Computational Study of the Migration of Rhenium from One Enantioface of an Olefin to the Other Facilitated by (C-H)center dot center dot center dot Re Interactions

The migration of a metal atom in a metal olefin complex from one pi face of the olefin to the opposite pi face has been rarely documented. Gladysz and co-workers showed that such a movement is indeed possible in monosubstituted chiral Re olefin complexes, resulting in diastereomerization. Interestingly, this isomerization occurred without dissociation, and on the basis of kinetic isotope effects, the involvement of a trans C-H bond was indicated. Either oxidative addition or an agostic interaction of the vinylic C-H(D) bond with the metal could account for the experimentally observed kinetic isotope effect. In this study we compute the free energy of activation for the migration of Re from one enantioface of the olefin to the other through various pathways. On the basis of DFT calculations at the B3LYP level we show that a trans (C-H)center dot center dot center dot Re interaction and trans C-H oxidative addition provide a nondissociative path for the diastereomerization. The trans (C-H)center dot center dot center dot Re interaction path is computed to be more favorable by 2.3 kcal mol(-1) than the oxidative addition path. While direct experimental evidence was not able to discount the migration of the metal through the formation of a eta(2)-arene complex (conducted tour mechanism), computational results at the B3LYP level show that it is energetically more expensive. Surprisingly, a similar analysis carried out at the M06 level computes a lower energy path for the conducted tour mechanism and is not consistent with the experimental isotope effects observed. Metal-(C-H) interactions and oxidative additions of the metal into C-H bonds are closely separated in energy and might contribute to unusual fluxional processes such as this diastereomerization.

Measurement Based Impromptu Deployment of a Multi-Hop Wireless Relay Network

We study the problem of optimal sequential (''as-you-go'') deployment of wireless relay nodes, as a person walks along a line of random length (with a known distribution). The objective is to create an impromptu multihop wireless network for connecting a packet source to be placed at the end of the line with a sink node located at the starting point, to operate in the light traffic regime. In walking from the sink towards the source, at every step, measurements yield the transmit powers required to establish links to one or more previously placed nodes. Based on these measurements, at every step, a decision is made to place a relay node, the overall system objective being to minimize a linear combination of the expected sum power (or the expected maximum power) required to deliver a packet from the source to the sink node and the expected number of relay nodes deployed. For each of these two objectives, two different relay selection strategies are considered: (i) each relay communicates with the sink via its immediate previous relay, (ii) the communication path can skip some of the deployed relays. With appropriate modeling assumptions, we formulate each of these problems as a Markov decision process (MDP). We provide the optimal policy structures for all these cases, and provide illustrations of the policies and their performance, via numerical results, for some typical parameters.

Cu(In,Al)Se-2 thin films by one-step electrodeposition for photovoltaics

Chalcopyrite Cu(In,Al)Se-2 (CIAS) thin films are grown on stainless steel substrate through one-step electrodeposition at room temperature. Indium is partially replaced with aluminum to increase the band gap of CuInSe2 without creating significant change in the original structure. The deposition potential is optimized at -0.8 V (vs. SCE) and annealing of the films is performed in vacuum to remove binary phases present in the as-deposited films. In/Al ratio is varied from 1/9 to 8/2, to find the suitability for solar cell fabrication. For In/Al ratio of less than 8/2, CuAlSe2 phase is formed in the film in addition to the CIAS phase. Depth profile X-ray photoelectron spectroscopy analysis of the CIAS sample prepared with In/Al ratio of 8/2 in the precursor solution confirmed the existence of single phase CIAS throughout the film. This film showed p-type conductivity while the rest of the samples with In/Al ratio less than 8/2 showed n-type conductivity. The band gap of the film varied from 1.06 to 1.45 eV, with variation in deposition potential. Structural, optical, morphological, compositional and electrical characterizations are carried out to establish the suitability of this film for solar cell fabrication. (C) 2013 Elsevier B.V. All rights reserved.

