paper, we address a scheduling problem for minimizing total weighted tardiness. The background for the paper is derived from the automobile gear manufacturing process. We consider the bottleneck operation of heat treatment stage of gear manufacturing. Real-life scenarios like unequal release times, incompatible job families, nonidentical job sizes, heterogeneous batch processors, and allowance for job splitting have been considered. We have developed a mathematical model which takes into account dynamic starting conditions. The problem considered in this study is NP-hard in nature, and hence heuristic algorithms have been proposed to address it. For real-life large-size problems, the performance of the proposed heuristic algorithms is evaluated using the method of estimated optimal solution available in literature. Extensive computational analyses reveal that the proposed heuristic algorithms are capable of consistently obtaining near-optimal statistically estimated solutions in very reasonable computational time.

Generating Efficient Data Movement Code for Heterogeneous Architectures with Distributed-Memory

Programming for parallel architectures that do not have a shared address space is extremely difficult due to the need for explicit communication between memories of different compute devices. A heterogeneous system with CPUs and multiple GPUs, or a distributed-memory cluster are examples of such systems. Past works that try to automate data movement for distributed-memory architectures can lead to excessive redundant communication. In this paper, we propose an automatic data movement scheme that minimizes the volume of communication between compute devices in heterogeneous and distributed-memory systems. We show that by partitioning data dependences in a particular non-trivial way, one can generate data movement code that results in the minimum volume for a vast majority of cases. The techniques are applicable to any sequence of affine loop nests and works on top of any choice of loop transformations, parallelization, and computation placement. The data movement code generated minimizes the volume of communication for a particular configuration of these. We use a combination of powerful static analyses relying on the polyhedral compiler framework and lightweight runtime routines they generate, to build a source-to-source transformation tool that automatically generates communication code. We demonstrate that the tool is scalable and leads to substantial gains in efficiency. On a heterogeneous system, the communication volume is reduced by a factor of 11X to 83X over state-of-the-art, translating into a mean execution time speedup of 1.53X. On a distributed-memory cluster, our scheme reduces the communication volume by a factor of 1.4X to 63.5X over state-of-the-art, resulting in a mean speedup of 1.55X. In addition, our scheme yields a mean speedup of 2.19X over hand-optimized UPC codes.

Determination of Internal Structures of Heterogeneous Nanocrystals Using Variable-Energy Photoemission Spectroscopy

This article describes the determination of the internal structure of heterogeneous nanoparticle systems including inverted core-shell (CdS core and CdSe shell) and alloyed (CdSeS) quantum dots using depth-resolved, variable-energy X-ray photoelectron spectroscopy (XPS). A unique feature of this work is the combination of photoelectron spectroscopy performed at lower X-ray energies (400-700 eV), to achieve surface sensitivity, with bulk sensitive measurements at high photon energies (>2000 eV), thereby providing detailed information about the whole nanoparticle structure with a great accuracy. The use of high photon energies furthermore allows us to investigate nanoparticles much larger than those studied thus far. This capability is a consequence of the much-increased mean free path of the photoelectron achieved at high excitation energies. Our results show that the actual structures of the synthesized nanoparticles are considerably different from the nominal, targeted structures, which can be post facto rationalized in terms of the reactivity of different constituents.

Lantana camara L. (Verbenaceae) invasion along streams in a heterogeneous landscape

Streams are periodically disturbed due to flooding, act as edges between habitats and also facilitate the dispersal of propagules, thus being potentially more vulnerable to invasions than adjoining regions. We used a landscape-wide transect-based sampling strategy and a mixed effects modelling approach to understand the effects of distance from stream, a rainfall gradient, light availability and fire history on the distribution of the invasive shrub Lantana camara L.(lantana) in the tropical dry forests of Mudumalai in southern India. The area occupied by lantana thickets and lantana stem abundance were both found to be highest closest to streams across this landscape with a rainfall gradient. There was no advantage in terms of increased abundance or area occupied by lantana when it grew closer to streams in drier areas as compared to moister areas. On an average, the area covered by lantana increased with increasing annual rainfall. Areas that experienced greater number of fires during 1989-2010 had lower lantana stem abundance irrespective of distance from streams. In this landscape, total light availability did not affect lantana abundance. Understanding the spatially variable environmental factors in a heterogeneous landscape influencing the distribution of lantana would aid in making informed management decisions at this scale.

