New possibilities in amplitude- and phase-comparison techniques for distance relays

The paper reports further work on the amplitude-comparison technique described by the same authors in a previous paper. This technique is extended to develop improved polar characteristics. Discontinuous polar characteristics, like directional parallelograms, are obtained by a single measuring gate with a simple mode of relay circuitry, whereas two measuring gates are required to provide a directional-quadrilateral characteristic of potentially general application. The paper also describes some new possibilities in phase-comparison methods for distance-protection schemes. Comparator models which effect the amplitude and phase comparison of the relaying signals are described in their schematic form. A comprehensive theoretical basis for comparison is also presented.

Structural analysis of dihydrofolate reductases enables rationalization of antifolate binding affinities and suggests repurposing possibilities

Antifolates are competitive inhibitors of dihydrofolate reductase ( DHFR), a conserved enzyme that is central to metabolism and widely targeted in pathogenic diseases, cancer and autoimmune disorders. Although most clinically used antifolates are known to be target specific, some display a fair degree of cross-reactivity with DHFRs from other species. A method that enables identification of determinants of affinity and specificity in target DHFRs from different species and provides guidelines for the design of antifolates is currently lacking. To address this, we first captured the potential druggable space of a DHFR in a substructure called the `supersite' and classified supersites of DHFRs from 56 species into 16 `site-types' based on pairwise structural similarity. Analysis of supersites across these site-types revealed that DHFRs exhibit varying extents of dissimilarity at structurally equivalent positions in and around the binding site. We were able to explain the pattern of affinities towards chemically diverse antifolates exhibited by DHFRs of different site-types based on these structural differences. We then generated an antifolate-DHFR network by mapping known high-affinity antifolates to their respective supersites and used this to identify antifolates that can be repurposed based on similarity between supersites or antifolates. Thus, we identified 177 human-specific and 458 pathogen-specific antifolates, a large number of which are supported by available experimental data. Thus, in the light of the clinical importance of DHFR, we present a novel approach to identifying differences in the druggable space of DHFRs that can be utilized for rational design of antifolates.

On the cytotoxicity of carbon nanotubes

The cytotoxicity of carbon nanotubes (CNTs) is a major concern today well before its unusual physicochemical, mechanical, and electrical properties are fully exploited for commercial interests and subsequent mass production leading to greater possibilities for its exposure to humans and the environment. Contradictory reports on cytotoxicity of CNTs often appear in the literature and a mechanistic explanation of the reported toxicity remains obscure. We review here the conflicting results to focus categorically on an array of issues in CNT cytotoxicity. They include dispersion, aggregation status, coating or functionalization and immobilization, cellular uptake or internalization, purity in terms of metal catalyst contaminants, size and size distribution, surface area, surface chemistry and surface reactivity, cell types selected for experimentation as well as bioassay of nanotoxicity itself attesting as an issue in cytotoxicity. Recently a general agreement has emerged towards the potential toxicity of CNTs, although various paradigms explaining the mechanisms of CNT cytotoxicity continue to be elusive in the literature. A lack of synergy among various issues while studying cytotoxicity and most developed paradigms for the mechanism of CNT toxicity is highlighted.

Theoretical Description of Time-Resolved Photoemission Spectroscopy: Application to Pump-Probe Experiments

The theory for time-resolved, pump-probe, photoemission spectroscopy and other pump-probe experiments is developed. The formal development is completely general, incorporating all of the nonequilibrium effects of the pump pulse and the finite time width of the probe pulse, and including possibilities for taking into account band structure and matrix element effects, surface states, and the interaction of the photoexcited electrons with the system leading to corrections to the sudden approximation. We also illustrate the effects of windowing that arise from the finite width of the probe pulse in a simple model system by assuming the quasiequilibrium approximation.

Large carrier mobilities in octathio[8]circulene crystals: a theoretical study

The electron and hole mobilities of octathio[8]circulene (sulflower) crystal have been calculated using quantum chemical methods, with accurate determination of reorganization energies and the rate of charge transfer, the key parameters controlling the charge carriers conductance. We find this molecular crystal to be an excellent conductor with large mobilities for both the charge carriers. Moreover, the hole mobility is found to be slightly larger than the electron mobility. Such an ambipolar organic crystal with substantial carrier mobilities shows possibilities of sophisticated device fabrication in advanced electronics.

