``Conformational Simulation'' of Sulfamethizole by Molecular Complexation and Insights from Charge Density Analysis: Role of Intramolecular S center dot center dot center dot O Chalcogen Bonding

Intramolecular S center dot center dot center dot O chalcogen bonding and its potential to lock molecular conformation have been examined in the crystal forms of sulfamethizole, a sulfonamide antibiotic. Molecular complexes of sulfamethizole, including salts and cocrystal, have been synthesized, and their crystal structures were analyzed in order to examine the possible conformational preferences of the molecule in various ionic states and supramolecular environments (neutral/cocrystal, anionic salt, and cationic salt forms). The electrostatic potential mapped on Hirshfeld surfaces generated for these crystal forms provides insights into the possible binding modes of the drug in different environments. Further, the observed conformation locking feature has been rationalized in terms of the experimental charge density features of the intramolecular S center dot center dot O chalcogen bonding in sulfamethizole. The study quantitatively illustrates and rationalizes an intriguing case of a local minimum of molecular conformation being exclusively preferred over the global minimum, as it facilitates more efficient intermolecular interactions in a supramolecular environment.

Highly Dense ZnO Nanowires Grown on Graphene Foam for Ultraviolet Photodetection

Growth of highly dense ZnO nanowires (ZnO NWs) is demonstrated on three-dimensional graphene foam (GF) using resistive thermal evaporation technique. Photoresponse of the as-grown hybrid structure of ZnO NWs on GF (ZnO NWs/GF) is evaluated for ultraviolet (UV) detection. Excellent photoresponse with fast response and recovery times of 9.5 and 38 s with external quantum efficiency of 2490.8% is demonstrated at low illumination power density of 1.3 mW/cm(2). In addition, due to excellent charge carrier transport, mobility of graphene reduces the recombination rate of photogenerated charge carriers, hence the lifetime of photogenerated free charge carriers enhances in the photodetectors.

High thermopower and ultra low thermal conductivity in Cd-based Zintl phase compounds

By combining first principles density functional theory and electronic as well as lattice Boltzmann transport calculations, we unravel the excellent thermoelectric properties of Zintl phase compounds ACd(2)Sb(2) (where, A = Ca, Ba, Sr). The calculated electronic structures of these compounds show charge carrier pockets and heavy light bands near the band edge, which lead to a large power factor. Furthermore, we report large Gruneisen parameters and low phonon group velocity indicating essential strong anharmonicity in these compounds, which resulted in low lattice thermal conductivity. The combination of low thermal conductivity and the excellent transport properties give a high ZT value of similar to 1.4-1.9 in CaCd2Sb2 and BaCd2Sb2 at moderate p and n-type doping. Our results indicate that well optimized Cd-based Zintl phase compounds have the potential to match the performance of conventional thermoelectric materials.

Crystal landscape in the orcinol:4,4 `-bipyridine system: synthon modularity, polymorphism and transferability of multipole charge density parameters

Polymorphism in the orcinol: 4,4'-bipyridine cocrystal system is analyzed in terms of a robust convergent modular phenol...pyridine supramolecular synthon. Employing the Synthon Based Fragments Approach (SBFA) to transfer the multipole charge density parameters, it is demonstrated that the crystal landscape can be quantified in terms of intermolecular interaction energies in the five crystal forms so far isolated in this complex system. There are five crystal forms. The first has an open, divergent O-H...N based structure with alternating orcinol and bipyridine molecules. The other four polymorphs have different three-dimensional packing but all of them are similar at an interaction level, and are based on a modular O-H...N mediated supramolecular synthon that consists of two orcinol and two bipyridine molecules in a closed, convergent structure. The SBFA method, which depends on the modularity of synthons, provides good agreement between experiment and theory because it takes into account the supramolecular contribution to charge density. The existence of five crystal forms in this system shows that polymorphism in cocrystals need not be considered to be an unusual phenomenon. Studies of the crystal landscape could lead to an understanding of the kinetic pathways that control the crystallization processes, in other words the valleys in the landscape. These pathways are traditionally not considered in exercises pertaining to computational crystal structure prediction, which rather monitors the thermodynamics of the various stable forms in the system, in other words the peaks in the landscape.

