New water-soluble calix[4]arene-based bipyridyl podands incorporating carboxylate groups

New calixarene-based bis-bipyridyl podands incorporating two sodium (4-oxo)-butanoate or four sodium carboxymethyl groups at the upper rim were synthesised and fully characterised. The (4-oxo)-butanoate derivative bearing unsubstituted bipyridyl arms was not soluble in water at neutral pH, while its 4,4′-dicarboxylate analogue was perfectly soluble, as were the carboxymethyl derivatives. The association of water solubility to the chelating behaviour of the bipyridyl subunits resulted in the ability to complex the unstable copper(I) cation in water, even in the presence of bovine serum albumin.     

Construction d'une paramétrixe pour des opérateurs différentiels hypoelliptiques marimaux sur un espace homogéne d'un groupe de Lie nilpotent gradué de rang 2

Soient G une alébre de Lie nilpotente stratifée de rang 2, une sous-algébre de G, _0, la représentation de G dans l'espace L ²( \ G) indiute par le caractére trivial C, P un opérateur homogène appartenant à l'algébre universelle enveloppante (complexifiée) U(G) tel que l'opérateur _0, (P) soit hypoelliptique maximal. Cet opérateur peut s'exprimer par une intégrale dépendant de la restriction du symbole p de P au sousensemble = G · décrit par les orbites des éléments de dans la représentation contragrédiente de G dans G ^*.Une algèbre de symboles définis sur est construite et permet de déterminer une paramétrixe de _0, (P); des résultats de réguralité de cet opérateur dans des espaces de Sobolev adaptés sont ensuite obtenus.     

Hamaker constants in integrated circuit metalization

A new method for determining Hamaker constants was examined for materials of interest in integrated circuit manufacture. An ultra-high vacuum atomic force microscope and an atomic force microscope operated in a nitrogen environment were used to measure the interaction forces between metals, dielectrics, and barriers used during the metalization portion of integrated circuit manufacturing. The materials studied included copper, silver, titanium nitride, silicon dioxide, poly(tetrafluoroethylene), and parylene-N. Spheres coated with a material of interest were mounted on AFM cantilevers and brought into contact with substrates of interest. The interaction force was measured as the cantilever approached the substrate but before the two surfaces came into contact, and also when the particle was pulled out of contact with the substrate. The Hamaker constant calculation from the contact measurement is based on an adhesion model that quantifies the contribution of geometrical, morphological and mechanical properties of materials to the measured adhesion force. Hamaker constants determined with this new approach were compared with values found by using the Derjaguin approximation for a sphere to describe the interaction force as the cantilever approaches the surface. Both approaches produced similar values for most of the systems studied, with variations of less than 10%.     

Simulation of the Adhesion of Particles to Surfaces

The removal of micrometer and submicrometer particles from dielectric and metal films represents a challenge in postchemical mechanical polishing cleaning. Proper modeling of the adhesive force between contaminant particles and these films is needed to develop optimal solutions to postchemical mechanical polishing cleaning. We have previously developed and experimentally validated a model to describe the adhesion between spherical particles and thin films. This simulation expands previous models to characterize the adhesive interaction between asymmetrical particles, characteristic of a polishing slurry, and various films. Our simulation accounts for the contact area between particles and substrates, as well as the morphology of the surfaces. Previous models fail to accurately describe the contact of asymmetrical particles interacting with surfaces. By properly accounting for nonideal and geometry and morphology, the simulation predicts a more accurate adhesive force than predictions based upon an ideal van der Waals model. The simulation is compared to experimental data taken for both semi-ideal particle-substrate systems (polystyrene latex spheres in contact with silicon films) and asymmetrical systems (alumina particles in contact with various films). Copyright 2001 Academic Press.     

Modelisation of the Electric Field Linear Response of an Infinite Aggregate of All-Trans Hexatriene Chains by Electrostatic Interaction Model

A classical electrostatic polarization scheme using the additive distribution procedure has been applied to determine the longitudinal polarizability of an all-trans hexatriene molecule in an infinite stretched fiber. The parameters have been derived from ab initio CPHF/6-31G calculations and the electrostatic scheme has been validated via comparison with ab initio results on small clusters. Upon packing the polarizability of all-trans hexatriene increases by 7%. This small increase results from the balance between the enhancement of the polarizability due to collinear packing and the reduction associated with lateral packing.     