Hydrophobic hydration driven self-assembly of curcumin in water: Similarities to nucleation and growth under large metastability, and an analysis of water dynamics at heterogeneous surfaces

As the beneficial effects of curcumin have often been reported to be limited to its small concentrations, we have undertaken a study to find the aggregation properties of curcumin in water by varying the number of monomers. Our molecular dynamics simulation results show that the equilibrated structure is always an aggregated state with remarkable structural rearrangements as we vary the number of curcumin monomers from 4 to 16 monomers. We find that the curcumin monomers form clusters in a very definite pattern where they tend to aggregate both in parallel and anti-parallel orientation of the phenyl rings, often seen in the formation of beta-sheet in proteins. A considerable enhancement in the population of parallel alignments is observed with increasing the system size from 12 to 16 curcumin monomers. Due to the prevalence of such parallel alignment for large system size, a more closely packed cluster is formed with maximum number of hydrophobic contacts. We also follow the pathway of cluster growth, in particular the transition from the initial segregated to the final aggregated state. We find the existence of a metastable structural intermediate involving a number of intermediate-sized clusters dispersed in the solution. We have constructed a free energy landscape of aggregation where the metatsable state has been identified. The course of aggregation bears similarity to nucleation and growth in highly metastable state. The final aggregated form remains stable with the total exclusion of water from its sequestered hydrophobic core. We also investigate water structure near the cluster surface along with their orientation. We find that water molecules form a distorted tetrahedral geometry in the 1st solvation layer of the cluster, interacting rather strongly with the hydrophilic groups at the surface of the curcumin. The dynamics of such quasi-bound water molecules near the surface of curcumin cluster is considerably slower than the bulk signifying a restricted motion as often found in protein hydration layer. (C) 2014 AIP Publishing LLC.

Insights on Defect-Mediated Heterogeneous Nucleation of Graphene on Copper

The grain size of monolayer large area graphene is key to its performance. Microstructural design for the desired grain size requires a fundamental understanding of graphene nucleation and growth. The two levers that can be used to control these aspects are the defect density, whose population can be controlled by annealing, and the gas-phase supersaturation for activation of nucleation at the defect sites. We observe that defects on copper surface, namely dislocations, grain boundaries, triple points, and rolling marks, initiate nucleation of graphene. We show that among these defects dislocations are the most potent nucleation sites, as they get activated at lowest supersaturation. As an illustration, we tailor the defect density and supersaturation to change the domain size of graphene from <1 mu m(2) to >100 mu m(2). Growth data reported in the literature has been summarized on a supersaturation plot, and a regime for defect-dominated growth has been identified. In this growth regime, we demonstrate the spatial control over nucleation at intentionally introduced defects, paving the way for patterned growth of graphene. Our results provide a unified framework for understanding the role of defects in graphene nucleation and can be used as a guideline for controlled growth of graphene.

Actin-Curcumin Interaction: Insights into the Mechanism of Actin Polymerization Inhibition

Curcumin, derived from rhizomes of the Curcuma longa plant, is known to possess a wide range of medicinal properties. We have examined the interaction of curcumin with actin and determined their binding and thermodynamic parameters using isothermal titration calorimetry. Curcumin is weakly fluorescent in aqueous solution, and binding to actin enhances fluorescence several fold with a large blue shift in the emission maximum. Curcumin inhibits microfilament formation, which is similar to its role in inhibiting microtubule formation. We synthesized a series of stable curcumin analogues to examine their affinity for actin and their ability to inhibit actin self-assembly. Results show that curcumin is a ligand with two symmetrical halves, each of which possesses no activity individually. Oxazole, pyrazole, and acetyl derivatives are less effective than curcumin at inhibiting actin self-assembly, whereas a benzylidiene derivative is more effective. Cell biology studies suggest that disorganization of the actin network leads to destabilization of filaments in the presence of curcumin. Molecular docking reveals that curcumin binds close to the cytochalasin binding site of actin. Further molecular dynamics studies reveal a possible allosteric effect in which curcumin binding at the barbed end of actin is transmitted to the pointed end, where conformational changes disrupt interactions with the adjacent actin monomer to interrupt filament formation. Finally, the recognition and binding of actin by curcumin is yet another example of its unique ability to target multiple receptors.

A Perspective to Adopt Continuous Dynamic Cognition for Malicious Node Detection in Heterogeneous Networks

The current day networks use Proactive networks for adaption to the dynamic scenarios. The use of cognition technique based on the Observe, Orient, Decide and Act loop (OODA) is proposed to construct proactive networks. The network performance degradation in knowledge acquisition and malicious node presence is a problem that exists. The use of continuous time dynamic neural network is considered to achieve cognition. The variance in service rates of user nodes is used to detect malicious activity in heterogeneous networks. The improved malicious node detection rates are proved through the experimental results presented in this paper. (C) 2015 The Authors. Published by Elsevier B.V.

