Measurement and Applications of Long-Range Heteronuclear Scalar Couplings: Recent Experimental and Theoretical Developments

The use of long-range heteronuclear couplings, in association with 1H1H scalar couplings and NOE restraints, has acquired growing importance for the determination of the relative stereochemistry, and structural and conformational information of organic and biological molecules. However, the routine use of such couplings is hindered by the inherent difficulties in their measurement. Prior to the advancement in experimental techniques, both long-range homo- and heteronuclear scalar couplings were not easily accessible, especially for very large molecules. The development of a large number of multidimensional NMR experimental methodologies has alleviated the complications associated with the measurement of couplings of smaller strengths. Subsequent application of these methods and the utilization of determined J-couplings for structure calculations have revolutionized this area of research. Problems in organic, inorganic and biophysical chemistry have also been solved by utilizing the short- and long-range heteronuclear couplings. In this minireview, we discuss the advantages and limitations of a number of experimental techniques reported in recent times for the measurement of long-range heteronuclear couplings and a few selected applications of such couplings. This includes the study of medium- to larger-sized molecules in a variety of applications, especially in the study of hydrogen bonding in biological systems. The utilization of these couplings in conjunction with theoretical calculations to arrive at conclusions on the hyperconjugation, configurational analysis and the effect of the electronegativity of the substituents is also discussed.

Microelectromechanical torsional varactors with low parasitic capacitances and high dynamic range

This work focuses on the design of torsional microelectromechanical systems (MEMS) varactors to achieve highdynamic range of capacitances. MEMS varactors fabricated through the polyMUMPS process are characterized at low and high frequencies for their capacitance-voltage characteristics and electrical parasitics. The effect of parasitic capacitances on tuning ratio is studied and an equivalent circuit is developed. Two variants of torsional varactors that help to improve the dynamic range of torsional varactors despite the parasitics are proposed and characterized. A tuning ratio of 1:8, which is the highest reported in literature, has been obtained. We also demonstrate through simulations that much higher tuning ratios can be obtained with the designs proposed. The designs and experimental results presented are relevant to CMOS fabrication processes that use low resistivity substrate. (C) 2012 Society of Photo-Optical Instrumentation Engineers (SPIE). DOI: 10.1117/1.JMM.11.1.013006]

Fermi-edge singularity in photoluminescence spectra of modulation-doped AlGaAs/InGaAs/GaAs quantum wells

The photoluminescence study of Fermi-edge singularity (FES) in modulation-doped pseudomorphic AlxGa1-xAs/InyGa1-yAs/GaAs quantum well (QW) heterostructures is presented. In the above QW structures the optical transitions between n = 1 and n = 2 electronic subband to the n = 1 heavy hole subband (E-11 and E-21 transitions, respectively) are observed with FES appearing as a lower energy shoulder to the E-21 transition. The observed FES is attributed to the Fermi wave vector in the first electronic subband under the conditions of population of the second electronic subband. The FES appears at about 10 meV below E-21 transition around 4.2 K. Initially it gets stronger with increasing temperature and becomes a distinct peak at about 20 K. Further increase in temperature quenches FES and reaches the base line at around 40 K.

Effect of magnetic field on Mott's variable-range hopping parameters in multiwall carbon nanotube mat

We report the temperature and magnetic field dependence of the conductivity of multiwall carbon nanotube mat in the temperature range 1.4-150 K and in magnetic fields up to 10 T. It is observed that charge transport in this system is governed by Mott's variable-range hopping of three-dimensional type in the higher temperature range and two-dimensional type in the lower temperature range. Mott's various parameters, such as localization length, hopping length, hopping energy and density of states at the Fermi level are deduced from the variable-range hopping fit. The resistance of the sample decreases with the magnetic field applied in the direction of tube axis of the nanotubes. The magnetic field gives rise to delocalization of states with the well-known consequence of a decrease in Mott's T-0 parameter in variable-range hopping. The application of magnetic field lowers the crossover temperature at which three-dimensional variable-range hopping turns to two-dimensional variable-range hopping. The conductivity on the lower temperature side is governed by the weak localization giving rise to positive magnetoconductance. Finally, a magnetic field-temperature diagram is proposed showing different regions for different kinds of transport mechanism.