Spatial Modulation Aided Zero-Padded Single Carrier Transmission for Dispersive Channels

In this paper, we consider spatial modulation (SM) operating in a frequency-selective single-carrier (SC) communication scenario and propose zero-padding instead of the cyclic-prefix considered in the existing literature. We show that the zero-padded single-carrier (ZP-SC) SM system offers full multipath diversity under maximum-likelihood (ML) detection, unlike the cyclic-prefix based SM system. Furthermore, we show that the order of ML detection complexity in our proposed ZP-SC SM system is independent of the frame length and depends only on the number of multipath links between the transmitter and the receiver. Thus, we show that the zero-padding applied in the SC SM system has two advantages over the cyclic prefix: 1) achieves full multipath diversity, and 2) imposes a relatively low ML detection complexity. Furthermore, we extend the partial interference cancellation receiver (PIC-R) proposed by Guo and Xia for the detection of space-time block codes (STBCs) in order to convert the ZP-SC system into a set of narrowband subsystems experiencing flat-fading. We show that full rank STBC transmissions over these subsystems achieves full transmit, receive as well as multipath diversity for the PIC-R. Furthermore, we show that the ZP-SC SM system achieves receive and multipath diversity for the PIC-R at a detection complexity order which is the same as that of the SM system in flat-fading scenario. Our simulation results demonstrate that the symbol error ratio performance of the proposed linear receiver for the ZP-SC SM system is significantly better than that of the SM in cyclic prefix based orthogonal frequency division multiplexing as well as of the SM in the cyclic-prefixed and zero-padded single carrier systems relying on zero-forcing/minimum mean-squared error equalizer based receivers.

Effect of viscosity contrast on plume formation in density stratified fluids

We perform two and three dimensional numerical simulations of plume formation in density and viscosity stratified fluid systems. We show that the ambient to plume fluid viscosity ratio strongly affects the near wall plume structures (line or sheet plumes) such as plume spacing and shape of plumes. We observe that where mushroom-like plumes are observed for lower viscosity ratios, taller plumes with bulbous heads form for high viscosity ratios. Plume structure and spacing are in good agreement with experimental results. By studying the geometry of the line plumes and the flow in the circulation cells, we discuss the mechanisms of their formation and the dynamics of merging. We show that an increase in the viscosity ratio decreases the total length of line plumes in the planform which indicates a decreased mixing at higher viscosity ratios. (C) 2015 Elsevier Ltd. All rights reserved.

Solid-state optical absorption from optimally tuned time-dependent range-separated hybrid density functional theory

We present a framework for obtaining reliable solid-state charge and optical excitations and spectra from optimally tuned range-separated hybrid density functional theory. The approach, which is fully couched within the formal framework of generalized Kohn-Sham theory, allows for the accurate prediction of exciton binding energies. We demonstrate our approach through first principles calculations of one- and two-particle excitations in pentacene, a molecular semiconducting crystal, where our work is in excellent agreement with experiments and prior computations. We further show that with one adjustable parameter, set to produce the known band gap, this method accurately predicts band structures and optical spectra of silicon and lithium fluoride, prototypical covalent and ionic solids. Our findings indicate that for a broad range of extended bulk systems, this method may provide a computationally inexpensive alternative to many-body perturbation theory, opening the door to studies of materials of increasing size and complexity.

The Structure of the Holo-Acyl Carrier Protein of Leishmania major Displays a Remarkably Different Phosphopantetheinyl Transferase Binding Interface

The genome of Leishmania major encodes a type II fatty acid biosynthesis pathway for which no structural or biochemical information exists. Here, for the first time, we have characterized the central player of the pathway, the acyl carrier protein (LmACP), using nuclear magnetic resonance (NMR). Structurally, the LmACP molecule is similar to other type II ACPs, comprising a four-helix bundle, enclosing a hydrophobic core. Dissimilarities in sequence, however, exist in helix II (recognition helix) of the protein. The enzymatic conversion of apo-LmACP into the holo form using type I (Escherichia coli AcpS) and type II (Sfp type) phosphopantetheinyl transferases (PPTs) is relatively slow. Mutagenesis studies underscore the importance of the residues present at the protein protein interaction interface of LmACP in modulating the activity of PPTs. Interestingly, the cognate PPT for this ACP, the L. major 4'-phosphopantetheinyl transferase (LmPPT), does not show any enzymatic activity toward it, though it readily converts other type I and type II ACPs into their holo forms. NMR chemical shift perturbation studies suggest a moderately tight complex between LmACP and its cognate PPT, suggesting inhibition. We surmise that the unique surface of LmACP might have evolved to complement its cognate enzyme (LmPPT), possibly for the purpose of regulation.

