The Coil-to-Helix Transition in IlvN Regulates the Allosteric Control of Escherichia coli Acetohydroxyacid Synthase I

The solution structure of IlvN, the regulatory subunit of Escherichia coil acetohydroxyacid synthase I, in the valine-bound form has been determined using high-resolution multidimensional, multinuclear nuclear magnetic resonance (NMR) methods. IlvN in the presence or absence of the effector molecule is present as a 22.5 kDa dimeric molecule. The ensemble of 20 low-energy structures shows a backbone root-mean-square deviation of 0.73 +/- 0.13 angstrom and a root-mean-square deviation of 1.16 +/- 0.13 angstrom for all heavy atoms. Furthermore, more than 98% of the backbone phi and psi dihedral angles occupy the allowed and additionally allowed regions of the Ramachandran map, which is indicative of the fact that the structures are of high stereochemical quality. Each protomer exhibits a beta alpha beta beta alpha beta alpha topology that is a characteristic feature of the ACT domain seen in metabolic enzymes. In the valine-bound form, IlvN exists apparently as a single conformer. In the free form, IlvN exists as a mixture of conformational states that are in intermediate exchange on the NMR time scale. Thus, a large shift in the conformational equilibrium is observed upon going from the free form to the bound form. The structure of the valine-bound form of IlvN was found to be similar to that of the ACT domain of the unliganded form of IlvH. Comparisons of the structures of the unliganded forms of these proteins suggest significant differences. The structural and conformational properties of IlvN determined here have allowed a better understanding of the mechanism of regulation of branched chain amino acid biosynthesis.

Variation in glass transition temperature of polymer nanocomposite films driven by morphological transitions

We report the variation of glass transition temperature in supported thin films of polymer nanocomposites, consisting of polymer grafted nanoparticles embedded in a homopolymer matrix. We observe a systematic variation of the estimated glass transition temperature T-g, with the volume fraction of added polymer grafted nanoparticles. We have correlated the observed T-g variation with the underlying morphological transitions of the nanoparticle dispersion in the films. Our data also suggest the possibility of formation of a low-mobility glass or gel-like layer of nanoparticles at the interface, which could play a significant role in determining T-g of the films provided. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4773442]

Effect of substrate surface roughness on electric current induced flow of liquid metals

Electric current can induce long-range flow of liquid metals over a conducting substrate. This work reports on the effect of the substrate surface roughness on the liquid metal-front velocity during such a flow. Experiments were conducted by passing electric current through liquid gallium placed over similar to 170 nm thick, 500 mu m wide gold and platinum films of varying roughness. The ensuing flow, thus, resembles micro-fluidics behavior in an open-channel. The liquid-front velocity decreased linearly with the substrate surface roughness; this is attributed to the reduction in the effective electric field along the liquid metal-substrate interface with the substrate surface roughness. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4790182]

Sharp raman anomalies and broken adiabaticity at a pressure induced transition from band to topological insulator in Sb2Se3

The nontrivial electronic topology of a topological insulator is thus far known to display signatures in a robust metallic state at the surface. Here, we establish vibrational anomalies in Raman spectra of the bulk that signify changes in electronic topology: an E-g(2) phonon softens unusually and its linewidth exhibits an asymmetric peak at the pressure induced electronic topological transition (ETT) in Sb2Se3 crystal. Our first-principles calculations confirm the electronic transition from band to topological insulating state with reversal of parity of electronic bands passing through a metallic state at the ETT, but do not capture the phonon anomalies which involve breakdown of adiabatic approximation due to strongly coupled dynamics of phonons and electrons. Treating this within a four-band model of topological insulators, we elucidate how nonadiabatic renormalization of phonons constitutes readily measurable bulk signatures of an ETT, which will facilitate efforts to develop topological insulators by modifying a band insulator. DOI: 10.1103/PhysRevLett.110.107401

