Electrical Breakdown of Gases Between Coaxial Cylindrical Electrodes in Crossed Electric and Magnetic Fields

Sparking potentials have been measured in nitrogen and dry air between coaxial cylindrical electrodes for values of n = R2/R1 = approximately 1 to 30 (R1 = inner electrode radius, R2 = outer electrode radius) in the presence of crossed uniform magnetic fields. The magnetic flux density was varied from 0 to 3000 Gauss. It has been shown that the minimum sparking potentials in the presence of the crossed magnetic field can be evaluated on the basis of the equivalent pressure concept when the secondary ionization coefficient does not vary appreciably with B/p (B = magnetic flux density, p = gas pressure). The values of secondary ionization coefficients �¿B in nitrogen in crossed fields calculated from measured values of sparking potentials and Townsend ionization coefficients taken from the literature, have been reported. The calculated values of collision frequencies in nitrogen from minimum sparking potentials in crossed fields are found to increase with increasing B/p at constant E/pe (pe = equivalent pressure). Studies on the similarity relationship in crossed fields has shown that the similarity theorem is obeyed in dry air for both polarities of the central electrode in crossed fields.

Gold(I)-selenolate complexes: Synthesis, characterization and ligand exchange reactions

In this paper, the synthesis and characterization of some imidazole-based gold-selenolates are described. This study indicates that the nature of selenolate plays an important role in ligand exchange reactions in gold(I) selenolates. Furthermore, the reactivity of imidazole-based gold(I) selenolates toward nucleophiles such as selenols and phosphines is strikingly different from that of the N,N-dimethylaminobenzylamine-based gold(I) complexes. The presence of Se ... N non-bonded interactions in N,N-dimethylaminobenzylamine-based gold(I) complexes modulates the reactivity of Au(I) centre towards incoming nucleophiles.

Thermoelectricity in graphene: Effects of a gap and magnetic fields

We calculate the thermopower of monolayer graphene in various circumstances. We consider acoustic phonon scattering which might be the operative scattering mechanism in freestanding films and predict that the thermopower will be linear in any induced gap in the system. Further, the thermopower peaks at the same value of chemical potential (tunable by gate voltage) independent of the gap. We show that in the semiclassical approximation, the thermopower in a magnetic field saturates at high field to a value which can be calculated exactly and is independent of the details of the scattering. This effect might be observable experimentally. We also note that a Yukawa scattering potential can be used to fit experimental data for the thermopower for reasonable values of the screening length parameter.

Stabilization of Co-3 - Oxoclusters in a pcu Net: Synthesis, Structure, Solvent Exchange (Single Crystal to Single Crystal) and Magnetic Studies

The solvothermal reaction of CoCl(2)4H(2)O and 4,4-sulfonyldibenzoic acid (H(2)SDBA) resulted in the formation of a three-dimensional coordination polymer Co-3(C14H8O6S)(3)(DMA)(2)(MeOH)].DMA (Ia) consisting of trinuclear Co-3 oxo-cluster units. The Co-3 trimeric units are connected by SDBA(2-) anions leading to a three dimensional structure with a pcu topology. The terminal methanol molecules could be exchanged in a single crystal to single crystal (SCSC) fashion by other similar solvent molecules (ethanol, acetonitrile, water, ethyleneglycol). Magnetic studies on the parent compound, Ia, indicate antiferromagnetic interactions between the central metal atoms.

Structural diversity and ligand specificity of lectins. The Bangalore effort

Structural studies in this laboratory encompass four of the five major classes of plant lectins, including the one discovered by us. In addition to addressing issues specific to individual lectins, the work provided insights into protein folding, quaternary association and generation of ligand specificity. Legume and beta-prism fold lectins constitute families of proteins in which small alterations in essentially the same tertiary structure lead to large variations in quaternary structure, including that involving an open structure. Strategies for generating ligand specificity include water bridges, variation in loop length, post translational modification and oligomerization. Three of the structural classes investigated have subunits with three-fold symmetry. The symmetry in the structure is reflected in the sequence to different extents in different subclasses. The evolutionary implications of this observation have been explored. The work on lectins has now been extended to those from mycobacteria.

Giant actuation in bulk carbon nanotubes under coupled electric and magnetic fields

We report an enhanced actuation in bulk carbon nanotubes (CNTs) under coupled electric and magnetic fields, which is much higher than that evaluated in the presence of individual fields. Coupled electric and magnetic fields induce a directional actuation demonstrating a transformation from polarity independent to dependent actuation behavior of CNTs. Both qualitative and quantitative analyses are performed to understand this transformation in the bulk CNTs. Moreover, actuations along radial and axial directions of CNTs have also demonstrated a similar directional behavior.

