Stereoselectivity in the addition of hydrogen chloride to cyclohex-1-enecarbonitrile: Possible role of chlorine lone pair-nitrile π-orbital pseudoallylic A1, 3 interaction

The (overall trans) addition of hydrogen chloride to cyclohex-1- enecarbonitrile in anhydrous alcoholic media proceeds to give cis-2-chlorocyclohexanecarboxylate (together with some cis-2- chlorocyclohexanecarboxamide): no corresponding products with the trans-configuration are detectable. In anhydrous ether the addition proceeds to give a single isomer, presumably cis-, of 2-chlorocyclohexanecarbonitrile, indicating that the configuration of the products may not be equilibrium-controlled in alcoholic media. An examination of the steric factors indicates that the transition state for protonation of the presumed intermediate, 2-chlorocyclohexylidenemethylideneimine, leading to cis-product is favoured if interaction between the lateral π-orbital of the C-N double bond and the lone-pairs on the chlorine atom at the 2-position is large. Consideration of interactions in the transition states meets Zimmerman's criticism that invoking A1, 3 interaction existing in ground states to explain product configuration takes insufficient account of the Curtin-Hammett principle.

Solvation dynamics in dipolar liquids

The time dependent response of a polar solvent to a changing charge distribution is studied in solvation dynamics. The change in the energy of the solute is measured by a time domain Stokes shift in the fluorescence spectrum of the solute. Alternatively, one can use sophisticated non-linear optical spectroscopic techniques to measure the energy fluctuation of the solute at equilibrium. In both methods, the measured dynamic response is expressed by the normalized solvation time correlation function, S(t). The latter is found to exhibit uniquefeatures reflecting both the static and dynamic characteristics of each solvent. For water, S(t) consists of a dominant sub-50 fs ultrafast component, followed by a multi-exponential decay. Acetonitrile exhibitsa sub-100 fs ultrafast component, followed by an exponential decay. Alcohols and amides show features unique to each solvent and solvent series. However, understanding and interpretation of these results have proven to be difficult, and often controversial. Theoretical studiesand computer simulations have greatly facilitated the understanding ofS(t) in simple systems. Recently solvation dynamics has been used extensively to explore dynamics of complex systems, like micelles and reverse micelles, protein and DNA hydration layers, sol-gel mixtures and polymers. In each case one observes rich dynamical features, characterized again by multi-exponential decays but the initial and final time constants are now widely separated. In this tutorial review, we discuss the difficulties in interpreting the origin of the observed behaviour in complex systems.

Truthful and Quality Conscious Query Incentive Networks

Query incentive networks capture the role of incentives in extracting information from decentralized information networks such as a social network. Several game theoretic tilt:Kids of query incentive networks have been proposed in the literature to study and characterize the dependence, of the monetary reward required to extract the answer for a query, on various factors such as the structure of the network, the level of difficulty of the query, and the required success probability.None of the existing models, however, captures the practical andimportant factor of quality of answers. In this paper, we develop a complete mechanism design based framework to incorporate the quality of answers, in the monetization of query incentive networks. First, we extend the model of Kleinberg and Raghavan [2] to allow the nodes to modulate the incentive on the basis of the quality of the answer they receive. For this qualify conscious model. we show are existence of a unique Nash equilibrium and study the impact of quality of answers on the growth rate of the initial reward, with respect to the branching factor of the network. Next, we present two mechanisms; the direct comparison mechanism and the peer prediction mechanism, for truthful elicitation of quality from the agents. These mechanisms are based on scoring rules and cover different; scenarios which may arise in query incentive networks. We show that the proposed quality elicitation mechanisms are incentive compatible and ex-ante budget balanced. We also derive conditions under which ex-post budget balance can beachieved by these mechanisms.

Polarographic and redox potential studies on copper(I) and copper(II) and their complexes. Part III. Copper (I and II)-ethylene diamine and edta complexes and theory of formation of step reduction waves in cupric copper systems

Polarographic and redox potential measurements on the cupric and cuprous complexes of ethylenediamine and EDTA have been carried out. From the ratio of the stability constants of the cupric and cuprous complexes, and the stability constant of the cupric complex, the stability constant of the cuprous-ethylenediamine complex is obtained. In the case of the EDTA complex it has been possible to obtain only βic/β2ous from the equilibrium concentrations of the cuprous and cupric complexes and the disproportionation constant. The inequalities for the appearance of step reduction waves have been given. The values of the stability constants of the cupric and cuprous complexes determined by the polarographic-redox potential method have been used to explain the appearance of step reduction waves in some systems and the non-appearance in other systems.