Geometry of static balancing during posture transition

The interaction between the digital human model (DHM) and environment typically occurs in two distinct modes; one, when the DHM maintains contacts with the environment using its self weight, wherein associated reaction forces at the interface due to gravity are unidirectional; two, when the DHM applies both tension and compression on the environment through anchoring. For static balancing in first mode of interaction, it is sufficient to maintain the projection of the centre of mass (COM) inside the convex region induced by the weight supporting segments of the body on a horizontal plane. In DHM, static balancing is required while performing specified tasks such as reach, manipulation and locomotion; otherwise the simulations would not be realistic. This paper establishes the geometric relationships that must be satisfied for maintaining static balance while altering the support configurations for a given posture and altering the posture for a given support condition. For a given location of the COM for a system supported by multiple point contacts, the conditions for simultaneous withdrawal of a specified set of contacts have been determined in terms of the convex hulls of the subsets of the points of contact. When the projection of COM must move beyond the existing support for performing some task, new supports must be enabled for maintaining static balance. This support seeking behavior could also manifest while planning for reduction of support stresses. Feasibility of such a support depends upon the availability of necessary features in the environment. Geometric conditions necessary for selection of new support on horizontal,inclined and vertical surfaces within the workspace of the DHM for such dynamic scenario have been derived. The concepts developed are demonstrated using the cases of sit-to-stand posture transition for manipulation of COM within the convex supporting polygon, and statically stable walking gaits for support seeking within the kinematic capabilities of the DHM. The theory developed helps in making the DHM realize appropriate behaviors in diverse scenarios autonomously.

Competing structural phase transition scenarios in the giant tetragonality ferroelectric BiFeO3-PbTiO3: Isostructural vs multiphase transition

A systematic x-ray and neutron powder diffraction study of the giant tetragonality multiferroic (1-x) BiFeO3-(x) PbTiO3 have revealed that the compositions close to the morphotropic phase boundary present two different structural phase transition scenarios on cooling from the cubic phase: (i) cubic -> tetragonal (T-2) + tetragonal (T-1) -> tetragonal (T-1) and (ii) cubic -> tetragonal (T-2) + tetragonal (T-1) + rhombohedral (R3c) -> tetragonal (T-1) + rhombohedral (R3c). The comparatively larger tetragonality (c/a - 1) of the T-1 phase as compared to the coexisting isostructural T-2 phase is shown to be a result of significantly greater degree of overlap of the Pb/Bi-6s and Ti/Fe-3d with the O-2p orbitals as compared to that in the T-2 phase. The formation/suppression of the minor metastable rhombohedral phase seems to be governed by subtle play of local kinetic factors. In the scenario when the minor rhombohedral (R) phase is formed along with the tetragonal phases it is able to accommodate the large transformation stress in the system due to formation of the tetragonal phases, and prevent the solid from disintegration into powder after sintering. When the metastable rhombohedral phase is not formed, the large transformation strain ruptures the grain boundaries leading to fragmentation of the dense solid to powder. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4792215]

Gap-Dependent Quasiparticle Dynamics and Coherent Acoustic Phonons in CaFe2As2 across Spin Density Wave Phase Transition

We report ultrafast quasiparticle (QP) dynamics and coherent acoustic phonons in undoped CaFe2As2 iron pnictide single crystals exhibiting spin-density wave (SDW) and concurrent structural phase transition at temperature T-SDW similar to 165K using femtosecond time-resolved pump-probe spectroscopy. The contributions in transient differential reflectivity arising from exponentially decaying QP relaxation and oscillatory coherent acoustic phonon mode show large variations in the vicinity of T-SDW. From the temperature-dependence of the QP recombination dynamics in the SDW phase, we evaluate a BCS-like temperature dependent charge gap with its zero-temperature value of similar to(1.6 perpendicular to 0.2)k(B)T(SDW), whereas, much above T-SDW, an electron-phonon coupling constant of similar to 0.13 has been estimated from the linear temperature-dependence of the QP relaxation time. The long-wavelength coherent acoustic phonons with typical time-period of similar to 100 ps have been analyzed in the light of propagating strain pulse model providing important results for the optical constants, sounds velocity and the elastic modulus of the crystal in the whole temperature range of 3 to 300 K.

Effective Mass-Driven Structural Transition in a Mn-Doped ZnS Nanoplatelet

Mn doping in ZnS nanoplatelets has been shown to induce a structural transition from the wurtzite to the zinc blende phase. We trace the origin of this transition to quantum confinement effects, which shift the valence band maximum of the wurtzite and zinc blende polyrnorphs of ZnS at different rates as a function of the nanocrystal size, arising from different effective hole masses in the two structures. This modifies the covalency associated with Mn incorporation and is reflected in the size-dependent binding energy difference for the two structures.