Synthesis, and crystal and electronic structure of sodium metal phosphate for use as a hybrid capacitor in non-aqueous electrolyte

Energy storage devices based on sodium have been considered as an alternative to traditional lithium based systems because of the natural abundance, cost effectiveness and low environmental impact of sodium. Their synthesis, and crystal and electronic properties have been discussed, because of the importance of electronic conductivity in supercapacitors for high rate applications. The density of states of a mixed sodium transition metal phosphate (maricite, NaMn1/3Co1/3Ni1/3PO4) has been determined with the ab initio generalized gradient approximation (GGA)+Hubbard term (U) method. The computed results for the mixed maricite are compared with the band gap of the parent NaFePO4 and the electrochemical experimental results are in good agreement. A mixed sodium transition metal phosphate served as an active electrode material for a hybrid supercapacitor. The hybrid device (maricite versus carbon) in a nonaqueous electrolyte shows redox peaks in the cyclic voltammograms and asymmetric profiles in the charge-discharge curves while exhibiting a specific capacitance of 40 F g(-1) and these processes are found to be quasi-reversible. After long term cycling, the device exhibits excellent capacity retention (95%) and coulombic efficiency (92%). The presence of carbon and the nanocomposite morphology, identified through X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) studies, ensures the high rate capability while offering possibilities to develop new cathode materials for sodium hybrid devices.

AN INVESTIGATION OF CUTTING MECHANISMS AND STRAIN FIELDS DURING ORTHOGONAL CUTTING IN CFRPs

Fiber-reinforced plastics (FRPs) are typically difficult to machine due to their highly heterogeneous and anisotropic nature and the presence of two phases (fiber and matrix) with vastly different strengths and stiffnesses. Typical machining damage mechanisms in FRPs include series of brittle fractures (especially for thermosets) due to shearing and cracking of matrix material, fiber pull-outs, burring, fuzzing, fiber-matrix debonding, etc. With the aim of understanding the influence of the pronounced heterogeneity and anisotropy observed in FRPs, ``Idealized'' Carbon FRP (I-CFRP) plates were prepared using epoxy resin with embedded equispaced tows of carbon fibers. Orthogonal cutting of these I-CFRPs was carried out, and the chip formation characteristics, cutting force signals and strain distributions obtained during machining were analyzed using the Digital Image Correlation (DIC) technique. In addition, the same procedure was repeated on Uni-Directional CFRPs (UD-CFRPs). Chip formation mechanisms in FRPs were found to depend on the depth of cut and fiber orientation with pure epoxy showing a pronounced ``size effect.'' Experimental results indicate that in-situ full field strain measurements from DIC coupled with force measurements using dynamometry provide an adequate measure of anisotropy and heterogeneity during orthogonal cutting.

A new expression of hardening coefficients for fcc-crystal and calibration of the material constants

In order to describe the effect of latent hardening on the macro-plastic behavior of foc-crystal, a new expression for hardening coefficient is proposed in which there are 12 material constants, each having clear physical meaning. And a method of material constant calibration is suggested and used to determine the material constants of copper and aluminum crystal. The simulated load-elongation curves along various crystallographic orientations are comparable with the experimental ones.

Guiding and confining fast electrons by transient electric and magnetic fields with a plasma inverse cone

The fast electron propagation in an inverse cone target is investigated computationally and experimentally. Two-dimensional particle-in-cell simulation shows that fast electrons with substantial numbers are generated at the outer tip of an inverse cone target irradiated by a short intense laser pulse. These electrons are guided and confined to propagate along the inverse cone wall, forming a large surface current. The propagation induces strong transient electric and magnetic fields which guide and confine the surface electron current. The experiment qualitatively verifies the guiding and confinement of the strong electron current in the wall surface. The large surface current and induced strong fields are of importance for fast ignition related researches.

Chemical-scale studies of G protein-coupled receptors and ligand-gated ion channels

This dissertation describes studies of G protein-coupled receptors (GPCRs) and ligand-gated ion channels (LGICs) using unnatural amino acid mutagenesis to gain high precision insights into the function of these important membrane proteins.

Chapter 2 considers the functional role of highly conserved proline residues within the transmembrane helices of the D2 dopamine GPCR. Through mutagenesis employing unnatural α-hydroxy acids, proline analogs, and N-methyl amino acids, we find that lack of backbone hydrogen bond donor ability is important to proline function. At one proline site we additionally find that a substituent on the proline backbone N is important to receptor function.

