Electric current induced flow of liquid metals: Mechanism and substrate-surface effects

Long range, continuous flow of liquid metals occurs upon application of an electric current. Here, we report experimental results elucidating the mechanism of current-induced liquid metal flow, and its dependence on substrate surface condition. It is shown that the observed flow is diffusion-controlled, with the flow-rate depending linearly on applied current density, indicating that it is driven by electromigration. The effective charge number for liquid electromigration, Z*, of several pure metals, such as Al, Bi, Ga, Sn, and Pb, were deduced from the experimental results and were found to be close to the elemental valency. With the exception of liquid Pb, Z* for all liquid metals tested in this study were positive, indicating that: (i) electron wind contributes much less to Z* in liquid metals than in solids, and (ii) with a few exceptions, liquid metals generally flow in the direction of the electric current. On smooth substrates which are wetted well by the liquid metal, flow occurs in a thin, continuous stream. On rough surfaces which are poorly wetted, on the other hand, discrete beads of liquid form, with mass transport between adjacent beads occurring by surface diffusion on the substrate. A rationale for the role of substrate roughness in fostering this observed transition in flow mechanism is presented. (C) 2014 AIP Publishing LLC.

On the mechanism of room temperature superconductivity in substitutionally doped graphene

A combined mechanism involving phononic and electronic processes is suggested for superconductivity in substitutionally doped graphene. The electronic mechanism is similar to the one used for doped fullerene system, MxC60 (M K, Rb, etc.) and triggered by bond polarization due to doped impurities such as B or Al. It is found that on increasing the doping, the superconducting critical temperature can be raised to room temperature. The details of the combined model are given along with the predicted values of T-c. (C) 2013 Elsevier Ltd. All rights reserved,

Allosteric regulation and substrate activation in cytosolic nucleotidase II from Legionella pneumophila

Cytosolic nucleotidase II (cN-II) from Legionellapneumophila (Lp) catalyzes the hydrolysis of GMP and dGMP displaying sigmoidal curves, whereas catalysis of IMP hydrolysis displayed a biphasic curve in the initial rate versus substrate concentration plots. Allosteric modulators of mammalian cN-II did not activate LpcN-II although GTP, GDP and the substrate GMP were specific activators. Crystal structures of the tetrameric LpcN-II revealed an activator-binding site at the dimer interface. A double mutation in this allosteric-binding site abolished activation, confirming the structural observations. The substrate GMP acting as an activator, partitioning between the allosteric and active site, is the basis for the sigmoidicity of the initial velocity versus GMP concentration plot. The LpcN-II tetramer showed differences in subunit organization upon activator binding that are absent in the activator-bound human cN-II structure. This is the first observation of a structural change induced by activator binding in cN-II that may be the molecular mechanism for enzyme activation. DatabaseThe coordinates and structure factors reported in this paper have been submitted to the Protein Data Bank under the accession numbers and . The accession number of GMP complexed LpcN-II is . Structured digital abstract andby() andby() Structured digital abstract was added on 5 March 2014 after original online publication]

Structural and kinetic studies on adenylosuccinate lyase from Mycobacterium smegmatis and Mycobacterium tuberculosis provide new insights on the catalytic residues of the enzyme

Adenylosuccinate lyase (ASL), an enzyme involved in purine biosynthesis, has been recognized as a drug target against microbial infections. In the present study, ASL from Mycobacteriumsmegmatis (MsASL) and Mycobacteriumtuberculosis (MtbASL) were cloned, purified and crystallized. The X-ray crystal structure of MsASL was determined at a resolution of 2.16 angstrom. It is the first report of an apo-ASL structure with a partially ordered active site C3 loop. Diffracting crystals of MtbASL could not be obtained and a model for its structure was derived using MsASL as a template. These structures suggest that His149 and either Lys285 or Ser279 of MsASL are the residues most likely to function as the catalytic acid and base, respectively. Most of the active site residues were found to be conserved, with the exception of Ser148 and Gly319 of MsASL. Ser148 is structurally equivalent to a threonine in most other ASLs. Gly319 is replaced by an arginine residue in most ASLs. The two enzymes were catalytically much less active compared to ASLs from other organisms. Arg319Gly substitution and reduced flexibility of the C3 loop might account for the low catalytic activity of mycobacterial ASLs. The low activity is consistent with the slow growth rate of Mycobacteria and their high GC containing genomes, as well as their dependence on other salvage pathways for the supply of purine nucleotides. Structured digital abstract andby()