Modeling of the non-isothermal liquid droplet impact on a heated solid substrate with heterogeneous wettability

A comprehensive numerical investigation on the impingement and spreading of a non-isothermal liquid droplet on a solid substrate with heterogeneous wettability is presented in this work. The time-dependent incompressible Navier-Stokes equations are used to describe the fluid flow in the liquid droplet, whereas the heat transfer in the moving droplet and in the solid substrate is described by the energy equation. The arbitrary Lagrangian-Eulerian (ALE) formulation with finite elements is used to solve the time-dependent incompressible Navier-Stokes equation and the energy equation in the time-dependent moving domain. Moreover, the Marangoni convection is included in the variational form of the Navier-Stokes equations without calculating the partial derivatives of the temperature on the free surface. The heterogeneous wettability is incorporated into the numerical model by defining a space-dependent contact angle. An array of simulations for droplet impingement on a heated solid substrate with circular patterned heterogeneous wettability are presented. The numerical study includes the influence of wettability contrast, pattern diameter, Reynolds number and Weber number on the confinement of the spreading droplet within the inner region, which is more wettable than the outer region. Also, the influence of these parameters on the total heat transfer from the solid substrate to the liquid droplet is examined. We observe that the equilibrium position depends on the wettability contrast and the diameter of the inner surface. Consequently. the heat transfer is more when the wettability contrast is small and/or the diameter of inner region is large. The influence of the Weber number on the total heat transfer is more compared to the Reynolds number, and the total heat transfer increases when the Weber number increases. (C) 2015 Elsevier Ltd. All rights reserved.

Falcon: A Graph Manipulation Language for Heterogeneous Systems

Graph algorithms have been shown to possess enough parallelism to keep several computing resources busy-even hundreds of cores on a GPU. Unfortunately, tuning their implementation for efficient execution on a particular hardware configuration of heterogeneous systems consisting of multicore CPUs and GPUs is challenging, time consuming, and error prone. To address these issues, we propose a domain-specific language (DSL), Falcon, for implementing graph algorithms that (i) abstracts the hardware, (ii) provides constructs to write explicitly parallel programs at a higher level, and (iii) can work with general algorithms that may change the graph structure (morph algorithms). We illustrate the usage of our DSL to implement local computation algorithms (that do not change the graph structure) and morph algorithms such as Delaunay mesh refinement, survey propagation, and dynamic SSSP on GPU and multicore CPUs. Using a set of benchmark graphs, we illustrate that the generated code performs close to the state-of-the-art hand-tuned implementations.

Dynamos driven by weak thermal convection and heterogeneous outer boundary heat flux

We use numerical dynamo models with heterogeneous core-mantle boundary (CMB) heat flux to show that lower mantle lateral thermal variability may help support a dynamo under weak thermal convection. In our reference models with homogeneous CMB heat flux, convection is either marginally supercritical or absent, always below the threshold for dynamo onset. We find that lateral CMB heat flux variations organize the flow in the core into patterns that favour the growth of an early magnetic field. Heat flux patterns symmetric about the equator produce non-reversing magnetic fields, whereas anti-symmetric patterns produce polarity reversals. Our results may explain the existence of the geodynamo prior to inner core nucleation under a tight energy budget. Furthermore, in order to sustain a strong geomagnetic field, the lower mantle thermal distribution was likely dominantly symmetric about the equator. (C) 2015 Elsevier B.V. All rights reserved.

Urea-Functionalized Self-Assembled Molecular Prism for Heterogeneous Catalysis in Water

Reaction of a ditopic urea ``strut'' (L-1) with cis-(tmen)Pd(NO3)(2) yielded a 3+3] self-assembled molecular triangle (T)L-1 = 1,4-di(4-pyridylureido)benzene; tmen = N,N,N',N'-tetrame-thylethane-1,2-diamine]. Replacing cis-(tmen)Pd(NO3)(2) in the above reaction with an equimolar mixture of Pd(NO3)(2) and a clip-type donor (L-2) yielded a template-free multicomponent 3D trigonal prism (P) decorated with multiple urea moieties L-2 = 3,3'-(1H-1,2,4-triazole-3,5-diyl)dipyridine]. This prism (P) was characterized by NMR. spectroscopy, and the structure was confirmed by X-ray crystallography. The P was employed as an effective hydrogen-bond-donor catalyst for Michael reactions of a series of water-insoluble nitro-olefins in an aqueous medium. The P showed better catalytic activity compared to the urea based ligand L-1 and the triangle T. Moreover, the confined nanospace of P in addition to large product outlet windows makes this 3D architecture a perfect molecular vessel to catalyze Diels-Alder reactions of 9-hydroxymethylanthracene with N-substituted maleimide in the aqueous medium. The present results demonstrate new observations on catalytic aqueous Diels-Alder and Michael reactions in heterogeneous fashion employing a discrete 3D architecture of Pd(II). The prism was recycled by simple filtration and reused several tithes without significant loss of activity.