A novel conformation of valinomycin in its barium complex

Knowledge of the molecular mechanisms involved in ionophore-mediated cation transport would be valuable for under-standing many essential functions of biological membranes1−3. Cations are transported in several stages, such as formation of the ionophore−cation complex, diffusion across the cell membrane and subsequent release of the cation. Several conformational rearrangements are involved in this process, and so a detailed understanding of all the conformational possibilities of the ionophore seems to be essential for elucidating the molecular mechanism of ion transport. We are carrying out spectroscopic and crystallographic studies to explore the possible conformational stages of ionophores by complexing them, in different solvents, with cations of various sizes and charges. We report here a novel conformation of the ionophore valinomycin in its barium complex. It can be described as an extended depsipeptide chain, without internal hydrogen bonds, wound in the form of an ellipse with the two barium ions located at the foci.

Modification of chemical reactivity by cyclodextrins. Observation of moderate effects on Norrish type I and type II photobehavior

The photochemistry and photophysics of organic molecules in organized assemblies are being studied with great interest in order to understand the features controlling the selectivity in the photoreactions brought about by these media.l These studies have paved the way to an intriguing number of possibilities by which photoreactivity can be modified. In this connection, we have investigated the photobehavior of a number of phenyl alkyl ketones and cu,cu-dimethylphenyl alkyl ketones (Scheme I) incorporated in the hydrophobic interior of cyclodextrin cavities.

Photodimerization of olefins in solid state

Photochemical transformations of organic solids provide an exciting area of research with new synthetic possibilities. These reactions are generally governed by topochemical factors rather than the normal rules of chemical reactivity. Defects play a crucial role in some of the reactions. Some of the transformations such as the photodimerization of 4, 4'-dimethoxystilbene occur in a single crystal fashion.

Appearance of "Fragile" Fermi Liquids in Finite-Width Mott Insulators Sandwiched between Metallic Leads

Using inhomogeneous dynamical mean-field theory, we show that the normal-metal proximity effect could force any finite number of Mott-insulating "barrier" planes sandwiched between semi-infinite metallic leads to become "fragile" Fermi liquids. They are fully Fermi-liquid-like at T=0, leading to a restoration of lattice periodicity at zero frequency, with a well-defined Fermi surface, and perfect (ballistic) conductivity. However, the Fermi-liquid character can rapidly disappear at finite omega, V, T, disorder, or magnetism, all of which restore the expected quantum tunneling regime, leading to fascinating possibilities for nonlinear response in devices.

Conformational Choices for the Stereochemically Constrained gamma-Amino Acid Residue Gabapentin: Theoretical Studies and Correlation With Experimental Results

Gabapentin (1-aminomethylcyclohexaneacetic acid, Gpn) is an achiral, conformationally constrained gamma amino acid residue. A survey of available crystal structures of Gpn peptides reveals that the torsion angles about the C-gamma-C-beta (theta(1)) and C-beta-C-alpha(theta(2)) bonds are overwhelmingly limited to gauche, gauche (g(+)g(+)/g(-)g(-)) conformations. The Gpn residue forms C-7 and C-9 hydrogen bonds in which the donor and acceptor atoms come from the flanking peptide units. In combination with alpha amino acid residues alpha gamma and gamma alpha segments can adopt C-12 hydrogen bonded structures. The conformational choices available to the Gpn residue have been probed using energy calculations, adopting a grid search strategy. Ramachandran phi-psi maps have been constructed for fixed values of theta(1) and theta(2), corresponding to the gauche and trans conformations. The sterically allowed and energetically favorable regions of conformational space have been defined and experimental observations compared. C-7 and C-9 hydrogen bonded conformational families have been identified using a grid search approach in which theta(1) and theta(2) values are varied over a range of +/- 10 degrees about ideal values at 1 degrees intervals. The theoretical analysis together with experimental observations for 59 Gpn residues from 35 crystal structures permits definition of the limited range of conformational possibilities at this gamma amino acid residue. .

