Polyferrocenylsilanes as Protective Charge Migration Coatings for Dielectrics

Polyferrocenylsilanes [Fe(η-C₅H₄)₂SiMePh] _n (3) and [Fe(η-C₅H₄)₂SiMe₂] _n (4) were prepared by transition metal-catalyzed ring-opening polymerization (ROP) and thin films of these materials were studied to investigate their potential utility as protective charge migration coatings for dielectrics. Films ( 15 μm) of 3 or 4 cast from a concentrated toluene solution coated on Mylar did not experience any arc discharging when exposed to a beam of low energy (20 keV) electrons for a 1 h time period. In order to further investigate the charge migration properties of polyferrocenylsilanes, thick shapes and films of 3 were prepared by mold-extrusion and solution-casting onto a Teflon substrate, respectively. Charge accumulation measurements on 3 using a nonintrusive electrostatic probe showed that even after a 1 h exposure to a 25 keV electron flux, no appreciable charge accumulation existed. The direction of current flow was explored by constructing a device consisting of a film (thickness ca. 100–130 μm) of polymer 3 coating a layer of copper. When positioned beneath a circular mask and exposed to a low energy electron flux (5–25 keV), measurements of the current at the surface of the polymer film either exposed to or not exposed to the electron flux were not significantly different, and the current recorded from the bare copper connection to the ground was significantly (100–1000 times) higher. Although the mechanism of charge migration in polyferrocenylsilanes is not fully understood, these experiments indicated it may arise from a conduction mechanism, however electron scattering may also be involved.Dedicated to Professor Richard J. Puddephatt in recognition of his outstanding and scholarly contributions to chemistry.     

Contaminant levels in sediments and asteroids (Asterias rubens L., Echinodermata) from the Belgian coast and Scheldt estuary: polychlorinated biphenyls and heavy metals

The Southern Bight of the North Sea is particularly exposed to anthropogenic contamination, due to heavy urbanisation and industrialisation of its catchment area. The present work focuses on polychlorinated biphenyl (PCB) and metal contamination of the marine environment along and off the Belgian coast. Its objectives were to compare the concentrations of seven PCB congeners and four heavy metals in the sediments (a repository for anthropogenic contaminants) and in the asteroid Asterias rubens (a recognized bioindicator species). Nineteen sampling stations were considered between the mouth of the Scheldt Estuary and the southern limit of the Belgian coast (asteroids were found in 10 out of the 19 stations). PCB and metal concentrations measured in sediments and asteroids were in the range of values reported in previous studies. Stations under direct influence of the Scheldt were the most impacted by the considered contaminants. Metal concentrations varied according to the grain-size fraction considered. In asteroids, PCBs and metals were found to be selectively distributed among body compartments, and pyloric caeca were found to most efficiently discriminate between sampling stations contamination levels. PCB and metal analysis of sediments provided a physicochemical evaluation of the contamination, whereas analysis of asteroids introduced a biological dimension to the approach by taking into account bioavailability of the contaminants.     

Greffage de molécules à la surface du silicium par voie électrochimique

The hydrogentated surface of silicon exhibits remarkable properties, but poor resistance to oxidation. To improve its stability, surface hydrogen has been replaced by several organic groups. Such grafting can be carried out chemically by a multi-step reaction scheme. However, an electrochemical approach allows direct reaction with the hydrogenated surface. The porous-silicon surface has been partially methoxylated by a controlled anodic dissolution. If has also been methylated using a non-destructive anodic process, with a yield of 80%, limited only by steric hindrance. The methylated surface of porous silicon exhibits a stability against oxidation increased by an order of magnitude.     

Role of Orai3 in the Pathophysiology of Cancer

The mammalian exclusive Orai3 channel participates in the generation and/or modulation of two independent Ca²⁺ currents, the store-operated current, I_crac, involving functional interactions between the stromal interaction molecules (STIM), STIM1/STIM2, and Orai1/Orai2/Orai3, as well as the store-independent arachidonic acid (AA) (or leukotriene C4)-regulated current I_arc, which involves Orai1, Orai3 and STIM1. Overexpression of functional Orai3 has been described in different neoplastic cells and cancer tissue samples as compared to non-tumor cells or normal adjacent tissue. In these cells, Orai3 exhibits a cell-specific relevance in Ca²⁺ influx. In estrogen receptor-positive breast cancer cells and non-small cell lung cancer (NSCLC) cells store-operated Ca²⁺ entry (SOCE) is strongly dependent on Orai3 expression while in colorectal cancer and pancreatic adenocarcinoma cells Orai3 predominantly modulates SOCE. On the other hand, in prostate cancer cells Orai3 expression has been associated with the formation of Orai1/Orai3 heteromeric channels regulated by AA and reduction in SOCE, thus leading to enhanced proliferation. Orai3 overexpression is associated with supporting several cancer hallmarks, including cell cycle progression, proliferation, migration, and apoptosis resistance. This review summarizes the current knowledge concerning the functional role of Orai3 in the pathogenesis of cancer.     

