Molecular simulation and experimental study of substituted polyacetylenes: fractional free volume, cavity size distributions and diffusion coefficients

Glassy, disubstituted acetylene-based polymers exhibit extremely high gas permeabilities and high vapor/gas selectivities, which is quite unusual for conventional glassy polymers such as polysulfone. Diffusion coefficients of poly[1-phenyl-2-[p-(trimethylsilyl)phenyl]acetylene] (PTMSDPA) and poly[diphenylacetylene] (PDPA) were obtained using both molecular simulation and experimental techniques. PTMSDPA, a disubstituted glassy acetylene-based polymer, exhibits higher diffusivity than its desilylated analogue, PDPA. Simulation results are in good agreement with experimental data. Cavity size (free volume) distributions of both polymers are also obtained using an energetic-based algorithm (in't Veld et al., J. Phys. Chem. B 2000, 104, 12028) developed recently. Larger cavities in PTMSDPA contribute to its higher diffusivity, and higher permeability.     

High-throughput screening and optimization of photoembossed relief structures

A methodology for the rapid design, screening, and optimization of coating systems with surface relief structures, using a combination of statistical experimental design, high-throughput experimentation, data mining, and graphical and mathematical optimization routines was developed. The methodology was applied to photopolymers used in photoembossing applications. A library of 72 films was prepared by dispensing a given amount of sample onto a chemically patterned substrate consisting of hydrophilic areas separated by fluorinated hydrophobic barriers. Film composition and film processing conditions were determined using statistical experimental design. The surface topology of the films was characterized by automated AFM. Subsequently, models explaining the dependence of surface topologies on sample composition and processing parameters were developed and used for screening a virtual 4000-membered in silico library of photopolymer lacquers. Simple graphical optimization or Pareto algorithms were subsequently used to find an ensemble of formulations, which were optimal with respect to a predefined set of properties, such as aspect ratio and shape of the relief structures.     

Ultrathin silver‐coated gold nanoparticles as suitable substrate for surface‐enhanced Raman scattering

Surface‐enhanced Raman scattering (SERS) is an extremely powerful tool for the analysis of the composition of bimetallic nanoparticle (BNP) surfaces because of the different adsorption schemes adopted by several molecules on different metals, such as Au and Ag. The preparation of BNPs normally implies a change in the plasmonic properties of the core metal. However, for technological applications it could be interesting to synthesize core–shell structures preserving these original plasmonic properties. In this work, we present a facile method for coating colloidal gold nanoparticles (NPs) in solution with a very thin shell of silver. The resulting bimetallic Au@Ag system maintains the optical properties of gold but shows the chemical surface affinity of silver. The effectiveness of the coating method, as well as the progressive silver enrichment of the outermost part of the Au NPs, has been monitored through the SERS spectra of several species (chloride, luteolin, thiophenol and lucigenin), which show different behaviors on gold and silver surfaces. A growth mechanism of the Ag shell is proposed on the basis of the spectroscopic and microscopic data consisting in the formation and deposit of Ag clusters on the Au NP surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Search for f(J)(2220) in radiative J/ψ decays

We present a search for f(J)(2220) production in radiative J/ψ→γf(J)(2220) decays using 460 fb?1 of data collected with the BABAR detector at the SLAC PEP-II e(+)e? collider. The f(J)(2220) is searched for in the decays to K(+)K? and K(S)?K(S)?. No evidence of this resonance is observed, and 90% confidence level upper limits on the product of the branching fractions for J/ψ→γf(J)(2220) and f(J)(2220)→K(+)K?(K(S)?K(S)?) as a function of spin and helicity are set at the level of 10??, below the central values reported by the Mark III experiment.     

Correlation of F0F1-ATPase inhibition and antiproliferative activity of apoptolidin analogues

[structure: see text] Apoptolidin (1) exhibits potent and highly selective apoptosis inducing activity against sensitive cancer cell lines and is hypothesized to act by inhibition of mitochondrial F(0)F(1)-ATP synthase. A series of apoptolidin derivatives, including a new intermolecular Diels-Alder adduct, were analyzed for antiproliferative activity in E1A-transformed rat fibroblasts. Potent F(0)F(1)-ATPase inhibition was not a sufficient determinant of antiproliferative activity for several analogues, suggesting the existence of a secondary biological target or more complex mode of action for apoptolidin.     