Mycobacterium tuberculosis FtsZ requires at least one arginine residue at the C-terminal end for polymerization in vitro

We examined whether C-terminal residues of soluble recombinant FtsZ of Mycobacterium tuberculosis (MtFtsZ) have any role in MtFtsZ polymerization in vitro. MtFtsZ-delta C1, which lacks C-terminal extreme Arg residue (underlined in the C-terminal extreme stretch of 13 residues, DDDDVDVPPFMRR), but retaining the penultimate Arg residue (DDDDVDVPPFMR), polymerizes like full-length MtFtsZ in vitro. However, MtFtsZ-delta C2 that lacks both the Arg residues at the C-terminus (DDDDVDVPPFM), neither polymerizes at pH 6.5 nor forms even single- or double-stranded filaments at pH 7.7 in the presence of 10 mM CaCl2. Neither replacement of the penultimate Arg residue, in the C-terminal Arg deletion mutant DDDDVDVPPFMR, with Lys or His or Ala or Asp (DDDDVDVPPFMK/H/A/D) enabled polymerization. Although MtFtsZ-delta C2 showed secondary and tertiary structural changes, which might have affected polymerization, GTPase activity of MtFtsZ-delta C2 was comparable to that of MtFtsZ. These data suggest that MtFtsZ requires an Arg residue as the extreme C-terminal residue for polymerization in vitro. The polypeptide segment containing C-terminal 67 residues, whose coordinates were absent from MtFtsZ crystal structure, was modeled on tubulin and MtFtsZ dimers. Possibilities for the influence of the C-terminal Arg residues on the stability of the dimer and thereby on MtFtsZ polymerization have been discussed.

Process variables in biomimetic synthesis of silver nanoparticles by aqueous extract of Azadirachta indica (Neem) leaves

Owing to widespread applications, synthesis and characterization of silver nanoparticles is recently attracting considerable attention. Increasing environmental concerns over chemical synthesis routes have resulted in attempts to develop biomimetic approaches. One of them is synthesis using plant parts, which eliminates the elaborate process of maintaining the microbial culture and often found to be kinetically favourable than other bioprocesses. The present study deals with investigating the effect of process variables like reductant concentrations, reaction pH, mixing ratio of the reactants and interaction time on the morphology and size of silver nanoparticles synthesized using aqueous extract of Azadirachta indica (Neem) leaves. The formation of crystalline silver nanoparticles was confirmed using X-ray diffraction analysis. By means of UV spectroscopy, Scanning and Transmission Electron Microscopy techniques, it was observed that the morphology and size of the nanoparticles were strongly dependent on the process parameters. Within 4 h interaction period, nanoparticles below 20-nm-size with nearly spherical shape were produced. On increasing interaction time (ageing) to 66 days, both aggregation and shape anisotropy (ellipsoidal, polyhedral and capsular) of the particles increased. In alkaline pH range, the stability of cluster distribution increased with a declined tendency for aggregation of the particles. It can be inferred from the study that fine tuning the bioprocess parameters will enhance possibilities of desired nano-product tailor made for particular applications.

Manifolds with nonnegative isotropic curvature

We prove that if (M-n, g), n >= 4, is a compact, orientable, locally irreducible Riemannian manifold with nonnegative isotropic curvature,then one of the following possibilities hold: (i) M admits a metric with positive isotropic curvature. (ii) (M, g) is isometric to a locally symmetric space. (iii) (M, g) is Kahler and biholomorphic to CPn/2. (iv) (M, g) is quaternionic-Kahler. This is implied by the following result: Let (M-2n, g) be a compact, locally irreducible Kahler manifold with nonnegative isotropic curvature. Then either M is biholomorphic to CPn or isometric to a compact Hermitian symmetric space. This answers a question of Micallef and Wang in the affirmative. The proof is based on the recent work of Brendle and Schoen on the Ricci flow.

Raman spectrum of dimethyl sulfoxide (DMSO) and the influence of solvents

The Raman spectrum of DMSO is recorded with a Hilger two-prism spectrograph andλ 4358 Å excitation. In addition to all the Raman lines reported earlier, six new lines at 898, 925, 1223, 1309, 2811 and 2871 cm.−1 are observed and tentative assignments are given. The influence of solvents (CCl4, CHCl3, CH3COOH) on the S=O bond is also studied. A shift from the liquid phase value,i.e., 1043 cm.−1 to 1054, 1052 and 1009 cm.−1 in the respective solvents is observed. The possibilities of association effects and hydrogen bonding are discussed.

Advanced transmission electron microscope triboprobe with automated closed-loop nanopositioning

Here the design and operation of a novel transmission electron microscope (TEM) triboprobe instrument with real-time vision control for advanced in situ electron microscopy is demonstrated. The NanoLAB triboprobe incorporates a new high stiffness coarse slider design for increased stability and positioning performance. This is linked with an advanced software control system which introduces both new and flexible in situ experimental functional testing modes, plus an automated vision control feedback system. This advancement in instrumentation design unlocks new possibilities of performing a range of new dynamical nanoscale materials tests, including novel friction and fatigue experiments inside the electron microscope.