Sliding wear behavior of plasma nitrided Austenitic Stainless Steel Type AISI 316LN in the temperature range from 25 to 400 degrees C at 10(-4) bar

There is a research knowledge gap for the dry wear data of nitride treated Stainless Steel in high temperature and high vacuum environment. In order to fill this gap, plasma nitriding was done on austenitic Stainless Steel type AISI 316LN (316LN SS) and dry sliding wear tests have been conducted at 25 degrees C, 200 degrees C and 400 degrees C in high vacuum of 1.6 x 10(-4) bar. The two different slider material (316LN SS and Colmonoy) and two different sliding speeds (0.0576 m/s and 0.167 m/s) have been used. The tribological parameters such as friction coefficient, wear mechanism and volume of metal loss have been evaluated. Scanning Electron Microscopy (SEM) was used to study the surface morphology of the worn pins and rings. Electronic balancing machine was used to record the mass of metal loss during wear tests. The 2D optical profilometer was used to measure the depth of the wear track. The Plasma Nitride treated 316LN SS rings (PN rings) exhibit excellent wear resistance against 316LN SS pin and Colmonoy pin at all temperatures. However, PN ring vs. Colmonoy pin Pair shows better wear resistance than PN ring vs. 316LN SS pin Pair at higher temperature. (C) 2012 Elsevier B.V. All rights reserved.

Effect of the Edge Type and Strain on the Structural, Electronic and Magnetic Properties of the BNRs

We present the effect of edge structures on the edge energy and stress of BN nanoribbons. Ab initio density functional calculations show that the armchair edge is lower in energy than the zigzag edge by 0.43 eV/angstrom. Both types of the edges are under the compressive stress. The zigzag edges are mechanically more stable than the armchair edges. Based on the calculated edge energies, the equilibrium shape of the BN flakes are found to be regular hexagonal, and dominated by the armchair edges. The zigzag ribbons are found to be half-metallic, whereas the armchair ribbons are semiconducting.

Continuum theory of edge states of topological insulators: variational principle and boundary conditions

We develop a continuum theory to model low energy excitations of a generic four-band time reversal invariant electronic system with boundaries. We propose a variational energy functional for the wavefunctions which allows us to derive natural boundary conditions valid for such systems. Our formulation is particularly suited for developing a continuum theory of the protected edge/surface excitations of topological insulators both in two and three dimensions. By a detailed comparison of our analytical formulation with tight binding calculations of ribbons of topological insulators modelled by the Bernevig-Hughes-Zhang (BHZ) Hamiltonian, we show that the continuum theory with a natural boundary condition provides an appropriate description of the low energy physics.

Mesh Simplification Based on Edge Collapsing Could Improve Computational Efficiency in Near Infrared Optical Tomographic Imaging

The diffusion equation-based modeling of near infrared light propagation in tissue is achieved by using finite-element mesh for imaging real-tissue types, such as breast and brain. The finite-element mesh size (number of nodes) dictates the parameter space in the optical tomographic imaging. Most commonly used finite-element meshing algorithms do not provide the flexibility of distinct nodal spacing in different regions of imaging domain to take the sensitivity of the problem into consideration. This study aims to present a computationally efficient mesh simplification method that can be used as a preprocessing step to iterative image reconstruction, where the finite-element mesh is simplified by using an edge collapsing algorithm to reduce the parameter space at regions where the sensitivity of the problem is relatively low. It is shown, using simulations and experimental phantom data for simple meshes/domains, that a significant reduction in parameter space could be achieved without compromising on the reconstructed image quality. The maximum errors observed by using the simplified meshes were less than 0.27% in the forward problem and 5% for inverse problem.

Magnetic-field-induced Fabry-Perot resonances in helical edge states

We study electronic transport across a helical edge state exposed to a uniform magnetic ((B) over right arrow) field over a finite length. We show that this system exhibits Fabry-Perot-type resonances in electronic transport. The intrinsic spin anisotropy of the helical edge states allows us to tune these resonances by changing the direction of the (B) over right arrow field while keeping its magnitude constant. This is in sharp contrast to the case of nonhelical one-dimensional electron gases with a parabolic dispersion, where similar resonances do appear in individual spin channels (up arrow and down arrow) separately which, however, cannot be tuned by merely changing the direction of the (B) over right arrow field. These resonances provide a unique way to probe the helical nature of the theory. We study the robustness of these resonances against a possible static impurity in the channel.

