Analysis of conducting-system frequency response data for an interfacial amorphous phase of copper-core oxide-shell nanocomposites

Complex electrical-conductivity experimental data sets for the interfacial amorphous phase in copper-core-copper-oxide-shell nanostructured composites have been analyzed using two Kohlrausch-related frequency response models recently developed for analysis of the dispersive electrical response of conductive materials. Such analysis has been carried out for both the precursor (herein referred to as the reference) glass as well as the glass in which the core-shell nanostructure was developed after suitable heat treatment. Complex nonlinear-least-squares data fitting at each temperature employed composite Kohlrausch models that included electrode effects. Because of the lack of sufficient high-frequency data, it was necessary to use fixed, rather than free, values of the shape parameter beta1 of the model. On the basis of topological considerations, its values were set at 13 and 23 for the reference glass and the core-shell structured glass, respectively. The activation energies of resistivity for the reference and the treated glasses were found to have values of about 2 and 0.4 eV, respectively, indicating two different mechanisms of electrical conduction. A blocking-electrode measurement on the reference glass indicated the presence of an electronic as well as an ionic component of the electrical conductivity, with the ionic part dominating at the temperatures for which the present analyses were carried out.     

Search for DeltaS = 2 nonleptonic hyperon decays

A sensitive search for the rare decays Omega(-)--> Lambdapi(-) and Xi(0)--> ppi(-) has been performed using data from the 1997 run of the HyperCP (Fermilab E871) experiment. Limits on other such processes do not exclude the possibility of observable rates for |DeltaS| = 2 nonleptonic hyperon decays, provided the decays occur through parity-odd operators. We obtain the branching-fraction limits B(Omega(-)-->Lambdapi(-)) < 2.9 x 10(-6) and B(Xi(0)--> ppi(-)) < 8.2 x 10(-6), both at 90% confidence level.     

Computing roadmaps of semi-algebraic sets on a variety

We consider a semi-algebraic set defined by polynomials in variables which is contained in an algebraic variety . The variety is assumed to have real dimension the polynomial and the polynomials defining have degree at most . We present an algorithm which constructs a roadmap on . The complexity of this algorithm is . We also present an algorithm which, given a point of defined by polynomials of degree at most , constructs a path joining this point to the roadmap. The complexity of this algorithm is These algorithms easily yield an algorithm which, given two points of defined by polynomials of degree at most , decides whether or not these two points of lie in the same semi-algebraically connected component of and if they do computes a semi-algebraic path in connecting the two points.

     

Template based growth of nanoscaled films: a brief review

Growth of ultrathin films of metals and inorganic materials using various templates — both solid and liquid has been reviewed. Such nanoscaled films have been found to be effective in fabrication of devices and sensors. Use of crystal nanochannels of some inorganic compounds has been found to induce novel properties to the films grown within them. It is expected the latter approach will lead to the synthesis of materials with hitherto unknown properties.     

Self assembled tetranuclear Cu4(II), Ni4(II) [2 × 2] square grids and a dicopper(II) complex of heterocycle based polytopic ligands - Magnetic studies

The ditopic ligand PyPzOAP (N-[(Z)-amino(pyridin-2-yl)methylidene]-5-methyl-1-(pyridin-2-yl)-1H-pyrazole-3-carbohydrazonic acid) and the polytopic ligand 2-PzCAP (N'(3),N'(5)-bis[(1E)-1-(pyridin-2-yl)ethylidene]-1H-pyrazole-3,5-dicarbohydrazide) were synthesized in situ by condensation of methyl imino picolinate with 5-methyl-1-(2-pyridyl) pyrazole-3-carbohydrazide and 2-acetyl pyridine with pyrazole-3,5-dicarbohydrazide respectively. The ligands PyPzOAP and PzOAP (reported earlier, Dalton Trans., 2007, 1229) self-assemble to form homoleptic [2 × 2] tetranuclear M(4) (M = Cu(II) and Ni(II)) square grids structures [Cu(4)(PyPzOAP)(4)](NO(3))(4) (1), [Cu(4)(PzOAP)(4)](ClO(4))(4) (2) and [Ni(4)(PyPzOAP)(4)](NO(3))(4)·8H(2)O·2CH(3)CN (3). While the ligand 2-PzCAP forms a dicopper(II) complex [Cu(2)(2-PzCAP)(OH)(NO(3))(H(2)O)](NO(3))·2H(2)O (4). The complex 1 is a perfect square grid (a = 4.201 ?), whereas, 2 and 3 are almost square grids. All these compounds have been characterized by X-ray structural analyses and variable temperature magnetic susceptibility measurements. EPR studies have also been carried out for complexes 1, 2 and 4. In the Cu(4) grid (1), all the Cu(II) centers are in a distorted octahedral environment with N(4)O(2) chromophore, while, in complex 2, all four Cu(II) centers have a square pyramidal environment with N(3)O(2) chromophore. In complex 3, all four Ni(II) centers have distorted octahedral geometry with N(4)O(2) chromophore. In compound 4, the Cu(II) centers are in square pyramidal environment with N(3)O(2) chromophore. The magnetic properties of compounds 1 and 2 show the presence of intramolecular ferromagnetic exchange interaction (J = 5.88 cm(-1) for 1 and 4.78 cm(-1) for 2). The complex 3 shows weak intramolecular antiferromagnetic interaction (J = -4.02 cm(-1)). While, complex 4, shows strong antiferromagnetic behavior (J = -443 cm(-1)).     

