Freeform fabrication of aluminum metal-matrix composites

A series of metal-matrix composites were formed by extrusion freeform, fabrication of a sinterable aluminum alloy in combination with silicon carbide particles and whiskers, carbon fibers, alumina particles, and hollow flyash cenospheres. Silicon carbide particles were most successful in that the composites retained high density with up to 20 vol% of reinforcement and the strength approximately doubles over the strength of the metal matrix alone. Comparison with simple models suggests that this unexpectedly high degree of reinforcement can be attributed to the concentration of small silicon carbide particles around the larger metal powder. This fabrication method also allows composites to be formed with hollow spheres that cannot be formed by other powder or melt methods.

Metal-insulator transition and charge ordering in the extended Hubbard model at one-quarter filling

We study, with exact diagonalization, the zero temperature properties of the quarter-filled extended Hubbard model on a square lattice. We find that increasing the ratio of the intersite Coulomb repulsion, V, to the bandwidth drives the system from a metal to a charge ordered insulator. The evolution of the optical conductivity spectrum with increasing V is in agreement with the observed optical conductivity of several layered molecular crystals with the theta and beta crystal structures.

Copper transfer from the Cu(I) chaperone, CopZ, to the repressor, Zn(II)CopY: Metal coordination environments and protein interactions

Extracellular copper regulates the DNA binding activity of the CopY repressor of Enterococcus hirae and thereby controls expression of the copper homeostatic genes encoded by the cop operon. CopY has a CxCxxxxCxC metal binding motif. CopZ, a copper chaperone belonging to a family of metallochaperones characterized by a MxCxxC metal binding motif, transfers copper to CopY. The copper binding stoichiometries of CopZ and CopY were determined by in vitro metal reconstitutions. The stoichiometries were found to be one copper(l) per CopZ and two copper(l) per CopY monomer. X-ray absorption studies suggested a mixture of two- and three-coordinate copper in Cu(1)CopZ, but a purely three-coordinate copper coordination with a Cu-Cu interaction for Cu(1)(2)CopY. The latter coordination is consistent with the formation of a compact binuclear Cu(l)-thiolate core in the CxCxxxxCxC binding motif of CopY. Displacement of zinc, by copper. from CopY was monitored with 2,4-pyridylazoresorcinol. Two copper(l) ions were required to release the single zinc(II) ion bound per CopY monomer. The specificity of copper transfer between CopZ and CopY was dependent on electrostatic interactions. Relative copper binding affinities of the proteins were investigated using the chelator, diethyldithiocarbamic acid (DDC). These data suggest that CopY has a higher affinity for copper than CopZ. However, this affinity difference is not the sole factor in the copper exchange: a charge-based interaction between the two proteins is required for the transfer reaction to proceed. Gain-of-function mutation of a CopZ homologue demonstrated the necessity of four lysine residues on the chaperone for the interaction with CopY. Taken together, these results suggest a mechanism for copper exchange between CopZ and CopY.

Organic microcavity light-emitting diodes with metal mirrors: dependence of the emission wavelength on the viewing angle

Organic microcavity light-emitting diodes typically exhibit a blueshift of the emitting wavelength with increasing viewing angle. We have modeled the shift of the resonance wavelength for several metal mirrors. Eight metals (Al, Ag, Cr, Ti, Au, Ni, Pt, and Cu) have been considered as top or bottom mirrors, depending on their work functions. The model fully takes into account the dependence of the phase change that occurs on reflection on angle and wavelength for both s and p polarization, as well as on dispersion in the organic layers. Different contributions to the emission wavelength shift are discussed. The influence of the thickness of the bottom mirror and of the choice and thickness of the organic materials inside the cavity has been investigated. Based on the results obtained, guidelines for a choice of materials to reduce blueshift; are given. (C) 2002 Optical Society of America.

Numerical study of hydrogenic effective mass theory for an impurity P donor in Si in the presence of an electric field and interfaces

In this paper we examine the effects of varying several experimental parameters in the Kane quantum computer architecture: A-gate voltage, the qubit depth below the silicon oxide barrier, and the back gate depth to explore how these variables affect the electron density of the donor electron. In particular, we calculate the resonance frequency of the donor nuclei as a function of these parameters. To do this we calculated the donor electron wave function variationally using an effective-mass Hamiltonian approach, using a basis of deformed hydrogenic orbitals. This approach was then extended to include the electric-field Hamiltonian and the silicon host geometry. We found that the phosphorous donor electron wave function was very sensitive to all the experimental variables studied in our work, and thus to optimize the operation of these devices it is necessary to control all parameters varied in this paper.