Methane and carbon dioxide adsorption on edge-functionalized graphene: a comparative DFT study

With a view towards optimizing gas storage and separation in crystalline and disordered nanoporous carbon-based materials, we use ab initio density functional theory calculations to explore the effect of chemical functionalization on gas binding to exposed edges within model carbon nanostructures. We test the geometry, energetics, and charge distribution of in-plane and out-of-plane binding of CO2 and CH4 to model zigzag graphene nanoribbons edge-functionalized with COOH, OH, NH2, H2PO3, NO2, and CH3. Although different choices for the exchange-correlation functional lead to a spread of values for the binding energy, trends across the functional groups are largely preserved for each choice, as are the final orientations of the adsorbed gas molecules. We find binding of CO2 to exceed that of CH4 by roughly a factor of two. However, the two gases follow very similar trends with changes in the attached functional group, despite different molecular symmetries. Our results indicate that the presence of NH2, H2PO3, NO2, and COOH functional groups can significantly enhance gas binding, making the edges potentially viable binding sites in materials with high concentrations of edge carbons. To first order, in-plane binding strength correlates with the larger permanent and induced dipole moments on these groups. Implications for tailoring carbon structures for increased gas uptake and improved CO2/CH4 selectivity are discussed. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4736568]

Acyclic Edge Coloring of Triangle-Free Planar Graphs

An acyclic edge coloring of a graph is a proper edge coloring such that there are no bichromatic cycles. The acyclic chromatic index of a graph is the minimum number k such that there is an acyclic edge coloring using k colors and is denoted by a'(G). It was conjectured by Alon, Sudakov and Zaks (and much earlier by Fiamcik) that a'(G) ? ? + 2, where ? = ?(G) denotes the maximum degree of the graph. If every induced subgraph H of G satisfies the condition |E(H)| ? 2|V(H)|-1, we say that the graph G satisfies Property A. In this article, we prove that if G satisfies Property A, then a'(G) ? ? + 3. Triangle-free planar graphs satisfy Property A. We infer that a'(G) ? ? + 3, if G is a triangle-free planar graph. Another class of graph which satisfies Property A is 2-fold graphs (union of two forests). (C) 2011 Wiley Periodicals, Inc. J Graph Theory

Adsorption on Edge-Functionalized Bilayer Graphene Nanoribbons: Assessing the Role of Functional Groups in Methane Uptake

A combination of ab initio and classical Monte Carlo simulations is used to investigate the effects of functional groups on methane binding. Using Moller-Plesset (MP2) calculations, we obtain the binding energies for benzene functionalized with NH2, OH, CH3, COOH, and H2PO3 and identify the methane binding sites. In all cases, the preferred binding sites are located above the benzene plane in the vicinity of the benzene carbon atom attached to the functional group. Functional groups enhance methane binding relative to benzene (-6.39 kJ/mol), with the largest enhancement observed for H2PO3 (-8.37 kJ/mol) followed by COOH and CH3 (-7.77 kJ/mol). Adsorption isotherms are obtained for edge-functionalized bilayer graphene nanoribbons using grand canonical Monte Carlo simulations with a five-site methane model. Adsorbed excess and heats of adsorption for pressures up to 40 bar and 298 K are obtained with functional group concentrations ranging from 3.125 to 6.25 mol 96 for graphene edges functionalized with OH, NH2, and COOH. The functional groups are found to act as preferred adsorption sites, and in the case of COOH the local methane density in the vicinity of the functional group is found to exceed that of bare graphene. The largest enhancement of 44.5% in the methane excess adsorbed is observed for COOH-functionalized nanoribbons when compared to H terminated ribbons. The corresponding enhancements for OH- and NH2-functionalized ribbons are 10.5% and 3.7%, respectively. The excess adsorption across functional groups reflects the trends observed in the binding energies from MP2 calculations. Our study reveals that specific site functionalization can have a significant effect on the local adsorption characteristics and can be used as a design strategy to tailor materials with enhanced methane storage capacity.