Dynamic instability of thin viscoelastic films under lateral stress

We study the influence of lateral stress on the stability of thin viscoelastic films. The free surface of a deposited film under stress is shown to undergo an instability initiated by an anisotropic diffusion of the polymer molecules. This instability ultimately results in the formation of holes provided that the initial surface fluctuations are larger than a critical value. The latter is found to decrease when increasing the stress. An increase of the holes number density with the stress is therefore predicted. Most interestingly, the holes number density is also predicted to increase when increasing the molecular weight of the polymers. Additionally, we demonstrate that the friction of the substrate suppresses any spatial coherence between holes on large length scales. These predictions explain recent experimental observations made on thin spin-coated polystyrene films [G. Reiter, Nat. Mater. 4, 754 (2005)10.1038/nmat1484].     

ACCURATE ATTENUATION CORRECTION FOR ALGEBRAIC RECONSTRUCTION TECHNIQUE IN SPECT

We present a new iterative reconstruction algorithm to improve the algebraic reconstruction technique （ART） for the Single-Photon Emission Computed Tomography. Our method is a generalization of the Kaczmarz iterative algorithm for solving linear systems of equations and introduces exact and implicit attenuation correction derived from the attenuated Radon transform operator at each step of the algorithm. The performances of the presented algorithm have been tested upon various numerical experiments in presence of both strongly non-uniform attenuation and incomplete measurements data. We also tested the ability of our algorithm to handle moderate noisy data. Simulation studies demonstrate that the proposed method has a significant improvement in the quality of reconstructed images over ART. Moreover, convergence speed was improved and stability was established, facing noisy data, once we incorporate filtration procedure in our algorithm.     

High oxygen pressures and the stabilization of six-coordinated Ir(VI) in an oxygen lattice

Abstract

During these last twenty five years a great efforts have been made in the Laboratoire de Chimie du Solide du CNRS in order to develop high oxygen pressure for the stabilization of unusual oxidation state of transition elements.

The aims of such research works was to correlate the increase of the Mⁿ⁺-O bond covalency versus the increase of the oxidation state n+ to the physicochemical properties of resulting oxides [1].

Iridium was an interesting element due to its position (5d) in the Periodic Table. In 1980 Ir(V) (d⁴) was stabilized in La₂LiIrO₆ in the perovskite structure [2]. Such a study had underlined the strong value of the spin-orbit coupling associated to Ir(V) [3].

The stabilization of Ir(VI) is interesting from two points of view : (i) its isotropic electronic configuration (d³), (ii) such a high oxidation state could lead to the strongest M-O bond in an oxygen lattice.

Selecting, through a specific methodology, the most appropriate local structural and chemical factors and with the help of high oxygen pressure, Ir(V1) was stabilized in the perovskite Ba₂CaIrO₆. Structural, magnetic and Mössbauer studies have been carried out in order to characterize the physicochemical properties induced by this unusual oxidation state.     

A simple constructive approach to quadratic BSDEs with or without delay

This paper provides a simple approach for the consideration of quadratic BSDEs with bounded terminal conditions. Using solely probabilistic arguments, we retrieve the existence and uniqueness result derived via PDE-based methods by Kobylanski (2000) [14]. This approach is related to the study of quadratic BSDEs presented by Tevzadze (2008) [19]. Our argumentation, as in Tevzadze (2008) [19], highly relies on the theory of BMO martingales which was used for the first time for BSDEs by Hu et al. (2005) [12]. However, we avoid in our method any fixed point argument and use Malliavin calculus to overcome the difficulty. Our new scheme of proof allows also to extend the class of quadratic BSDEs, for which there exists a unique solution: we incorporate delayed quadratic BSDEs, whose driver depends on the recent past of the Y$Y$ component of the solution. When the delay vanishes, we verify that the solution of a delayed quadratic BSDE converges to the solution of the corresponding classical non-delayed quadratic BSDE.     

Zero‐valent Iron Nanoparticles Modified Screen‐printed Electrode for FIA or HPLC Amperometric Detection of Metronidazole in Pharmaceutical Formulations

A zero‐valent iron nanoparticles modified electrode was employed as an amperometric detector in flow conditions to determine metronidazole and 2‐methyl‐5‐nitroimidazole in pharmaceutical formulations. Flow injection analysis at ?0.6 V (vs. Ag) achieved limits of detection of 2 and 6 μM for metronidazole and 2‐methyl‐5‐nitroimidazole, respectively, but the analysis was not discriminative between the two compounds. When reverse phase high performance liquid chromatography was applied previous to the electrochemical detection both analytes could be analysed simultaneously. However, the limits of detection slightly increased (10 μM) as a consequence of the use of an organic solvent and a lower sample volume. The relative standard deviation of analytical repeatability was <4.0 % in both techniques. The methods were validated by comparing the results obtained from the analysis of commercial samples with those provided by HPLC‐DAD and no significant differences were detected. Results probed that the modified electrode was a successful tool in the FIA and HPLC analysis of nitro compounds.