Quantum Phase Diagram of One-Dimensional Spin and Hubbard Models with Transitions to Bond Order Wave Phases

Similar quantum phase diagrams and transitions are found for three classes of one-dimensional models with equally spaced sites, singlet ground states (GS), inversion symmetry at sites and a bond order wave (BOW) phase in some sectors. The models are frustrated spin-1/2 chains with variable range exchange, half-filled Hubbard models with spin-independent interactions and modified Hubbard models with site energies for describing organic charge transfer salts. In some range of parameters, the models have a first order quantum transition at which the GS expectation value of the sublattice spin < S-A(2)> of odd or even-numbered sites is discontinuous. There is an intermediate BOW phase for other model parameters that lead to two continuous quantum transitions with continuous < S-A(2)>. Exact diagonalization of finite systems and symmetry arguments provide a unified picture of familiar 1D models that have appeared separately in widely different contexts.

Quantum Phase Diagram of One-Dimensional Spin and Hubbard Models with Transitions to Bond Order Wave Phases

Similar quantum phase diagrams and transitions are found for three classes of one-dimensional models with equally spaced sites, singlet ground states (GS), inversion symmetry at sites and a bond order wave (BOW) phase in some sectors. The models are frustrated spin-1/2 chains with variable range exchange, half-filled Hubbard models with spin-independent interactions and modified Hubbard models with site energies for describing organic charge transfer salts. In some range of parameters, the models have a first order quantum transition at which the GS expectation value of the sublattice spin < S-A(2)> of odd or even-numbered sites is discontinuous. There is an intermediate BOW phase for other model parameters that lead to two continuous quantum transitions with continuous < S-A(2)>. Exact diagonalization of finite systems and symmetry arguments provide a unified picture of familiar 1D models that have appeared separately in widely different contexts.

Novel 2,6-bis(4-methoxyphenyl)-1-methylpiperidin-4-one oxime esters: synthesis and a new insight into their antioxidant and antimicrobial potential

A simple and efficient protocol for the synthesis of novel 2,6-bis(4-methoxyphenyl)-1-methylpiperidin-4-one oxime esters 4(a-q) is described. Initially, p-anisaldehyde 1 was condensed (Mannich reaction) with acetone and ammonium acetate trihydrate afforded 2,6-bis(4-methoxyphenyl)piperidin-4-one 2. Then, methylation followed by oximation with hydroxylamine hydrochloride (NH(2)OHa (TM) HCl) furnished a key scaffold 4. Further, to explore the enhanced biological properties of the piperidin-4-one core i.e. the key scaffold 4 was conjugated with substituted benzoyl chlorides in the presence of anhydrous K2CO3 as base to obtain novel 2,6-bis(4-methoxyphenyl)-1-methylpiperidin-4-one oxime esters 4(a-q) in excellent yields. The newly synthesized compounds were characterized by elemental analysis, IR, H-1 NMR, C-13 NMR and mass spectroscopic techniques, and screened for their in vitro antioxidant and antimicrobial activities. Most of the compounds exerted positive efficacy towards the biological assays performed. Among the synthesized analogues, compounds 4l and 4m exhibited promising antioxidant activity and on the other hand compounds 4b and 4d manifested persuasive antibacterial activity, whereas compound 4b displayed stupendous antifungal activity against A. flavus strain.

Three-Dimensional Study of Natural Convection in a Horizontal Channel With Discrete Heaters on One of Its Vertical Walls

Three-dimensional natural convection in a horizontal channel with an array of discrete flush-mounted heaters on one of its vertical walls is numerically studied. Effects of thermal conductivities of substrate and heaters and convection on outer sides of the channel walls on heat transfer are examined. The substrate affects heat transfer in a wider range of thermal conductivities than do the heaters. At lower heater thermal conductivities a higher heat portion is transferred by direct convection from the heaters to the adjacent coolant. However, higher substrate conductivity is associated with higher heat portion transferred through the substrate. The innermost heater column is found to become the hottest heater column due to the lower coolant accessibility. The heat transfer in the channel is strongly influenced by convection on the outer sides of the channel walls. Correlations are presented for dimensionless temperature maximum and average Nusselt number.

