Probing acid-amide intermolecular hydrogen bonding by NMR spectroscopy and DFT calculations

Benzene carboxylic acids and Benzamide act as their self-complement in molecular recognition to form inter-molecular hydrogen bonded dimers between amide and carboxylic acid groups, which have been investigated by H-1, C-13 and N-15 NMR spectroscopy. Extensive NMR studies using diffusion ordered spectroscopy (DOSY), variable temperature 1D, 2D NMR, established the formation of heterodimers of benzamide with benzoic acid, salicylic acid and phenyl acetic acid in deuterated chloroform solution. Association constants for the complex formation in the solution state have been determined. The results are ascertained by X-ray diffraction in the solid state. Intermolecular interactions in solution and in solid state were found to be similar. The structural parameters obtained by X-ray diffraction studies are compared with those obtained by DFT calculations. (C) 2012 Elsevier B.V. All rights reserved.

Diffusion ordered spectroscopy for resolution of double bonded cis, trans-isomers

NMR spectroscopic separation of double bonded cis- and trans-isomers, that have different molecular shapes but identical mass have been carried out using Diffusion Ordered Spectroscopy (DOSY). The mixtures of fumaric acid and maleic acid, that have similar hydrodynamic radii, have resolved been on the basis of their diffusion coefficients arising due to their different tendencies to associate with micelles or reverse micelles. Sodium dodecyl sulfate (SDS) and Dioctyl sulfosuccinate sodium salt (AOT) have been used as the media to mimic the chromatographic conditions, modify the average mobility and to achieve differential diffusion rates. The best separation of the components has been achieved by Dioctyl sulfosuccinate sodium salt (AOT) in D2O solution. (C) 2012 Elsevier B.V. All rights reserved.

ENTANGLEMENT IN A 3-SPIN HEISENBERG-XY CHAIN WITH NEAREST-NEIGHBOR INTERACTIONS, SIMULATED IN AN NMR QUANTUM SIMULATOR

The evolution of entanglement in a 3-spin chain with nearest-neighbor Heisenberg-XY interactions for different initial states is investigated here. In an NMR experimental implementation, we generate multipartite entangled states starting from initial separable pseudo-pure states by simulating nearest-neighbor XY interactions in a 3-spin linear chain of nuclear spin qubits. For simulating XY interactions, we follow algebraic method of Zhang et al. Phys. Rev. A 72 (2005) 012331]. Bell state between end qubits has been generated by using only the unitary evolution of the XY Hamiltonian. For generating W-state and GHZ-state a single qubit rotation is applied on second and all the three qubits, respectively after the unitary evolution of the XY Hamiltonian.

Design for sustainability: The role of CAD

The term design in this paper particularly refers to the process (verb) and less-to the outcome or product. Design comprises a complex set of activities today involving both man and machine. Sustainability is a fundamental paradigm and carries significance in any process, natural or manmade, and its outcome. In simple terms, sustainability implies a state of sustainable living, viz, health and continuity, nurtured by diversity and evolution (innovations) in an ever-changing world. Design, in a similar line, has been comprehensively investigated and its current manifestations including design-aids (Computer Aided Design) have been evaluated in terms of sustainability. The paper investigates the rationale of sustainability to design as a whole - its purpose, its adoption in the natural world, its relevance to humankind and the technologies involved. Throughout its history, technology has been used to aid design. But in the current context of advanced algorithms and computational capacity, design no longer remains an exclusively animate faculty. Given this scenario, investigating sustainability in the light of advanced design aids such as CAD becomes pertinent. Considering that technology plays a part in design activities, the paper explores where technology must play a part and to what degree amongst the various activities that comprise design. The study includes an examination of the morphology of design and the development of a systems-thinking integrated forecasting model to evaluate the implications of CAD tools in design and sustainability. The results of the study along with a broad range of recommendations have been presented. (c) 2012 Elsevier Ltd. All rights reserved.

A versatile resolving agent for diffusion edited separation of enantiomers, complex mixtures and constitutional isomers

The study is the first report of the utilization of a crown ether as a new and versatile resolving agent for the diffusion edited separation of enantiomers, complex mixtures and constitutional isomers. As a consequence of different binding affinities of enantiomers of a chiral molecule and individual components of the complex mixtures with the crown ether, the molecules diffuse at different rates. The enhanced separation achieved due to matrix assisted diffusion permitted their separation in the diffusion dimension. The generality and wide utility of the new resolving agent and the methodology are demonstrated on diverse examples, such as an organic chiral molecule, constitutional isomers and complex mixture of molecules possessing different functional groups that possess nearly identical molecular weights.