Ex Situ X-ray Diffraction, X-ray Absorption Near Edge Structure, Electron Spin Resonance, and Transmission Electron Microscopy Study of the Hydrothermal Crystallization of Vanadium Oxide Nanotubes: An Insight into the Mechanism of Formation

The nucleation and growth of vanadium oxide nanotubes (VOx-NT) have been followed by a combination of numerous ex situ techniques. long the hydrothermal process. Intermediate solid phases extracted at different reaction times have been characterized by powder X-ray diffraction, scanning and transmission electron microscopy, electron spin resonance, and V-K edge :X-ray absorption near-edge structure spectroscopy. The supernatant vanadate solutions extracted during the hydrothermal treatment have been studied by liquid V-51 NMR and flame. spectroscopy. For short durations of the hydrothermal synthesis, the initial V2O5-surfactant intercalate. is progressively transformed into VOx-NT whose crystallization starts to be detected after a hydrothermal treatment of 24 h. Upon heating from 24 h to 7 days, VOx-NT are obtained in larger amount and with an improved crystallinity. The detection of soluble amines and cyclic metavanadate V4O12](4-) in the supernatant solution along the hydrothermal process suggests that VOx-NT result from a dissolution precipitation mechanism. Metavanadate species V4O12](4-) could behave as molecular precursors in the polymerization reactions leading to VOx-NT.

The hazard potential of the western segment of the Makran subduction zone, northern Arabian Sea

Evaluating the hazard potential of the Makran subduction zone requires understanding the previous records of the large earthquakes and tsunamis. We address this problem by searching for earthquake and tectonic proxies along the Makran Coast and linking those observations with the available constraints on historical seismicity and the tell-tale characteristics of sea floor morphology. The earthquake of Mw 8.1 of 1945 and the consequent tsunami that originated on the eastern part of the Makran are the only historically known hazardous events in this region. The seismic status of the western part of the subduction zone outside the rupture area of the 1945 earthquake remains an enigma. The near-shore shallow stratigraphy of the central part of Makran near Chabahar shows evidence of seismically induced liquefaction that we attribute to the distant effects of the 1945 earthquake. The coastal sites further westward around Jask are remarkable for the absence of liquefaction features, at least at the shallow level. Although a negative evidence, this possibly implies that the western part of Makran Coast region may not have been impacted by near-field large earthquakes in the recent past-a fact also supported by the analysis of historical data. On the other hand, the elevated marine terraces on the western Makran and their uplift rates are indicative of comparable degree of long-term tectonic activity, at least around Chabahar. The offshore data suggest occurrences of recently active submarine slumps on the eastern part of the Makran, reflective of shaking events, owing to the great 1945 earthquake. The ocean floor morphologic features on the western segment, on the contrary, are much subdued and the prograding delta lobes on the shelf edge also remain intact. The coast on the western Makran, in general, shows indications of progradation and uplift. The various lines of evidence thus suggest that although the western segment is potentially seismogenic, large earthquakes have not occurred there in the recent past, at least during the last 600 years. The recurrence period of earthquakes may range up to 1,000 years or more, an assessment based on the age of the youngest dated coastal ridge. The long elapsed time points to the fact that the western segment may have accumulated sufficient slip to produce a major earthquake.

Efficient external memory structures for range-aggregate queries

We present external memory data structures for efficiently answering range-aggregate queries. The range-aggregate problem is defined as follows: Given a set of weighted points in R-d, compute the aggregate of the weights of the points that lie inside a d-dimensional orthogonal query rectangle. The aggregates we consider in this paper include COUNT, sum, and MAX. First, we develop a structure for answering two-dimensional range-COUNT queries that uses O(N/B) disk blocks and answers a query in O(log(B) N) I/Os, where N is the number of input points and B is the disk block size. The structure can be extended to obtain a near-linear-size structure for answering range-sum queries using O(log(B) N) I/Os, and a linear-size structure for answering range-MAX queries in O(log(B)(2) N) I/Os. Our structures can be made dynamic and extended to higher dimensions. (C) 2012 Elsevier B.V. All rights reserved.