Polarographic and redox potential studies on copper(I) and copper(II) and their complexes. Part I. Copper(I and II)-ammonia and methylamine complexes

The equilibrium between cuprous ion, cupric ion and metallic copper has been studied using polarographic and redox potential measurements, by reducing cupric ion with copper gauze until equilibrium. Using the well-defined anodic diffusion current plateau, an amperometric method for estimating cuprous copper based on the titration of cuprous ion with dichromate or permanganate has been developed. The diffusion current constant and the disproportionation constant of cuprous ion and the standard potential for the reduction reaction of Cu2+ → Cu+ have been determined. Polarograms have been taken after reducing cupric complexes of ammonia and methylamine with copper until equilibrium. In the case of the copper-ammonia system, reduction to the cuprous state is practically complete while in the case of the cupric-methylamine system, the first cathodic wave occurs to some extent. A new method, called the polarographic-redox potential method, for determining the stability constants of cuprous and cupric complexes has been developed. The method depends upon the determination of the concentration of complexes by polarographic wave heights, and free cupric anc cuprous ions by redox potentials. The stability constants of the following complexes have been obtained: Cu(NH3)2+4, Cu(NH3)+2, Cu(CH3NH2)2(OH)2, Cu(CH3NH2)+2. The stability constants determined by the new method and the half-wave potential shift method agree and the value for the cupric-ammonia complex is in good agreement with Bjerrum method, indicating the reliability of this method.

Nature of the colour-forming species in peroxy titanium sulphate

ALTHOUGH titanium is determined colorimetrically in aqueous sulphuric acid medium in presence of excess of hydrogen peroxide, the nature of the colour-forming species is not known definitely. Schwarz1 suggested that the colour was due to the peroxo-disulphato titanate anion [O 2Ti(SO4)2]2-. On the other hand, Jahr2 and later Gastinger3 considered that the colour of the compound was due to the peroxy titanyl cation [TiO2 aq.] 2+, and suggested the following equilibrium in solution: Schaeppi and Treadwell4 attributed the colour bo O2TiSO4 or [O2Ti(SO4)2]2-, whereas Babko and Volkova5 represented the coloured complex ion as [Ti(H 2O2)]4+. Mori, Shibata, Kyuno and Ito 6 regarded the coloured species as [TiO2 aq.]2+ or [Ti(OH)2 (H2O)(H2O2)] 2+, assuming the co-ordination number of titanium to be four. Thus, a variety of constitutions has been proposed to explain the colour-forming species of the titanium complex, based on the investigations carried out in dilute sulphuric acid medium, but the complex has not been isolated so far.

Symmetry and shape issues in nanostructure growth

Symmetry plays a key role in dictating the equilibrium morphology of crystals. However, several growth morphologies that deviate from the point group symmetry are routinely observed under several different growth conditions. In this article, we present a summary of symmetry-breaking mechanisms that are operative for crystals grown from the vapour phase as well as those formed as a result of wet chemical synthesis. This understanding is crucial for rationalizing the variety of morphologies observed during nanocrystal synthesis and also providesa rational framework for the synthesis of anisotropic nanostructures.

A study of the slow reaction in Al-5 wt.% Ag alloy by resistivity measurements

The slow reaction in an Al-5 wt.% Ag alloy has been investigated by resistivity measurements. The "slope change" method gave an activation energy of 1.25 eV for silver diffusion during the slow reaction. The existence of an excess concentration of vacancies in equilibrium with the dislocation loops seems to be responsible for the slow reaction. The presence of silver inhibits the nucleation of dislocation loops by holding up the quenched-in vacancies in solution. There is no indication of the presence of a third stage in the low-temperature ageing process of this alloy.

Equivalent constitutive model-based design of wave-absorbing material system and controller

A design methodology for wave-absorbing active material system is reported. The design enforces equivalence between an assumed material model having wave-absorbing behavior and a set of target feedback controllers for an array of microelectro-mechanical transducers which are integral part of the active material system. The proposed methodology is applicable to problems involving the control of acoustic waves in passive-active material system with complex constitutive behavior at different length-scales. A stress relaxation type one-dimensional constitutive model involving viscous damping mechanism is considered, which shows asymmetric wave dispersion characteristics about the half-line. The acoustic power flow and asymptotic stability of such material system are studied. A single sensor non-collocated linear feedback control system in a one-dimensional finite waveguide, which is a representative volume element in an active material system, is considered. Equivalence between the exact dynamic equilibrium of these two systems is imposed. It results in the solution space of the design variables, namely the equivalent damping coefficient, the wavelength(s) to be controlled and the location of the sensor. The characteristics of the controller transfer functions and their pole-placement problem are studied. (c) 2005 Elsevier Ltd. All rights reserved.