In Chapter 3, side chain conformation is probed by mutagenesis of GPCRs and the muscle-type nAChR. Specific side chain rearrangements of highly conserved residues have been proposed to accompany activation of these receptors. These rearrangements were probed using conformationally-biased β-substituted analogs of Trp and Phe and unnatural stereoisomers of Thr and Ile. We also modeled the conformational bias of the unnatural Trp and Phe analogs employed.

Chapters 4 and 5 examine details of ligand binding to nAChRs. Chapter 4 describes a study investigating the importance of hydrogen bonds between ligands and the complementary face of muscle-type and α4β4 nAChRs. A hydrogen bond involving the agonist appears to be important for ligand binding in the muscle-type receptor but not the α4β4 receptor.

Chapter 5 describes a study characterizing the binding of varenicline, an actively prescribed smoking cessation therapeutic, to the α7 nAChR. Additionally, binding interactions to the complementary face of the α7 binding site were examined for a small panel of agonists. We identified side chains important for binding large agonists such as varenicline, but dispensable for binding the small agonist ACh.

Chapter 6 describes efforts to image nAChRs site-specifically modified with a fluorophore by unnatural amino acid mutagenesis. While progress was hampered by high levels of fluorescent background, improvements to sample preparation and alternative strategies for fluorophore incorporation are described.

Chapter 7 describes efforts toward a fluorescence assay for G protein association with a GPCR, with the ultimate goal of probing key protein-protein interactions along the G protein/receptor interface. A wide range of fluorescent protein fusions were generated, expressed in Xenopus oocytes, and evaluated for their ability to associate with each other.

Microwave dynamics of quasiparticles and critical fields in superconducting films

The microwave response of the superconducting state in equilibrium and non-equilibrium configurations was examined experimentally and analytically. Thin film superconductors were mostly studied in order to explore spatial effects. The response parameter measured was the surface impedance.

For small microwave intensity the surface impedance at 10 GHz was measured for a variety of samples (mostly Sn) over a wide range of sample thickness and temperature. A detailed analysis based on the BCS theory was developed for calculating the surface impedance for general thickness and other experimental parameters. Experiment and theory agreed with each other to within the experimental accuracy. Thus it was established that the samples, thin films as well as bulk, were well characterised at low microwave powers (near equilibrium).

Thin films were perturbed by a small dc supercurrent and the effect on the superconducting order parameter and the quasiparticle response determined by measuring changes in the surface resistance (still at low microwave intensity and independent of it) due to the induced current. The use of fully superconducting resonators enabled the measurement of very small changes in the surface resistance (< 10^-9 Ω/sq.). These experiments yield information regarding the dynamics of the order parameter and quasiparticle systems. For all the films studied the results could be described at temperatures near T_c by the thermodynamic depression of the order parameter due to the static current leading to a quadratic increase of the surface resistance with current.

For the thinnest films the low temperature results were surprising in that the surface resistance decreased with increasing current. An explanation is proposed according to which this decrease occurs due to an additional high frequency quasiparticle current caused by the combined presence of both static and high frequency fields. For frequencies larger than the inverse of the quasiparticle relaxation time this additional current is out of phase (by π) with the microwave electric field and is observed as a decrease of surface resistance. Calculations agree quantitatively with experimental results. This is the first observation and explanation of this non-equilibrium quasiparticle effect.

For thicker films of Sn, the low temperature surface resistance was found to increase with applied static current. It is proposed that due to the spatial non-uniformity of the induced current distribution across the thicker films, the above purely temporal analysis of the local quasiparticle response needs to be generalised to include space and time non-equilibrium effects.

The nonlinear interaction of microwaves arid superconducting films was also examined in a third set of experiments. The surface impedance of thin films was measured as a function of the incident microwave magnetic field. The experiments exploit the ability to measure the absorbed microwave power and applied microwave magnetic field absolutely. It was found that the applied surface microwave field could not be raised above a certain threshold level at which the absorption increased abruptly. This critical field level represents a dynamic critical field and was found to be associated with the penetration of the app1ied field into the film at values well below the thermodynamic critical field for the configuration of a field applied to one side of the film. The penetration occurs despite the thermal stability of the film which was unequivocally demonstrated by experiment. A new mechanism for such penetration via the formation of a vortex-antivortex pair is proposed. The experimental results for the thinnest films agreed with the calculated values of this pair generation field. The observations of increased transmission at the critical field level and suppression of the process by a metallic ground plane further support the proposed model.