Studies On Hydrogen Bonds: Part IV. Proposed Working Criteria for Assessing Qualitative Strength of Hydrogen Bonds

The data obtained in the earlier parts of this series for the donor and acceptor end parameters of N-H. O and O-H. O hydrogen bonds have been utilised to obtain a qualitative working criterion to classify the hydrogen bonds into three categories: "very good" (VG), "moderately good" (MG) and weak (W). The general distribution curves for all the four parameters are found to be nearly of the Gaussian type. Assuming that the VG hydrogen bonds lie between 0 and ± la, MG hydrogen bonds between ± 1 and ± 2, W hydrogen bonds beyond ± 2 (where is the standard deviation), suitable cut-off limits for classifying the hydrogen bonds in the three categories have been derived. These limits are used to get VG and MG ranges for the four parameters 1 and θ (at the donor end) and ± and ± (at the acceptor end). The qualitative strength of a hydrogen bond is decided by the cumulative application of the criteria to all the four parameters. The criterion has been further applied to some practical examples in conformational studies such as α-helix and can be used for obtaining suitable location of hydrogen atoms to form good hydrogen bonds. An empirical approach to the energy of hydrogen bonds in the three categories has also been presented.

Thermal and photochemical cycloaddition reactions of thiocarbonyls: a qualitative molecular orbital analysis

A comprehensive analysis of thermal and photochemical reactions of thiocarbonyls has been undertaken within the PMO framework employing MINDO/3 orbital energies and wavefunctions. The model is generally successful in rationalizing the observed regiochemistry of such reactions. In particular, the indicated regiochemistry for [4 + 2] thermal cycloadditions of saturated thiones to 2-substituted dienes, for the dimerization of α,β-unsaturated thiones, and for the photochemical cycloadditions of thioketones and thioenones are all in agreement with experimental observations. Interesting predictions are also made concerning cycloadditions of saturated, conjugated, and arylalkyl thiones which have not yet been studied experimentally. The analysis reveals the decisive role played by secondary orbital interactions in determining the observed product selectivity in the photochemical reactions between thioenone and olefins.

Bicriterion differential games with qualitative outcomes

Combat games are studied as bicriterion differential games with qualitative outcomes determined by threshold values on the criterion functions. Survival and capture strategies of the players are defined using the notion of security levels. Closest approach survival strategies (CASS) and minimum risk capture strategies (MRCS) are important strategies for the players identified as solutions to four optimization problems involving security levels. These are used, in combination with the preference orderings of the qualitative outcomes by the players, to delineate the win regions and the secured draw and mutual kill regions for the players. It is shown that the secured draw regions and the secured mutual kill regions for the two players are not necessarily the same. Simple illustrative examples are given.

Lacunary Fourier series and a qualitative uncertainty principle for compact Lie groups

We define lacunary Fourier series on a compact connected semisimple Lie group G. If f is an element of L-1 (G) has lacunary Fourier series and f vanishes on a non empty open subset of G, then we prove that f vanishes identically. This result can be viewed as a qualitative uncertainty principle.

Thermodynamic modeling to analyse composition of carbonaceous coatings of MnO and other oxides of manganese grown by MOCVD

Equilibrium thermodynamic analysis has been applied to the low-pressure MOCVD process using manganese acetylacetonate as the precursor. ``CVD phase stability diagrams'' have been constructed separately for the processes carried out in argon and oxygen ambient, depicting the compositions of the resulting films as functions of CVD parameters. For the process conduced in argon ambient, the analysis predicts the simultaneous deposition of MnO and elemental carbon in 1: 3 molar proportion, over a range of temperatures. The analysis predicts also that, if CVD is carried out in oxygen ambient, even a very low flow of oxygen leads to the complete absence of carbon in the film deposited oxygen, with greater oxygen flow resulting in the simultaneous deposition of two different manganese oxides under certain conditions. The results of thermodynamic modeling have been verified quantitatively for low-pressure CVD conducted in argon ambient. Indeed, the large excess of carbon in the deposit is found to constitute a MnO/C nanocomposite, the associated cauliflower-like morphology making it a promising candidate for electrode material in supercapacitors. CVD carried out in oxygen flow, under specific conditions, leads to the deposition of more than one manganese oxide, as expected from thermodynamic analysis ( and forming an oxide-oxide nanocomposite). These results together demonstrate that thermodynamic analysis of the MOCVD process can be employed to synthesize thin films in a predictive manner, thus avoiding the inefficient trial-and-error method usually associated with MOCVD process development. The prospect of developing thin films of novel compositions and characteristics in a predictive manner, through the appropriate choice of CVD precursors and process conditions, emerges from the present work.

Qualitative theorem proving in linear constraints

We know, from the classical work of Tarski on real closed fields, that elimination is, in principle, a fundamental engine for mechanized deduction. But, in practice, the high complexity of elimination algorithms has limited their use in the realization of mechanical theorem proving. We advocate qualitative theorem proving, where elimination is attractive since most processes of reasoning take place through the elimination of middle terms, and because the computational complexity of the proof is not an issue. Indeed what we need is the existence of the proof and not its mechanization. In this paper, we treat the linear case and illustrate the power of this paradigm by giving extremely simple proofs of two central theorems in the complexity and geometry of linear programming.