Large-scale structures in turbulent and reverse-transitional sink flow boundary layers

Aspects of large-scale organized structures in sink flow turbulent and reverse-transitional boundary layers are studied experimentally using hot-wire anemometry. Each of the present sink flow boundary layers is in a state of 'perfect equilibrium' or 'exact self-preservation' in the sense of Townsend (The Structure of Turbulent Shear Flow, 1st and 2nd edns, 1956, 1976, Cambridge University Press) and Rotta (Progr. Aeronaut. Sci., vol. 2, 1962, pp. 1-220) and conforms to the notion of 'pure wall-flow' (Coles, J. Aerosp. Sci., vol. 24, 1957, pp. 495-506), at least for the turbulent cases. It is found that the characteristic inclination angle of the structure undergoes a systematic decrease with the increase in strength of the streamwise favourable pressure gradient. Detectable wall-normal extent of the structure is found to be typically half of the boundary layer thickness. Streamwise extent of the structure shows marked increase as the favourable pressure gradient is made progressively severe. Proposals for the typical eddy forms in sink flow turbulent and reverse-transitional flows are presented, and the possibility of structural self-organization (i.e. individual hairpin vortices forming streamwise coherent hairpin packets) in these flows is also discussed. It is further indicated that these structural ideas may be used to explain, from a structural viewpoint, the phenomenon of soft relaminarization or reverse transition of turbulent boundary layers when subjected to strong streamwise favourable pressure gradients. Taylor's 'frozen turbulence' hypothesis is experimentally shown to be valid for flows in the present study even though large streamwise accelerations are involved, the flow being even reverse transitional in some cases. Possible conditions, which are required to be satisfied for the safe use of Taylor's hypothesis in pressure-gradient-driven flows, are also outlined. Measured convection velocities are found to be fairly close to the local mean velocities (typically 90% or more) suggesting that the structure gets convected downstream almost along with the mean flow.

Optimum Design for External Seismic Stability of Geosynthetic Reinforced Soil Walls: Reliability Based Approach

In this paper, an analytical study considering the effect of uncertainties in the seismic analysis of geosynthetic-reinforced soil (GRS) walls is presented. Using limit equilibrium method and assuming sliding wedge failure mechanism, analysis is conducted to evaluate the external stability of GRS walls when subjected to earthquake loads. Target reliability based approach is used to estimate the probability of failure in three modes of failure, viz., sliding, bearing, and eccentricity failure. The properties of reinforced backfill, retained backfill, foundation soil, and geosynthetic reinforcement are treated as random variables. In addition, the uncertainties associated with horizontal seismic acceleration and surcharge load acting on the wall are considered. The optimum length of reinforcement needed to maintain the stability against three modes of failure by targeting various component and system reliability indices is obtained. Studies have also been made to study the influence of various parameters on the seismic stability in three failure modes. The results are compared with those given by first-order second moment method and Monte Carlo simulation methods. In the illustrative example, external stability of the two walls, Gould and Valencia walls, subjected to Northridge earthquake is reexamined.

Two-Phase Thermodynamic Model for Efficient and Accurate Absolute Entropy of Water from Molecular Dynamics Simulations

Presented here is the two-phase thermodynamic (2PT) model for the calculation of energy and entropy of molecular fluids from the trajectory of molecular dynamics (MD) simulations. In this method, the density of state (DoS) functions (including the normal modes of translation, rotation, and intramolecular vibration motions) are determined from the Fourier transform of the corresponding velocity autocorrelation functions. A fluidicity parameter (f), extracted from the thermodynamic state of the system derived from the same MD, is used to partition the translation and rotation modes into a diffusive, gas-like component (with 3Nf degrees of freedom) and a nondiffusive, solid-like component. The thermodynamic properties, including the absolute value of entropy, are then obtained by applying quantum statistics to the solid component and applying hard sphere/rigid rotor thermodynamics to the gas component. The 2PT method produces exact thermodynamic properties of the system in two limiting states: the nondiffusive solid state (where the fluidicity is zero) and the ideal gas state (where the fluidicity becomes unity). We examine the 2PT entropy for various water models (F3C, SPC, SPC/E, TIP3P, and TIP4P-Ew) at ambient conditions and find good agreement with literature results obtained based on other simulation techniques. We also validate the entropy of water in the liquid and vapor phases along the vapor-liquid equilibrium curve from the triple point to the critical point. We show that this method produces converged liquid phase entropy in tens of picoseconds, making it an efficient means for extracting thermodynamic properties from MD simulations.