Bacterial adhesion on hybrid cationic nanoparticle-polymer brush surfaces: ionic strength tunes capture from monovalent to multivalent binding

This paper describes the creation of hybrid surfaces containing cationic nanoparticles and biocompatible PEG (polyethylene glycol) brushes that manipulate bacterial adhesion for potential diagnostic and implant applications. Here, ～10 nm cationically functionalized gold nanoparticles are immobilized randomly on negative silica surfaces at tightly controlled surface loadings, and the remaining areas are functionalized with a hydrated PEG brush, using a graft copolymer of poly-l-lysine and PEG (PLL-PEG), containing 2000 molecular weight PEG chains and roughly 30% functionalization of the PLL. The cationic nanoparticles attract the negative surfaces of suspended Staphylococcus aureus bacteria while the PEG brush exerts a steric repulsion. With the nanoparticle and PEG brush heights on the same lengthscale, variations in ionic strength are demonstrated to profoundly influence the capture of S. aureus on these surfaces. For bacteria captured from gentle flow, a crossover from multivalent to univalent binding is demonstrated as the Debye length is increased from 1 to 4 nm. In the univalent regime, 1 um diameter spherical bacteria are captured and held by single nanoparticles. In the multivalent regime, there is an adhesion threshold in the surface density of nanoparticles needed for bacterial capture. The paper also documents an interesting effect concerning the relaxations in the PLL-PEG brush itself. For brushy surfaces containing no nanoparticles, bacterial adhesion persists on newly formed brushes, but is nearly eliminated after these brushes relax, at constant mass in buffer for 12h. Thus brushy relaxations increase biocompatibility.     

Synthesis, crystal structure, spectroscopic and photoluminescence studies of manganese(II), cobalt(II), cadmium(II), zinc(II) and copper(II) complexes with a pyrazole derived Schiff base ligand

Varying coordination modes of the Schiff base ligand H₂L [5-methyl-1-H-pyrazole-3-carboxylic acid (1-pyridin-2-yl-ethylidene)-hydrazide] towards different metal centers are reported with the syntheses and characterization of four mononuclear Mn(II), Co(II), Cd(II) and Zn(II) complexes, [Mn(H₂L)(H₂O)₂](ClO₄)₂(MeOH) (1), [Co(H₂L)(NCS)₂] (2), [Cd(H₂L)(H₂O)₂](ClO₄)₂ (3) and [Zn(H₂L)(H₂O)₂](ClO₄)₂ (4), and a binuclear Cu(II) complex, [Cu₂(L)₂](ClO₄)₂ (5). In the complexes 1-4 the neutral ligand serves as a 3N,2O donor where the pyridine ring N, two azomethine N and two carbohydrazine oxygen atoms are coordinatively active, leaving the pyrazole-N atoms inactive. In the case of complex 5, each ligand molecule behaves as a 4N,O donor utilizing the pyridine N, one azomethine N, the nitrogen atom proximal to the azomethine of the remaining pendant arm and one pyrazole-N atom to one metal center and the carbohydrazide oxygen atom to the second metal center. The complexes 1-4 are pentagonal bipyramidal in geometry. In each case, the ligand molecule spans the equatorial plane while the apical positions are occupied by water molecules in 1, 3 and 4 and two N bonded thiocyanate ions in 2. In complex 5, the two Cu(II) centers have almost square pyramidal geometry (τ = 0.05 for Cu1 and 0.013 for Cu2). Four N atoms from a ligand molecule form the basal plane and the carbohydrazide oxygen atom of a second ligand molecule sits in the apex of the square pyramid. All the complexes have been X-ray crystallographically characterized. The Zn(II) and Cd(II) complexes show considerable fluorescence emission while the remaining complexes and the ligand molecule are fluorescent silent.     

Ab initio calculations on XFnq (X = I,Xe, Cs,and Ba; n=1, 2, 4, and 6; q=−1, 0, +1, and +2) molecules

Ab initio calculations employing relativistic effective core potentials were carried out to investigate the electronic structure of xenon fluoride molecules. The chemical bonds and geometrical stability of some isoelectronic ions, which have the central atom replaced by iodine, cesium, and barium ions, were also investigated. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 81: 238–245, 2001