S center dot center dot center dot O chalcogen bonding in sulfa drugs: insights from multipole charge density and X-ray wavefunction of acetazolamide

Experimental charge density analysis combined with the quantum crystallographic technique of X-ray wavefunction refinement (XWR) provides quantitative insights into the intra-and intermolecular interactions formed by acetazolamide, a diuretic drug. Firstly, the analysis of charge density topology at the intermolecular level shows the presence of exceptionally strong interaction motifs such as a DDAA-AADD (D-donor, A-acceptor) type quadruple hydrogen bond motif and a sulfonamide dimer synthon. The nature and strength of intra-molecular S center dot center dot center dot O chalcogen bonding have been characterized using descriptors from the multipole model (MM) and XWR. Although pure geometrical criteria suggest the possibility of two intra-molecular S center dot center dot center dot O chalcogen bonded ring motifs, only one of them satisfies the ``orbital geometry'' so as to exhibit an interaction in terms of an electron density bond path and a bond critical point. The presence of `s-holes' on the sulfur atom leading to the S center dot center dot center dot O chalcogen bond has been visualized on the electrostatic potential surface and Laplacian isosurfaces close to the `reactive surface'. The electron localizability indicator (ELI) and Roby bond orders derived from the `experimental wave function' provide insights into the nature of S center dot center dot center dot O chalcogen bonding.

A Pd-8 Tetrafacial Molecular Barrel as Carrier for Water Insoluble Fluorophore

A new carbazole-based tetraimidazole ligand 1,3,6,8-tetra(1H-imidazol-1-yl)-9-methyl-9H-carbazole (L) has been synthesized. The unsymmetrical nature of L as well as the rotational freedom of imidazole donor moieties around C-N bond make it a special building unit, which upon treatment with cis-(tmeda)Pd(NO3)(2) produced an unprecedented single linkage-isomeric Pd-8 tetrafacial molecular nanobarrel (PSMBR-1) tmeda N,N,N',N'-tetramethylethane-1,2-diamine]. Unlike closed architectures, open barrel architecture of water-soluble PSMBR-1 makes it an ideal host for some water insoluble polyaromatic hydrocarbons in aqueous medium; one such inclusion complex coroneneCPSMBR-1 was characterized by X-ray diffraction study. Moreover, the potential application of PSMER-1 as carrier in aqueous medium for the transportation of water insoluble fluorophore (perylene) for live cell imaging is explored.

ABSOLUTE/CONVECTIVE INSTABILITY TRANSITION IN A BACKWARD FACING STEP COMBUSTOR: FUNDAMENTAL MECHANISM AND INFLUENCE OF DENSITY GRADIENT

Hydrodynamic instabilities of the flow field in lean premixed gas turbine combustors can generate velocity perturbations that wrinkle and distort the flame sheet over length scales that are smaller than the flame length. The resultant heat release oscillations can then potentially result in combustion instability. Thus, it is essential to understand the hydrodynamic instability characteristics of the combustor flow field in order to understand its overall influence on combustion instability characteristics. To this end, this paper elucidates the role of fluctuating vorticity production from a linear hydrodynamic stability analysis as the key mechanism promoting absolute/convective instability transitions in shear layers occurring in the flow behind a backward facing step. These results are obtained within the framework of an inviscid, incompressible, local temporal and spatio-temporal stability analysis. Vorticity fluctuations in this limit result from interaction between two competing mechanisms - (1) production from interaction between velocity perturbations and the base flow vorticity gradient and (2) baroclinic torque in the presence of base flow density gradients. This interaction has a significant effect on hydrodynamic instability characteristics when the base flow density and velocity gradients are co-located. Regions in the space of parameters characterizing the base flow velocity profile, i.e. shear layer thickness and ratio of forward to reverse flow velocity, corresponding to convective and absolute instability are identified. The implications of the present results on prior observations of flow instability in other flows such as heated jets and bluff-body stabilized flames is discussed.