Relating decision under uncertainty and multicriteria decision making models

This short overview paper points out the striking similarity between decision under uncertainty and multicriteria decision making problems, two areas which have been developed in an almost completely independent way until now. This pertains both to additive and non‐additive (including qualitative) approaches existing for the two decision paradigms. This leads to an emphasis on the remarkable formal equivalence between postulates underlying these approaches (like between the “sure‐thing principle” and mutual preferential independence of criteria). This analogy is exploited by surveying classical results as well as very recent advances. This unified view should be fruitful for a better understanding of the postulates underlying the approaches, for cross‐fertilization, and for adapting artificial intelligence uncertainty representation frameworks to preference modelling. © 2000 John Wiley & Sons, Inc.     

Shelf Life Prediction of Propellants Using a Reaction Severity Index

Shelf life predictions for solid rocket propellant formulations depend upon the existence of a reliable and efficient accelerated aging method. Results presented in this paper demonstrate the failure of simple models like Arrhenius to predict the aging behavior of some composite propellants. This work proposes a new approach for accelerated aging studies of the degradation of the polymeric binder in such propellant formulations. Using a reaction severity index, simple kinetic models have been demonstrated to adequately model the degradation behavior of various propellants submitted to isothermal aging. Furthermore, the versatility of the method allows shelf life predictions for samples experiencing temperature cycles during aging.     

Optimization of Advanced Live-Cell Imaging through Red/Near-Infrared Dye Labeling and Fluorescence Lifetime-Based Strategies

Fluorescence microscopy is essential for a detailed understanding of cellular processes; however, live-cell preservation during imaging is a matter of debate. In this study, we proposed a guide to optimize advanced light microscopy approaches by reducing light exposure through fluorescence lifetime (τ) exploitation of red/near-infrared dyes. Firstly, we characterized key instrumental elements which revealed that red/near-infrared laser lines with an 86x (Numerical Aperture (NA) = 1.2, water immersion) objective allowed high transmission of fluorescence signals, low irradiance and super-resolution. As a combination of two technologies, i.e., vacuum tubes (e.g., photomultiplier) and semiconductor microelectronics (e.g., avalanche photodiode), type S, X and R of hybrid detectors (HyD-S, HyD-X and HyD-R) were particularly adapted for red/near-infrared photon counting and τ separation. Secondly, we tested and compared lifetime-based imaging including coarse τ separation for confocal microscopy, fitting and phasor plot analysis for fluorescence lifetime microscopy (FLIM), and lifetimes weighting for enhanced stimulated emission depletion (STED) nanoscopy, in light of red/near-infrared multiplexing. Mainly, we showed that the choice of appropriate imaging approach may depend on fluorochrome number, together with their spectral/lifetime characteristics and STED compatibility. Photon-counting mode and sensitivity of HyDs together with phasor plot analysis of fluorescence lifetimes enabled the flexible and fast imaging of multi-labeled living H28 cells. Therefore, a combination of red/near-infrared dyes labeling with lifetime-based strategies offers new perspectives for live-cell imaging by enhancing sample preservation through acquisition time and light exposure reduction.     

Photovieillissement d'un copolymère d'éthylène et d'acétate de vinyle en présence de sueur artificielle. II. Evolution morphologique

An artificial photoaging cell was arranged with the goal to study the behaviour of polymers partly immersed in artificial sweat. A poly(ethylene-co-vinyl acetate) (EVA) was photoaged in this cell. On the other hand, photoaging was realized without artificial sweat in order to understand the action of this substrate. Similar studies were carried out with light stabilized EVA. The morphological evolution of the crystalline structures of the polymer was studied by differential scanning calorimetry, mainly the evolution of the melting temperatures, and secondly those of the glass transition temperatures and of the melting enthalpies. Thus, it was possible to understand the reorganization of two crystalline structures contained in the fresh EVA, the first one rich in poly(vinyl acetate) and the second one in rich in polyethylene.     

Polymerization of β-butyrolactone initiated with Al(OiPr)3

Polymerization of β-butyrolactone has been studied in toluene with Al(OⁱPr)₃ as an initiator. The ring-opening polyaddition proceeds through a coordination–insertion mechanism at a very low rate. Well defined α-isopropylester, ω-hydroxy poly(β-butyrolactone)s (PBL) are formed with a narrow molecular weight distribution at low monomer-to-initiator molar ratios, When this ratio is higher (ca. 170), a competition occurs between propagation and side reactions, i.e. elimination, inter- and intra-molecular transesterifications and thermal degradation, which is responsible for a loss of control of the PBL molecular charcteristics. The addition of a Lewis base (1 equivalent of nicotine/Al) to the Al-alkoxide initiator has no significant effect on the polymerization rate, although the chain microstructure is deeply affected since predominantly syndiotactic PBL chains are formed (63% syndio-diads) in contrast to a completely atactic polymer in the absence of nicotine.