Ratiometric, reversible, and parts per billion level detection of multiple toxic transition metal ions using a single probe in micellar media

We present the selective sensing of multiple transition metal ions in water using a synthetic single probe. The probe is made up of pyrene and pyridine as signaling and interacting moiety, respectively. The sensor showed different responses toward metal ions just by varying the medium of detection. In organic solvent (acetonitrile), the probe showed selective detection of Hg2+ ion. In water, the fluorescence quenching was observed with three metal ions, Cu2+, Hg2+, and Ni2+. Further, just by varying the surface charge on the micellar aggregates, the probe could detect and discriminate the above-mentioned three different toxic metal ions appropriately. In neutral micelles (Brij 58), the probe showed a selective interaction with Hg2+ ion as observed in acetonitrile medium. However, in anionic micellar medium (sodium dodecyl sulfate, SDS), the probe showed changes with both Cu2+ and Ni2+. under UV-vis absorption spectroscopy. The discrimination between these two ions was achieved by recording their emission spectra, where it showed selective quenching with Cu2+.

The effect of minor addition of Ni on the microstructural evolution and mechanical properties of suction cast Al-0.14 at. pct Sc binary alloy

Aluminum scandium binary alloys represent a promising precipitation-hardening alloy system. However, the hardness of the binary alloys decreases with the rapid coarsening of Al3Sc precipitate during high-temperature aging. In the current study, we report a new approach to compensate for the loss of mechanical properties by combining rapid solidification with very small ternary addition of transition metal Ni. This addition yields dispersion, and at a critical concentration improves the mechanical properties. We explore additions of a maximum of 0.06 at. pct of Nickel to a binary Al-0.14 at. pct Sc alloy, which yield nickel-rich dispersions. We report two kinds of biphasic dispersions containing AlNi2Sc/Al9Ni2 and alpha-Al/Al9Ni2 phase combinations. The maximum improvement in mechanical properties occurs with the addition of 0.045 at. pct Ni with a yield strength of 239 +/- A 7 MPa for an aging treatment at 583 K (310 A degrees C) for 15 hours. DOI: 10.1007/s11661-013-1624-z (C) The Minerals, Metals & Materials Society and ASM International 2013

An unusual temperature induced isostructural phase transition in a scheelite, Li0.5Ce0.5MoO4

High resolution synchrotron X-ray diffraction, dielectric and Raman scattering study of a scheelite compound Li0.5Ce0.5MoO4 (LCM) revealed that it transforms to a self similar structure above 400 degrees C. The thermally induced isostructural phase transition (IPT), a phenomenon which has rarely been reported in the literature, is preceded by partial softening of the zone centre phonons followed by their hardening above the IPT transition temperature. The high temperature isostructural phase, which exhibits expanded lattice parameters and cell volume, nucleates and grows in the low temperature matrix over a very wide temperature range. Both the phases show nearly identical thermal expansion suggesting similarities in symmetry, unaltered coordination environments around the atoms across the transition.

Performance limits of transition metal dichalcogenide (MX2) nanotube surround gate ballistic field effect transistors

We theoretically analyze the performance of transition metal dichalcogenide (MX2) single wall nanotube (SWNT) surround gate MOSFET, in the 10 nm technology node. We consider semiconducting armchair (n, n) SWNT of MoS2, MoSe2, WS2, and WSe2 for our study. The material properties of the nanotubes are evaluated from the density functional theory, and the ballistic device characteristics are obtained by self-consistently solving the Poisson-Schrodinger equation under the non-equilibrium Green's function formalism. Simulated ON currents are in the range of 61-76 mu A for 4.5 nm diameter MX2 tubes, with peak transconductance similar to 175-218 mu S and ON/OFF ratio similar to 0.6 x 10(5)-0.8 x 10(5). The subthreshold slope is similar to 62.22 mV/decade and a nominal drain induced barrier lowering of similar to 12-15 mV/V is observed for the devices. The tungsten dichalcogenide nanotubes offer superior device output characteristics compared to the molybdenum dichalcogenide nanotubes, with WSe2 showing the best performance. Studying SWNT diameters of 2.5-5 nm, it is found that increase in diameter provides smaller carrier effective mass and 4%-6% higher ON currents. Using mean free path calculation to project the quasi-ballistic currents, 62%-75% reduction from ballistic values in drain current in long channel lengths of 100, 200 nm is observed.