Integrating AlGaN/GaN high electron mobility transistor with Si: A comparative study of integration schemes

AlGaN/GaN high electron mobility transistor stacks deposited on a single growth platform are used to compare the most common transition, AlN to GaN, schemes used for integrating GaN with Si. The efficiency of these transitions based on linearly graded, step graded, interlayer, and superlattice schemes on dislocation density reduction, stress management, surface roughness, and eventually mobility of the 2D-gas are evaluated. In a 500 nm GaN probe layer deposited, all of these transitions result in total transmission electron microscopy measured dislocations densities of 1 to 3 x 10(9)/cm(2) and <1 nm surface roughness. The 2-D electron gas channels formed at an AlGaN-1 nm AlN/GaN interface deposited on this GaN probe layer all have mobilities of 1600-1900 cm(2)/V s at a carrier concentration of 0.7-0.9 x 10(13)/cm(2). Compressive stress and changes in composition in GaN rich regions of the AlN-GaN transition are the most effective at reducing dislocation density. Amongst all the transitions studied the step graded transition is the one that helps to implement this feature of GaN integration in the simplest and most consistent manner. (C) 2015 AIP Publishing LLC.

Tungsten-based nanomaterials (WO3 & Bi2WO6): Modifications related to charge carrier transfer mechanisms and photocatalytic applications

Heterogeneous photocatalysis is an ideal green energy technology for the purification of wastewater. Although titania dominates as the reference photocatalyst, its wide band gap is a bottleneck for extended utility. Thus, search for non-TiO2 based nanomaterials has become an active area of research in recent years. In this regard, visible light absorbing polycrystalline WO3 (2.4-2.8 eV) and Bi2WO6 (2.8 eV) with versatile structure-electronic properties has gained considerable interest to promote the photocatalytic reactions. These materials are also explored in selective functional group transformation in organic reactions, because of low reduction and oxidation potential of WO3 CB and Bi2WO6 VB, respectively. In this focused review, various strategies such as foreign ion doping, noble metal deposition and heterostructuring with other semiconductors designed for efficient photocatalysis is discussed. These modifications not only extend the optical response to longer wavelengths, but also prolong the life-time of the charge carriers and strengthen the photocatalyst stability. The changes in the surface-bulk properties and the charge carrier transfer dynamics associated with each modification correlating to the high activity are emphasized. The presence of oxidizing agents, surface modification with Cu2+ ions and synthesis of exposed facets to promote the degradation rate is highlighted. In depth study on these nanomaterials is likely to sustain interest in wastewater remediation and envisaged to signify in various green energy applications. (C) 2015 Elsevier B.V. All rights reserved.

Estimation of background carrier concentration in fully depleted GaN films

Buffer leakage is an important parasitic loss mechanism in AlGaN/GaN high electron mobility transistors (HEMTs) and hence various methods are employed to grow semi-insulating buffer layers. Quantification of carrier concentration in such buffers using conventional capacitance based profiling techniques is challenging due to their fully depleted nature even at zero bias voltages. We provide a simple and effective model to extract carrier concentrations in fully depleted GaN films using capacitance-voltage (C-V) measurements. Extensive mercury probe C-V profiling has been performed on GaN films of differing thicknesses and doping levels in order to validate this model. Carrier concentrations as extracted from both the conventional C-V technique for partially depleted films having the same doping concentration, and Hall measurements show excellent agreement with those predicted by the proposed model thus establishing the utility of this technique. This model can be readily extended to estimate background carrier concentrations from the depletion region capacitances of HEMT structures and fully depleted films of any class of semiconductor materials.

Electronic and Magnetic Properties of Yttrium-doped Silicon Carbide Nanotubes: Density Functional Theory Investigations

The electronic structure of yttrium-doped Silicon Carbide Nanotubes has been theoretically investigated using first principles density functional theory (DFT). Yttrium atom is bonded strongly on the surface of the nanotube with a binding energy of 2.37 eV and prefers to stay on the hollow site at a distance of around 2.25 angstrom from the tube. The semi-conducting nanotube with chirality (4, 4) becomes half mettalic with a magnetic moment of 1.0 mu(B) due to influence of Y atom on the surface. There is strong hybridization between d orbital of Y with p orbital of Si and C causing a charge transfer from d orbital of the Y atom to the tube. The Fermi level is shifted towards higher energy with finite Density of States for only upspin channel making the system half metallic and magnetic which may have application in spintronic devices.