Molecular Basis for the Differential Quinolone Susceptibility of Mycobacterial DNA Gyrase

DNA gyrase is a type II topoisomerase that catalyzes the introduction of negative supercoils in the genomes of eubacteria. Fluoroquinolones (FQs), successful as drugs clinically, target the enzyme to trap the gyrase-DNA complex, leading to the accumulation of double-strand breaks in the genome. Mycobacteria are less susceptible to commonly used FQs. However, an 8-methoxy-substituted FQ, moxifloxacin (MFX), is a potent antimycobacterial, and a higher susceptibility of mycobacterial gyrase to MFX has been demonstrated. Although several models explain the mechanism of FQ action and gyrase-DNA-FQ interaction, the basis for the differential susceptibility of mycobacterial gyrase to various FQs is not understood. We have addressed the basis of the differential susceptibility of the gyrase and revisited the mode of action of FQs. We demonstrate that FQs bind both Escherichia coli and Mycobacterium tuberculosis gyrases in the absence of DNA and that the addition of DNA enhances the drug binding. The FQs bind primarily to the GyrA subunit of mycobacterial gyrase, while in E. coli holoenzyme is the target. The binding of MFX to GyrA of M. tuberculosis correlates with its effectiveness as a better inhibitor of the enzyme and its efficacy in cell killing.

A Vision-Based Micro-Newton Static Force Sensor Using a Displacement-Amplifying Compliant Mechanism (DaCM)

A micro-newton static force sensor is presented here as a packaged product. The sensor, which is based on the mechanics of deformable objects, consists of a compliant mechanism that amplifies the displacement caused by the force that is to be measured. The output displacement, captured using a digital microscope and analyzed using image processing techniques, is used to calculate the force using precalibrated force-displacement curve. Images are scanned in real time at a frequency of 15 frames per second and sampled at around half the scanning frequency. The sensor was built, packaged, calibrated, and tested. It has simulated and measured stiffness values of 2.60N/m and 2.57N/m, respectively. The smallest force it can reliably measure in the presence of noise is about 2 mu N over a range of 1.4mN. The off-the-shelf digital microscope aside, all of its other components are purely mechanical; they are inexpensive and can be easily made using simple machines. Another highlight of the sensor is that its movable and delicate components are easily replaceable. The sensor can be used in aqueous environment as it does not use electric, magnetic, thermal, or any other fields. Currently, it can only measure static forces or forces that vary at less than 1Hz because its response time and bandwidth are limited by the speed of imaging with a camera. With a universal serial bus (USB) connection of its digital microscope, custom-developed graphical user interface (GUI), and related software, the sensor is fully developed as a readily usable product.

Conserved water-mediated recognition and dynamics of NAD(+) (carboxamide group) to hIMPDH enzyme: water mimic approach toward the design of isoform-selective inhibitor

Inosine monophosphate dehydrogenase (IMPDH) enzyme involves in GMP biosynthesis pathway. Type I hIMPDH is expressed at lower levels in all cells, whereas type II is especially observed in acute myelogenous leukemia, chronic myelogenous leukemia cancer cells, and 10 ns simulation of the IMP-NAD(+) complex structures (PDB ID. 1B3O and 1JCN) have revealed the presence of a few conserved hydrophilic centers near carboxamide group of NAD(+). Three conserved water molecules (W1, W, and W1 `) in di-nucleotide binding pocket of enzyme have played a significant role in the recognition of carboxamide group (of NAD(+)) to D274 and H93 residues. Based on H-bonding interaction of conserved hydrophilic (water molecular) centers within IMP-NAD(+)-enzyme complexes and their recognition to NAD(+), some covalent modification at carboxamide group of di-nucleotide (NAD(+)) has been made by substituting the -CONH(2)group by -CONHNH2 (carboxyl hydrazide group) using water mimic inhibitor design protocol. The modeled structure of modified ligand may, though, be useful for the development of antileukemic agent or it could be act as better inhibitor for hIMPDH-II.