Freezing of the octahedral tilt near ferromagnetic transition and appearance of a glassy phase at low temperature driven by the tilt instabilities in SrRuO3

The emergence of low temperature glassy phase in widely known itinerant ferromagnet SrRuO3 is remotely understood. In order to understand this aspect, we have undertaken a detailed temperature dependent (5-250 K) neutron diffraction study. We observe a freezing of the octahedral tilt near the ferromagnetic transition and an unusual deviation in the octahedral tilt near the onset of low temperature spin glass like phase. A reduction of the ordered magnetic moment and a decline in the total integrated magnetic intensity is observed around the temperature where the glassy behaviour starts to appear. The magnetotransport study also reveals the possibility for an additional magnetic ordering by demonstrating a peak in magnetoresistance at the low temperature side as well. The neutron diffraction study presented here provides useful information to understand the observed unusual low temperature magnetic phenomena in SrRuO3.

A multifold reduction in the transition Reynolds number, and ultra-fast mixing, in a micro-channel due to a dynamical instability induced by a soft wall

A dynamical instability is observed in experimental studies on micro-channels of rectangular cross-section with smallest dimension 100 and 160 mu m in which one of the walls is made of soft gel. There is a spontaneous transition from an ordered, laminar flow to a chaotic and highly mixed flow state when the Reynolds number increases beyond a critical value. The critical Reynolds number, which decreases as the elasticity modulus of the soft wall is reduced, is as low as 200 for the softest wall used here (in contrast to 1200 for a rigid-walled channel) The instability onset is observed by the breakup of a dye-stream introduced in the centre of the micro-channel, as well as the onset of wall oscillations due to laser scattering from fluorescent beads embedded in the wall of the channel. The mixing time across a channel of width 1.5 mm, measured by dye-stream and outlet conductance experiments, is smaller by a factor of 10(5) than that for a laminar flow. The increased mixing rate comes at very little cost, because the pressure drop (energy requirement to drive the flow) increases continuously and modestly at transition. The deformed shape is reconstructed numerically, and computational fluid dynamics (CFD) simulations are carried out to obtain the pressure gradient and the velocity fields for different flow rates. The pressure difference across the channel predicted by simulations is in agreement with the experiments (within experimental errors) for flow rates where the dye stream is laminar, but the experimental pressure difference is higher than the simulation prediction after dye-stream breakup. A linear stability analysis is carried out using the parallel-flow approximation, in which the wall is modelled as a neo-Hookean elastic solid, and the simulation results for the mean velocity and pressure gradient from the CFD simulations are used as inputs. The stability analysis accurately predicts the Reynolds number (based on flow rate) at which an instability is observed in the dye stream, and it also predicts that the instability first takes place at the downstream converging section of the channel, and not at the upstream diverging section. The stability analysis also indicates that the destabilization is due to the modification of the flow and the local pressure gradient due to the wall deformation; if we assume a parabolic velocity profile with the pressure gradient given by the plane Poiseuille law, the flow is always found to be stable.

Stabilization of diborane(4) by transition metal fragments and a novel metal to pi Dewar-Chatt-Duncanson model of back donation

The feasibility of using transition metal fragments to stabilize B2H4 in planar configuration by donating 2 electrons to the boron moiety is investigated. Building upon the existing theoretical and experimental data and aided by the isolobal analogy, the model transition metal complexes Cr(CO)(4)B2H4 (6), Mn(CO)-CpB2H4 (7), Fe(CO)(3)B2H4 (8) and CoCpB2H4 (9) are chosen to illustrate this unique bonding feature bond strengthening with pi-back donation. Other possible types of complexes with B2H4 and the metal fragment are also explored and the energies are compared. One of the low energy isomers wherein the planar B2H4 interacts with the metal fragment in an in-plane fashion represents a unique case study for the Dewar-Chatt-Duncanson model. In this complex the back-donation from the metal fills the p bonding orbital between the two boron atoms thus forming a B=B double bond.