Spin State Selective Excitation of Single Quantum Transitions Using Multiple Quantum Spectroscopy- an Aid to Analyse Complex Proton NMR spectra of Oriented Molecules

NMR spectra of molecules oriented in liquid-crystalline matrix provide information on the structure and orientation of the molecules. Thermotropic liquid crystals used as an orienting media result in the spectra of spins that are generally strongly coupled. The number of allowed transitions increases rapidly with the increase in the number of interacting spins. Furthermore, the number of single quantum transitions required for analysis is highly redundant. In the present study, we have demonstrated that it is possible to separate the subspectra of a homonuclear dipolar coupled spin system on the basis of the spin states of the coupled heteronuclei by multiple quantum (MQ)−single quantum (SQ) correlation experiments. This significantly reduces the number of redundant transitions, thereby simplifying the analysis of the complex spectrum. The methodology has been demonstrated on the doubly 13C labeled acetonitrile aligned in the liquid-crystal matrix and has been applied to analyze the complex spectrum of an oriented six spin system.

Studies on hydrogen-bonds .4. proposed working criteria for assessing qualitative strength of hydrogen-bonds

The data obtained in the earlier parts of this series for the donor and acceptor end parameters of N-H. O and O-H. O hydrogen bonds have been utilised to obtain a qualitative working criterion to classify the hydrogen bonds into three categories: “very good” (VG), “moderately good” (MG) and weak (W). The general distribution curves for all the four parameters are found to be nearly of the Gaussian type. Assuming that the VG hydrogen bonds lie between 0 and ± la, MG hydrogen bonds between ± 1s̀ and ± 2s̀, W hydrogen bonds beyond ± 2s̀ (where s̀ is the standard deviation), suitable cut-off limits for classifying the hydrogen bonds in the three categories have been derived. These limits are used to get VG and MG ranges for the four parameters 1 and θ (at the donor end) and ± and ± (at the acceptor end). The qualitative strength of a hydrogen bond is decided by the cumulative application of the criteria to all the four parameters. The criterion has been further applied to some practical examples in conformational studies such as α-helix and can be used for obtaining suitable location of hydrogen atoms to form good hydrogen bonds. An empirical approach to the energy of hydrogen bonds in the three categories has also been presented.

The design of polyaniline based sensor for the qualitative estimation of malonaldehyde

The detection of contaminated food in every stage of processing required new technology for fast identification and isolation of toxicity in food. Since effect of food contaminant are severe to human health, the need of pioneer technologies also increasing over last few decades. In the current study, MDA was prepared by hydrolysis of 1,1,3,3-tetramethoxypropane in HCl media and used in the electrochemical studies. The electrochemical sensor was fabricated with modified glassy carbon electrode with polyaniline. These sensors were used for detection of sodium salt of malonaldehyde and observed that a high sensitivity in the concentration range similar to 1 x 10(-1) M and 1 x 10(-2) M. Tafel plots show the variation of over potential from -1.73 V to -3.74 V up to 10(-5) mol/L indicating the lower limit of detection of the system. (C) 2013 Elsevier Ltd. All rights reserved.

Qualitative toxicity assessment of silver nanoparticles on the fresh water bacterial isolates and consortium at low level of exposure concentration

Silver nanoparticles (AgNPs) pose a high risk of exposure to the natural environment owing to their extensive usage in various consumer products. In the present study we attempted to understand the harmful effect of AgNPs at environmentally relevant low concentration levels (<= 1 ppm) towards two different freshwater bacterial isolates and their consortium. The standard plate count assay suggested that the AgNPs were toxic towards the fresh water bacterial isolates as well as the consortium, though toxicity was significantly reduced for the cells in the consortium. The oxidative stress assessment and membrane permeability studies corroborated with the toxicity data. The detailed electron microscopic studies suggested the cell degrading potential of the AgNPs, and the FT-IR studies confirmed the involvement of the surface groups in the toxic effects. No significant ion leaching from the AgNPs was observed at the applied concentration levels signifying the dominant role of the particle size, and size distribution in bacterial toxicity. The reduced toxicity for the cells in the consortium than the individual isolates has major significance in further studies on the ecotoxicity of the AgNPs. (C) 2014 Elsevier Inc. All rights reserved.

Application of Qualitative Imaging Methods to Electrical Performance-Aware Package Board Design

Package-board co-design plays a crucial role in determining the performance of high-speed systems. Although there exist several commercial solutions for electromagnetic analysis and verification, lack of Computer Aided Design (CAD) tools for SI aware design and synthesis lead to longer design cycles and non-optimal package-board interconnect geometries. In this work, the functional similarities between package-board design and radio-frequency (RF) imaging are explored. Consequently, qualitative methods common to the imaging community, like Tikhonov Regularization (TR) and Landweber method are applied to solve multi-objective, multi-variable package design problems. In addition, a new hierarchical iterative piecewise linear algorithm is developed as a wrapper over LBP for an efficient solution in the design space.

Doping dependence of fluctuation diamagnetism in high T-c superconductors

Using a recently proposed Ginzburg-Landau-like lattice free energy functional due to Banerjee et al. (2011) we calculate the fluctuation diamagnetism of high -T-c superconductors as a function of doping, magnetic field and temperature. We analyse the pairing fluctuations above the superconducting transition temperature in the cuprates, ranging from the strong phase fluctuation dominated underdoped limit to the more conventional amplitude fluctuation dominated overdoped regime. We show that a model where the pairing scale increases and the superfluid density decreases with underdoping produces features of the observed magnetization in the pseudogap region, in good qualitative and reasonable quantitative agreement with the experimental data. In particular, we explicitly show that even when the pseudogap has a pairing origin the magnetization actually tracks the superconducting dome instead of the pseudogap temperature, as seen in experiment. We discuss the doping dependence of the `onset' temperature for fluctuation diamagnetism and comment on the role of vortex core -energy jn our model. (C) 2015 Elsevier Inc. All rights reserved.