Formation and Thermal Stability of Gold-Silica Nanohybrids: Insight into the Mechanism and Morphology by Electron Tomography

Gold-silica hybrids are appealing in different fields of applications like catalysis, sensorics, drug delivery, and biotechnology. In most cases, the morphology and distribution of the heterounits play significant roles in their functional behavior. Methods of synthesizing these hybrids, with variable ordering of the heterounits, are replete; however, a complete characterization in three dimensions could not be achieved yet. A simple route to the synthesis of Au-decorated SiO2 spheres is demonstrated and a study on the 3D ordering of the heterounits by scanning transmission electron microscopy (STEM) tomography is presentedat the final stage, intermediate stages of formation, and after heating the hybrid. The final hybrid evolves from a soft self-assembled structure of Au nanoparticles. The hybrid shows good thermal stability up to 400 degrees C, beyond which the Au particles start migrating inside the SiO2 matrix. This study provides an insight in the formation mechanism and thermal stability of the structures which are crucial factors for designing and applying such hybrids in fields of catalysis and biotechnology. As the method is general, it can be applied to make similar hybrids based on SiO2 by tuning the reaction chemistry as needed.

Titanium promoted reduction of imines with Grignards, silanes, and zinc: identification of a new mechanism with silanes

Aldimines react with reducing agents, such as Grignards, phenylsilane or zinc in the presence of titanium(IV) isopropoxide to form amines and reductively coupled imines (diamines). Using deuterium labeled reagents, the mechanism of reduction to form amines is described. Reducing agents, such as the Grignard and zinc result in the formation of low valent titanium (LVT), which in turn reduces the imine. On the other hand, phenylsilane reacts by a distinctly different mechanism and where a hydrogen atom from silicon is directly transferred to the titanium coordinated imine. (c) 2014 Elsevier Ltd. All rights reserved.

Unexpected mechanism for formal 2+2] cycloadditions of metallacyclocumulenes

The formation of radialene complex 6M proceeds through a three-membered metallacyclopropene complex 7M, contrary to the prevailing notion of simple dimerization of metallacyclocumulene 1M. The 1M-7M equilibrium, which is predominantly governed by the size-dependent ligand binding of the metal atoms, plays a decisive role in the chemistry of Cp2M-ligand complexes. This size dependency is further fine-tuned by the substituents on the substrates and helps in exploiting these classes of metallacycles to generate new chemistry.

KINEMATIC SYNTHESIS AND ANALYSIS OF THE RACK AND PINION MULTIPURPOSE MECHANISM

The general procedure for synthesizing the rack and pinion mechanism up to seven precision conditions is developed. To illustrate the method, the mechanism has been synthesized in closed form for three precision conditions of path generation, two positions of function generation, and a velocity condition at one of the precision points. This mechanism has a number of advantages over conventional four bar mechanisms. First, since the rack is always tangent to the pinion, the transmission angle is always 90 deg minus the pressure angle of the rack. Second, with both translation and rotation of the rock occurring, multiple outputs are available. Other advantages include the generation of monotonic functions for a wide variety of motion and nonmonotonic functions for a full range of motion as well as nonlinear amplified motions. In this work the mechanism is made to satisfy a number of amplified motions. In this work the mechanism is made to satisfy a number of practical design requirements such as completely rotatable input crank and others. By including the velocity specification, the designer has considerably more control of the output motion. The method of solution developed in this work uses the complex number method of mechanism synthesis. A numerical example is included

Kinematic Synthesis and Analysis of the Rack and Pinion Multi-Purpose Mechanism

The general procedure for synthesizing the rack and pinion mechanism up to seven precision conditions is developed. To illustrate the method, the mechanism has been synthesized in closed form for three precision conditions of path generation, two positions of function generation, and a velocity condition at one of the precision points. This mechanism has a number of advantages over conventional four bar mechanisms. First, since the rack is always tangent to the pinion, the transmission angle is always 90 deg minus the pressure angle of the rack. Second, with both translation and rotation of the rack occurring, multiple outputs are available. Other advantages include the generation of monotonic functions for a wide variety of motion and nonmonotonic functions for a full range of motion as well as nonlinear amplified motions. In this work the mechanism is made to satisfy a number of practical design requirements such as completely rotatable input crank and others. By including the velocity specification, the designer has considerably more control of the output motion. The method of solution developed in this work uses the complex number method of mechanism synthesis. A numerical example is included.