Supersolid in a one-dimensional model of hard-core bosons

We study a system of hard-core boson on a one-dimensional lattice with frustrated next-nearest-neighbor hopping and nearest-neighbor interaction. At half filling, for equal magnitude of nearest- and next-nearest-neighbor hopping, the ground state of this system exhibits a first-order phase transition from a bond-ordered solid to a charge-density-wave solid as a function of the nearest- neighbor interaction. Moving away from half filling we investigate the system at incommensurate densities, where we find a supersolid phase which has concurrent off-diagonal long-range order and density-wave order which is unusual in a system of hard-core bosons in one dimension. Using the finite-size density-matrix renormalization group method, we obtain the complete phase diagram for this model.

Designing one dimensional Co-Ni/Co3O4-NiO core/shell nano-heterostructure electrodes for high-performance pseudocapacitor

A high-performance supercapacitor electrode based on unique 1D Co-Ni/Co3O4-NiO core/shell nano-heterostructures is designed and fabricated. The nano-heterostructures exhibit high specific capacitance (2013 F g(-1) at 2.5 A g(-1)), high energy and power density (23Wh kg(-1) and 5.5kW kg(-1), at the discharge current density of 20.8 A g(-1)), good capacitance retention and long cyclicality. The remarkable electrochemical property of the large surface area nano-heterostructures is demonstrated based on the effective nano-architectural design of the electrode with the coexistence of the two highly redox active materials at the surface supported by highly conducting metal alloy channel at the core for faster charge transport. (C) 2014 AIP Publishing LLC.

IS A DEEP ONE-CELL MERIDIONAL CIRCULATION ESSENTIAL FOR THE FLUX TRANSPORT SOLAR DYNAMO?

The solar activity cycle is successfully modeled by the flux transport dynamo, in which the meridional circulation of the Sun plays an important role. Most of the kinematic dynamo simulations assume a one-cell structure of the meridional circulation within the convection zone, with the equatorward return flow at its bottom. In view of the recent claims that the return flow occurs at a much shallower depth, we explore whether a meridional circulation with such a shallow return flow can still retain the attractive features of the flux transport dynamo (such as a proper butterfly diagram, the proper phase relation between the toroidal and poloidal fields). We consider additional cells of the meridional circulation below the shallow return flow-both the case of multiple cells radially stacked above one another and the case of more complicated cell patterns. As long as there is an equatorward flow in low latitudes at the bottom of the convection zone, we find that the solar behavior is approximately reproduced. However, if there is either no flow or a poleward flow at the bottom of the convection zone, then we cannot reproduce solar behavior. On making the turbulent diffusivity low, we still find periodic behavior, although the period of the cycle becomes unrealistically large. In addition, with a low diffusivity, we do not get the observed correlation between the polar field at the sunspot minimum and the strength of the next cycle, which is reproduced when diffusivity is high. On introducing radially downward pumping, we get a more reasonable period and more solar-like behavior even with low diffusivity.

Optimal sequential wireless relay placement on a random lattice path

Our work is motivated by impromptu (or ``as-you-go'') deployment of wireless relay nodes along a path, a need that arises in many situations. In this paper, the path is modeled as starting at the origin (where there is the data sink, e.g., the control center), and evolving randomly over a lattice in the positive quadrant. A person walks along the path deploying relay nodes as he goes. At each step, the path can, randomly, either continue in the same direction or take a turn, or come to an end, at which point a data source (e.g., a sensor) has to be placed, that will send packets to the data sink. A decision has to be made at each step whether or not to place a wireless relay node. Assuming that the packet generation rate by the source is very low, and simple link-by-link scheduling, we consider the problem of sequential relay placement so as to minimize the expectation of an end-to-end cost metric (a linear combination of the sum of convex hop costs and the number of relays placed). This impromptu relay placement problem is formulated as a total cost Markov decision process. First, we derive the optimal policy in terms of an optimal placement set and show that this set is characterized by a boundary (with respect to the position of the last placed relay) beyond which it is optimal to place the next relay. Next, based on a simpler one-step-look-ahead characterization of the optimal policy, we propose an algorithm which is proved to converge to the optimal placement set in a finite number of steps and which is faster than value iteration. We show by simulations that the distance threshold based heuristic, usually assumed in the literature, is close to the optimal, provided that the threshold distance is carefully chosen. (C) 2014 Elsevier B.V. All rights reserved.