Stability of developing film flow down an inclined surface

Film flows on inclined surfaces are often assumed to be of constant thickness, which ensures that the velocity profile is half-Poiseuille. It is shown here that by shallow water theory, only flows in a portion of Reynolds number-Froude number (Re-Fr) plane can asymptotically attain constant film thickness. In another portion on the plane, the constant thickness solution appears as an unstable fixed point, while in other regions the film thickness seems to asymptote to a positive slope. Our simulations of the Navier-Stokes equations confirm the predictions of shallow water theory at higher Froude numbers, but disagree with them at lower Froude numbers. We show that different regimes of film flow show completely different stability behaviour from that predicted earlier. Supercritical decelerating flows are shown to be always unstable, whereas accelerating flows become unstable below a certain Reynolds number for a given Froude number. Subcritical flows on the other hand are shown to be unstable above a certain Reynolds number. In some range of parameters, two solutions for the base flowexist, and the attached profile is found to be more stable. All flows except those with separation become more stable as they proceed downstream. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4758299]

Engagement of CF3 Group in N-H center dot center dot center dot F-C Hydrogen Bond in the Solution State: NMR Spectroscopy and MD Simulation Studies

Unambiguous evidence for the engagement of CF3 group in N-H center dot center dot center dot F-C hydrogen bond in a low polarity solvent, the first observation of its kind, is reported. The presence of such weak molecular interactions in the solution state is convincingly established by one and two-dimensional H-1, F-19, and natural abundant N-15 NMR spectroscopic studies. The strong and direct evidence is derived by the observation of through-space couplings, such as, (1h)J(FH), (1h)J(FN), and (2h)J(FF), where the spin polarization is transmitted through hydrogen bond. In an interesting example of a molecule containing two CF3 groups getting simultaneously involved in hydrogen bond, where hydrogen bond mediated couplings are not reflected in the NMR spectrum, F-19-F-19 NOESY experiment yielded confirmatory evidence. Significant deviations in the strengths of (1)J(NH), variable temperature, and the solvent induced perturbations yielded additional support. The NMR results are corroborated by both DFT calculations and MD simulations, where the quantitative information on different ways of involvement of fluorine in two and three centered hydrogen bonds, their percentage of occurrences, and geometries have been obtained. The hydrogen bond interaction energies have also been calculated.

Improving query focused summarization using look-ahead strategy

Query focused summarization is the task of producing a compressed text of original set of documents based on a query. Documents can be viewed as graph with sentences as nodes and edges can be added based on sentence similarity. Graph based ranking algorithms which use 'Biased random surfer model' like topic-sensitive LexRank have been successfully applied to query focused summarization. In these algorithms, random walk will be biased towards the sentences which contain query relevant words. Specifically, it is assumed that random surfer knows the query relevance score of the sentence to where he jumps. However, neighbourhood information of the sentence to where he jumps is completely ignored. In this paper, we propose look-ahead version of topic-sensitive LexRank. We assume that random surfer not only knows the query relevance of the sentence to where he jumps but he can also look N-step ahead from that sentence to find query relevance scores of future set of sentences. Using this look ahead information, we figure out the sentences which are indirectly related to the query by looking at number of hops to reach a sentence which has query relevant words. Then we make the random walk biased towards even to the indirect query relevant sentences along with the sentences which have query relevant words. Experimental results show 20.2% increase in ROUGE-2 score compared to topic-sensitive LexRank on DUC 2007 data set. Further, our system outperforms best systems in DUC 2006 and results are comparable to state of the art systems.

A stylometric study and assessment of machine translators

In this work we present a statistical approach inspired by stylometry -measurement of author style- to study the characteristics of machine translators. Our approach quantifies the style of a translator in terms of the properties derived from the distribution of stopwords in its output - a standard approach in modern stylometry. Our study enables us to match translated text to the source machine translator that generated them. Also, the stylometric closeness of human generated text to that generated by machine translators provides handles to assess the quality of machine translators.

Detection of glycated hemoglobin using 3-Aminophenylboronic acid modified graphene oxide

This paper presents the chemical synthesis of 3-Aminophenylboronic acid (APBA) modified graphene oxide (GO) and its application to the electrochemical detection of glycated hemoglobin (GHb). The compound (GO-APBA) was synthesized by forming an amide linkage between the amino group (-NH2) of APBA and the carboxylic group (-COOH) of GO. The compound was characterized using IR spectroscopy. Detection of GHb was carried out using Electrochemical Impedance Spectroscopic (EIS) measurements with GO-APBA modified glassy carbon electrode as the working electrode.