A review of drainage and spontaneous rupture in free standing thin films with tangentially immobile interfaces

A review of spontaneous rupture in thin films with tangentially immobile interfaces is presented that emphasizes the theoretical developments of film drainage and corrugation growth through the linearization of lubrication theory in a cylindrical geometry. Spontaneous rupture occurs when corrugations from adjacent interfaces become unstable and grow to a critical thickness. A corrugated interface is composed of a number of waveforms and each waveform becomes unstable at a unique transition thickness. The onset of instability occurs at the maximum transition thickness, and it is shown that only upper and lower bounds of this thickness can be predicted from linear stability analysis. The upper bound is equivalent to the Freakel criterion and is obtained from the zeroth order approximation of the H-3 term in the evolution equation. This criterion is determined solely by the film radius, interfacial tension and Hamaker constant. The lower bound is obtained from the first order approximation of the H-3 term in the evolution equation and is dependent on the film thinning velocity A semi-empirical equation, referred to as the MTR equation, is obtained by combining the drainage theory of Manev et al. [J. Dispersion Sci. Technol., 18 (1997) 769] and the experimental measurements of Radoev et al. [J. Colloid Interface Sci. 95 (1983) 254] and is shown to provide accurate predictions of film thinning velocity near the critical thickness of rupture. The MTR equation permits the prediction of the lower bound of the maximum transition thickness based entirely on film radius, Plateau border radius, interfacial tension, temperature and Hamaker constant. The MTR equation extrapolates to Reynolds equation under conditions when the Plateau border pressure is small, which provides a lower bound for the maximum transition thickness that is equivalent to the criterion of Gumerman and Homsy [Chem. Eng. Commun. 2 (1975) 27]. The relative accuracy of either bound is thought to be dependent on the amplitude of the hydrodynamic corrugations, and a semiempirical correlation is also obtained that permits the amplitude to be calculated as a function of the upper and lower bound of the maximum transition thickness. The relationship between the evolving theoretical developments is demonstrated by three film thickness master curves, which reduce to simple analytical expressions under limiting conditions when the drainage pressure drop is controlled by either the Plateau border capillary pressure or the van der Waals disjoining pressure. The master curves simplify solution of the various theoretical predictions enormously over the entire range of the linear approximation. Finally, it is shown that when the Frenkel criterion is used to assess film stability, recent studies reach conclusions that are contrary to the relevance of spontaneous rupture as a cell-opening mechanism in foams. (C) 2003 Elsevier Science B.V. All rights reserved.

Structural variations and formation constants of first-row transition metal complexes of biologically active aroylhydrazones

Iron chelators of the 2-pyridinecarbaldehyde isonicotinoylhydrazone (HPCIH) class show high potential for the treatment of iron overload diseases. In the present study, selected first-row transition metal (from Mn to Zn) complexes with HPCIH and 2-pyridinecarbaldehyde (4'-aminobenzoyl)hydrazone (HPCAH) were synthesised and characterised. Crystallography reveals that HPCAH exclusively forms bis complexes with divalent transition metals, with each ligand coordinating meridionally through its pyridine-N, imine-N and carbonyl-O atoms, forming distorted octahedral cis-MN4O2 complexes. Complexes of HPCIH were more varied and unpredictable, with metal/ligand ratios of 1:1, 1:2, 2:2 and 3:2 obtained with different metal ions. The isonicotinoyl ring N-atom in HPCIH was found to be an effective ligand, and this resulted in the varied metal/ligand ratios observed. The formation constants of divalent metal complexes with HPCIH were determined by potentiometric titrations and the values obtained were consistent with similar tridentate ligands and with the Irving-Williams order. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

Functionalized macrocyclic compounds: potential sensors of small molecules and ions

The potential applications of macrocycles in chemistry and at its interfaces with biology and physics continue to emerge, one of which is as receptors for small molecules and ions. This review illustrates these applications with examples from the last ten years employing complexation as the binding mechanism; some of the systems presented have already found real-world sensor applications. In any case, the challenges remain to design more selective and sensitive receptors for guests.