Bi-Domain Protein Tyrosine Phosphatases Reveal an Evolutionary Adaptation to Optimize Signal Transduction

Significance: The bi-domain protein tyrosine phosphatases (PTPs) exemplify functional evolution in signaling proteins for optimal spatiotemporal signal transduction. Bi-domain PTPs are products of gene duplication. The catalytic activity, however, is often localized to one PTP domain. The inactive PTP domain adopts multiple functional roles. These include modulation of catalytic activity, substrate specificity, and stability of the bi-domain enzyme. In some cases, the inactive PTP domain is a receptor for redox stimuli. Since multiple bi-domain PTPs are concurrently active in related cellular pathways, a stringent regulatory mechanism and selective cross-talk is essential to ensure fidelity in signal transduction. Recent Advances: The inactive PTP domain is an activator for the catalytic PTP domain in some cases, whereas it reduces catalytic activity in other bi-domain PTPs. The relative orientation of the two domains provides a conformational rationale for this regulatory mechanism. Recent structural and biochemical data reveal that these PTP domains participate in substrate recruitment. The inactive PTP domain has also been demonstrated to undergo substantial conformational rearrangement and oligomerization under oxidative stress. Critical Issues and Future Directions: The role of the inactive PTP domain in coupling environmental stimuli with catalytic activity needs to be further examined. Another aspect that merits attention is the role of this domain in substrate recruitment. These aspects have been poorly characterized in vivo. These lacunae currently restrict our understanding of neo-functionalization of the inactive PTP domain in the bi-domain enzyme. It appears likely that more data from these research themes could form the basis for understanding the fidelity in intracellular signal transduction.

A MICROMACHINED WIDE-BAND IN-PLANE SINGLE-AXIS CAPACITIVE ACCELEROMETER WITH A DISPLACEMENT-AMPLIFYING COMPLIANT MECHANISM

With the premise that electronic noise dominates mechanical noise in micromachined accelerometers, we present here a method to enhance the sensitivity and resolution at kHz bandwidth using mechanical amplification. This is achieved by means of a Displacement-amplifying Compliant Mechanism (DaCM) that is appended to the usual sensing element comprising a proof-mass and a suspension. Differential comb-drive arrangement is used for capacitive-sensing. The DaCM is designed to match the stiffness of the suspension so that there is substantial net amplification without compromising the bandwidth. A spring-mass-lever model is used to estimate the lumped parameters of the system. A DaCM-aided accelerometer and another without a DaCM-both occupying the same footprint-are compared to show that the former gives enhanced sensitivity: 8.7 nm/g vs. 1.4 nm/g displacement at the sensing-combs under static conditions. A prototype of the DaCM-aided micromachined acclerometer was fabricated using bulk-micromachining. It was tested at the die-level and then packaged on a printed circuit board with an off-the-shelf integrated chip for measuring change in capacitance. Under dynamic conditions, the measured amplification factor at the output of the DaCM was observed to be about 11 times larger than the displacement of the proof-mass and thus validating the concept of enhancing the sensitivity of accelerometers using mechanical amplifiers. The measured first in-plane natural frequency of the fabricated accelerometer was 6.25 kHz. The packaged accelerometer with the DaCM was measured to have 26.7 mV/g sensitivity at 40 Hz.

Synthesis and Mechanism of Composition and Size Dependent Morphology Selection in Nanoparticles of Ag-Cu Alloys Processed by Laser Ablation Under Liquid Medium

We have synthesized Ag-Cu alloy nanoparticles of four different compositions by using the laser ablation technique with the target under aqueous medium. Following this, we report a morphological transition in the nanoparticles from a normal two-phase microstructure to a structure with random segregation and finally a core shell structure at small sizes as a function of Cu concentration. To illustrate the composition dependence of morphology, we report observations carried out on nanoparticles of two different sizes: similar to 5 and similar to 20 nm. The results could be rationalized through the thermodynamic modeling of free energy of phase mixing and wettability of the alloying phases.