Reliability Analysis of Earth Dams

In the present study, results of reliability analyses of four selected rehabilitated earth dam sections, i.e., Chang, Tapar, Rudramata, and Kaswati, under pseudostatic loading conditions, are presented. Using the response surface methodology, in combination with first order reliability method and numerical analysis, the reliability index (beta) values are obtained and results are interpreted in conjunction with conventional factor of safety values. The influence of considering variability in the input soil shear strength parameters, horizontal seismic coefficient (alpha(h)), and location of reservoir full level on the stability assessment of the earth dam sections is discussed in the probabilistic framework. A comparison of results with those obtained from other method of reliability analysis, viz., Monte Carlo simulations combined with limit equilibrium approach, provided a basis for discussing the stability of earth dams in probabilistic terms, and the results of the analysis suggest that the considered earth dam sections are reliable and are expected to perform satisfactorily.

Optimum Design for External Seismic Stability of Geosynthetic Reinforced Soil Walls: Reliability Based Approach

In this paper, an analytical study considering the effect of uncertainties in the seismic analysis of geosynthetic-reinforced soil (GRS) walls is presented. Using limit equilibrium method and assuming sliding wedge failure mechanism, analysis is conducted to evaluate the external stability of GRS walls when subjected to earthquake loads. Target reliability based approach is used to estimate the probability of failure in three modes of failure, viz., sliding, bearing, and eccentricity failure. The properties of reinforced backfill, retained backfill, foundation soil, and geosynthetic reinforcement are treated as random variables. In addition, the uncertainties associated with horizontal seismic acceleration and surcharge load acting on the wall are considered. The optimum length of reinforcement needed to maintain the stability against three modes of failure by targeting various component and system reliability indices is obtained. Studies have also been made to study the influence of various parameters on the seismic stability in three failure modes. The results are compared with those given by first-order second moment method and Monte Carlo simulation methods. In the illustrative example, external stability of the two walls, Gould and Valencia walls, subjected to Northridge earthquake is reexamined.

Studies on interaction of colloidal Ag nanoparticles with Bovine Serum Albumin (BSA)

Biofunctionalization of noble metal nanoparticles like Ag, Au is essential to obtain biocompatibility for specific biomedical applications. Silver nanciparticles are being increasingly used in bio-sensing applications owing to excellent optoelectronic properties. Among the serum albumins, the most abundant proteins in plasma, a wide range of physiological functions of Bovine Serum Albumin (BSA) has made it a model system for biofunctionalization. In absence of adequate prior reports, this study aims to investigate the interaction between silver nanoparticles and BSA. The interaction of BSA [0.05-0.85% concentrations] with Ag nanoparticles [50 ppm concentration] in aqueous dispersion was Studied through UV-vis spectral changes, morphological and surface structural changes. At pH 7, which is More than the isoelectric point of BSA, a decrease in absorbance at plasmon peak of uninteracted nanciparticles (425 mn) was noted till 0.45% BSA, beyond that a blue shift towards 410 urn was observed. The blue shift may be attributed to enhanced electron density on the particle surfaces. Increasing pH to 12 enhanced the blue shift further to 400 rim. The conformational changes in BSA at alkaline pH ranges and consequent hydrophobic interactions also played an important role. The equilibrium adsorption data fitted better to Freundlich isotherm compared to Langmuir Curve. The X-ray diffraction study revealed complete coverage of Ag nanoparticles by BSA. The scanning electron microscopic study of the interacted nanoparticles was also carried Out to decipher morphological changes. This study established that tailoring the concentration of BSA and pH of the interaction it was possible to reduce aggregation of nanoparticles. Biofunctionalized Ag nanoparticles with reduced aggregation will be more amenable towards bio-sensing applications. (C) 2009 Elsevier B.V. All rights reserved.