Impacts of modern transitions on thermal comfort in vernacular dwellings in warm-humid climate of Sugganahalli (India)

Sugganahalli, a rural vernacular community in a warm-humid region in South India, is under transition towards adopting modern construction practices. Vernacular local building elements like rubble walls and mud roofs are given way to burnt brick walls and reinforced cement concrete (RCC)/tin roofs. Over 60% of Indian population is rural, and implications of such transitions on thermal comfort and energy in buildings are crucial to understand. Vernacular architecture evolves adopting local resources in response to the local climate adopting passive solar designs. This paper investigates the effectiveness of passive solar elements on the indoor thermal comfort by adopting modern climate-responsive design strategies. Dynamic simulation models validated by measured data have also been adopted to determine the impact of the transition from vernacular to modern material-configurations. Age-old traditional design considerations were found to concur with modern understanding into bio-climatic response and climate-responsiveness. Modern transitions were found to increase the average indoor temperatures in excess of 7 degrees C. Such transformations tend to shift the indoor conditions to a psychrometric zone that is likely to require active air-conditioning. Also, the surveyed thermal sensation votes were found to lie outside the extended thermal comfort boundary for hot developing countries provided by Givoni in the bio-climatic chart.

Laterally structured ripple and square phases with one and two dimensional thickness modulations in a model bilayer system

Molecular dynamics simulations of bilayers in a surfactant/co-surfactant/water system with explicit solvent molecules show formation of topologically distinct gel phases depending upon the bilayer composition. At low temperatures, the bilayers transform from the tilted gel phase, L beta', to the one dimensional (1D) rippled, P beta' phase as the surfactant concentration is increased. More interestingly, we observe a two dimensional (2D) square phase at higher surfactant concentration which, upon heating, transforms to the gel L beta' phase. The thickness modulations in the 1D rippled and square phases are asymmetric in two surfactant leaflets and the bilayer thickness varies by a factor of similar to 2 between maximum and minimum. The 1D ripple consists of a thinner interdigitated region of smaller extent alternating with a thicker non-interdigitated region. The 2D ripple phase is made up of two superimposed square lattices of maximum and minimum thicknesses with molecules of high tilt forming a square lattice translated from the lattice formed with the thickness minima. Using Voronoi diagrams we analyze the intricate interplay between the area-per-head-group, height modulations and chain tilt for the different ripple symmetries. Our simulations indicate that composition plays an important role in controlling the formation of low temperature gel phase symmetries and rippling accommodates the increased area-per-head-group of the surfactant molecules.

Characterization of Interactions Involving Bromine in 2,2-Dibromo2,3-dihydroinden-1-one via Experimental Charge Density Analysis

Experimental and theoretical charge density analyses on 2,2-dibromo-2,3-dihydroinden-1-one have been carried out to quantify the topological features of a short CBr....O halogen bond with nearly linear geometry (2.922 angstrom, angle CBr....O = 172.7 degrees) and to assess the strength of the interactions using the topological features of the electron density. The electrostatic potential map indicates the presence of the s-hole on bromine, while the interaction energy is comparable to that of a moderate OH....O hydrogen bond. In addition, the energetic contribution of CH.....Br interaction is demonstrated to be on par with that of the CBr....O halogen bond in stabilizing the crystal structure.

One-pot synthesis of functionalized beta-amino sulfides/beta-amino selenides via ring opening of cyclic sulfamidates

A number of functionalized beta-amino and gamma-amino sulfides and selenides have been synthesized involving a one-pot process of ring opening of cyclic sulfamidates with `in situ' generated thiolate and selenoate species from diaryl disulfides and diphenyl diselenide using rongalite. A mild and efficient method has been developed for the synthesis of cysteines from serine.