Structure and properties of hydrophobically end-capped poly(ethylene oxide) solutions in the presence of monovalent and divalent cations

Hydrophobically modified poly(ethylene oxide), HMPEO, was studied in concentrated salt solutions. The influence of salts was compared to the effect of temperature on poly(ethylene oxide), PEO. As expected, the addition of monovalent cations (Na(+), K(+)) has the same effect as an increase in temperature in agreement with the thermodynamic properties of PEO: a decrease in solubility, micelle size, and viscosity was observed. Moreover, the intensity of neutron scattering peaks (characteristic of the semi-dilute solutions of these associative polymers) increases due to the collapse of PEO coronae in micelles. Very peculiar behavior was observed in the presence of divalent cations (Ca(2+), Mg(2+)): larger micelle aggregates and higher viscosities, relaxation times, and activation energies were observed by dynamic rheology. This behavior is attributed to interactions between divalent cations and oxygen in PEO backbones close to the micelle core, which may reinforce intermicellar bridges.     

Biocompatible polymers for antibody support on gold surfaces

The elimination or minimization of non-specific protein adsorption from serum is critical for the use of surface plasmon resonance (SPR) sensors for in vitro and in vivo analysis of complex biological solutions. The ultimate goals in this application are to minimize non-specific adsorption of protein and to maximize analyte signal. A reduction of the non-specific protein adsorption from serum of up to 73% compared to carboxymethylated-dextran 500 kDa (CM-dextran) was achieved following a survey of eight biocompatible polymers and 10 molecular weights of CM-dextran. These coatings minimize non-specific adsorption on the sensor while also serving as immobilization matrices for antibody fixation to the probes. Polymers including polysaccharides: CM-dextrans, CM-hyaluronic acid, hyaluronic acid, and alginic acid were investigated. Humic acid, polylactic acid, polyacrylic acid, orthopyridyldisuldfide–polyethyleneglycol–N-hydroxysuccinimide (OPSS–PEG–NHS), and a synthesized polymer; polymethacrylic-acid-co-vinyl-acetate (PMAVA) were also used. The non-specific protein adsorption reduction was measured over a 14 day period at 0 °C for each polymer. Calibration curves using some of these polymers were constructed to show the performance and low detection limit possibilities of these new antibody supports. For many of the polymers, this is the first demonstration of employment as an antibody support for an optical or surface active sensor. CM-dextran is the polymer offering the largest signal for the antigen detection. However, the biocompatible polymers demonstrate a greater stability to non-specific binding in serum. These biocompatible polymers offer different alternatives for CM-dextran.     

Diffraction dissociation of nuclei in 450 GeV/c proton-nucleus collisions

Diffractive dissociation of nuclei (Be, Al, W) in collisions with 450 GeV/c protons,pApX, has been measured with the HELIOS spectrometer at the CERN Super Proton synchrotron. The dependence of the single-diffraction cross-section on the nuclear massA can be parametrized as _SD mb×A ^0.35±0.02, showing the peripheral nature of the process. The differential cross-section d_SD=(3.8±0.3)mb ×A ^0.35±0.02, is exponential with the slope parameter, increasing from 6.2±0.4 (GeV/c)^–2 for beryllium to 7.9±0.5 (GeV/c)^–2 for tungsten. The slope parameter also increases with increasing massM _X of the diffractively produced state. The rapidity, multiplicity, and transverse-momentum distributions of the particles of the diffractively produced stateX show a longitudinal phase-space population and are remarkably insensitive to the nuclear mass. This, together with theA ^1/3 dependence of _SD, suggests that the dominant process of nuclear diffractive excitation is the dissociation of single nucleons.Deceased     

Synthesis of chiral α-substituted N-[((2S)-2-hydroxy-2-phenyl)-ethyl]-2-phenylglycine derivatives by diastereocontrolled alkylation of (6 R)-2,3,5,6-tetrahydro-3,6-diaryl-N-[(2′R)-(2′-methyl)phenyl-methyl]-4H-1,4-oxazin-2-ones

The synthesis of α-substituted N-[((2S)-2-hydroxy-2-phenyl)-ethyl]-2-phenylglycine derivatives is reported. The key step of the sequence is the highly diastereoselective alkylation of (6R)-2,3,5,6-tetrahydro-3,6-diaryl-N-[(2′R)-(2′-methyl)phenylmethyl]-4H-1,4-oxazin-2-ones after deprotonation with t-BuOK. Opening of the resulting oxazinone with ethanolic KOH, followed by hydrogenolysis of the corresponding N-[(2R)-(2-methyl)phenylmethyl] compound to furnish the expected 2-phenylglycine derivative, is also described.