Trends and Variability of AVHRR-Derived NPP in India

In this paper, we estimate the trends and variability in Advanced Very High Resolution Radiometer (AVHRR)-derived terrestrial net primary productivity (NPP) over India for the period 1982-2006. We find an increasing trend of 3.9% per decade (r = 0.78, R-2 = 0.61) during the analysis period. A multivariate linear regression of NPP with temperature, precipitation, atmospheric CO2 concentration, soil water and surface solar radiation (r = 0.80, R-2 = 0.65) indicates that the increasing trend is partly driven by increasing atmospheric CO2 concentration and the consequent CO2 fertilization of the ecosystems. However, human interventions may have also played a key role in the NPP increase: non-forest NPP growth is largely driven by increases in irrigated area and fertilizer use, while forest NPP is influenced by plantation and forest conservation programs. A similar multivariate regression of interannual NPP anomalies with temperature, precipitation, soil water, solar radiation and CO2 anomalies suggests that the interannual variability in NPP is primarily driven by precipitation and temperature variability. Mean seasonal NPP is largest during post-monsoon and lowest during the pre-monsoon period, thereby indicating the importance of soil moisture for vegetation productivity.

The Relationship of Solid-State Plasticity to Mechanochromic Luminescence in Difluoroboron Avobenzone Polymorphs

In solid-state mechanochromic luminescence (ML) materials, it remains a challenge to establish the origin of fluorescence color changes upon mechanical action and to determine why only some fluorophores exhibit ML behavior. The study of mechanical properties by nanoindentation, followed by ML experiments on green- and cyan-emitting polymorphs of difluoroboron avobenzone reveals that upon smearing, the plastically deformable cyan form shows a prominent color change to yellow, while in the harder green form the redshifted emission is barely detectable. Crystal structure analysis reveals the presence of slip planes in the softer cyan form that can facilitate the formation of recoverable and low energy defects in the structure. Hence, the cyan form exhibits prominent and reversible ML behavior. This suggests a potential design strategy for efficient ML materials.

Mixed-ligand nickel(II) thiosemicarbazone complexes: Synthesis, characterization and biological evaluation

The syntheses and characterization of some new mixed-ligand nickel(II) complexes {Ni(L-1)(PPh3)] (1), Ni(L-1)(Py)] (2), Ni(L-2)(PPh3)]center dot DMSO (3), Ni(L-2)(Imz)] (4), Ni(L-3)(4-pic)] (5) and RNi(L-3))(2)(mu-4,4'-byp)]center dot 2DMSO (6)1 of three selected thiosemicarbazones the 4-(p-X-phenyl)thiosemicarbazones of salicylaldehyde) (H2L1-3) (A, Scheme 1) are described in the present study, differing in the inductive effect of the substituent X (X = F, Br and OCH3), in order to observe its influence, if any, on the redox potentials and biological activity of the complexes. All the synthesized ligands and the metal complexes were successfully characterized by elemental analysis, IR, UV-Vis, NMR spectroscopy and cyclic voltammetry. The molecular structures of four mononuclear (1-3 and 5) and one dinuclear (6) Ni(II) complex have been determined by X-ray crystallography. The complexes have been screened for their antibacterial activity against Escherichia coli and Bacillus. The minimum inhibitory concentrations of these complexes and their antibacterial activities indicate that compound 4 is the potential lead molecule for drug designing. (C) 2012 Elsevier Ltd. All rights reserved.

Violation of entropic Leggett-Garg inequality in nuclear spins

We report an experimental study of recently formulated entropic Leggett-Garg inequality (ELGI) by Usha Devi et al. Phys. Rev. A 87, 052103 (2013)]. This inequality places a bound on the statistical measurement outcomes of dynamical observables describing a macrorealistic system. Such a bound is not necessarily obeyed by quantum systems, and therefore provides an important way to distinguish quantumness from classical behavior. Here we study ELGI using a two-qubit nuclear magnetic resonance system. To perform the noninvasive measurements required for the ELGI study, we prepare the system qubit in a maximally mixed state as well as use the ``ideal negative result measurement'' procedure with the help of an ancilla qubit. The experimental results show a clear violation of ELGI by over four standard deviations. These results agree with the predictions of quantum theory. The violation of ELGI is attributed to the fact that certain joint probabilities are not legitimate in the quantum scenario, in the sense they do not reproduce all the marginal probabilities. Using a three-qubit system, we also demonstrate that three-time joint probabilities do not reproduce certain two-time marginal probabilities.

Ancilla-assisted quantum state tomography in multiqubit registers

The standard method of quantum state tomography (QST) relies on the measurement of a set of noncommuting observables, realized in a series of independent experiments. Ancilla-assisted QST (AAQST) proposed by Nieuwenhuizen and co-workers Phys. Rev. Lett. 92, 120402 (2004)] greatly reduces the number of independent measurements by exploiting an ancilla register in a known initial state. In suitable conditions AAQST allows mapping out density matrix of an input register in a single experiment. Here we describe methods for explicit construction of AAQST experiments in multiqubit registers. We also report nuclear magnetic resonance studies on AAQST of (i) a two-qubit input register using a one-qubit ancilla in an isotropic liquid-state system and (ii) a three-qubit input register using a two-qubit ancilla register in a partially oriented system. The experimental results confirm the effectiveness of AAQST in such multiqubit registers.