One-electron reduction of superoxide radical-anions by 3-alkylpolyhydroxyflavones in micelles. Effect of antioxidant alkyl chain length on micellar structure and reactivity

In micellar solutions, one-electron reduction of (*)O 2 (-) radical-anions by 3-alkylpolyhydroxyflavones (FnH) with alkyl chains of n = 1, 4, 6, 10 carbons produces phenoxyl radicals ( (*)Fn) identical to those obtained by one-electron oxidation by (*)Br 2 (-) radical-anions or by repair of tryptophan radicals. In cetyltrimethylammonium bromide (CTAB), F1H localizes in the Stern layer, and alkyl chains of other FnH solubilize in the hydrophobic interior, interacting with cetyl tails. This interaction produces more compact micelles with lower intramicellar fluidity, as suggested by the increase in the pseudo-first-order rate constant of (*)Fn formation ( k 1) from approximately 390 s (-1) for n = 1 to 610 s (-1) for n = 10, leading to an intramicellar bimolecular rate constant of 1 x 10 (5) M (-1) s (-1). Additionally, (*)F1 and (*)F4 decay by intermicellar bimolecular reaction (2 k = 20 and 2 x 10 (5) M (-1) s (-1), respectively) whereas other (*)Fn radicals are stable over seconds due to increased localization with regards to the Stern layer. In contrast, the thick uncharged hydrophilic palisade layer and the compact hydrophobic core of Triton X100 micelles are responsible for a much higher microviscosity resulting in a decrease in k 1 from approximately 15.6 s (-1) for n = 1 to 9.6 s (-1) for n = 10.     

Synthese et reactivite d''organometalliques perfluores. VII [1] reactivite comparee de derives perfluoroalkyles satures et insatures de l''etain et du mercure vis-a-vis d''electrophiles.

The reactivity of some derivatives of perfluorooctenyl-tin, perfluorooctenyl-mercury and perfluorooctyl-mercury towards protic acids, especially hydrogen chloride, is studied.

The easy cleavage of the tin - sp² carbon bond is painted out, and used to study possibilities of transferring the perfluorooctenyl radical on mercury, upon reaction with mercuric salts.

The mercury-perfluoroalkyl radical bond is shown to be, on the contrary, very resistant to an electrophilic attack.

These results are compared to those concerning the hydrocarbon analogs, and an interpretation, relied to the electronic density on the carbon atom bound to the metallic atom, is given.     

Elemental Analyses Using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) of Geological Samples Fused with Li2B4O7 and Calibrated Without Matrix-Matched Standards

 Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used as a complementary technique to X-ray fluorescence (XRF), for multi-element analysis of geological samples fused with lithium-tetraborate Li₂B₄O₇). Different calibration strategies using external non-matrix matched reference materials were investigated. Various internal standards were tested, including the use of Li from the flux, and the use of the naturally occurring internal standards, Si or Ca. The use of a naturally occurring standard is not as efficient as this required a prior analysis of the samples using XRF. The obtained values for the analysis of geological reference materials were compared with consensus literature values, and satisfactory agreement was found. Laser pits, which were formed, had a diameter of 80 μm and 3–5 replicates on each fused disc were measured. The reproducibility of the method was better than 10% for concentrations above 1 μg/g and better than 15% for lower concentrations. The use of Li as the internal standard offers the possibility of multi-element determinations in geological samples, which have an unknown composition when the laser ablation analysis is carried out. However, using the calculated stoichiometric composition of the lithium-tetraborate for the calculation of the Li concentration leads to a constant deviation from the recommended values. Therefore, it was necessary to determine the Li concentration within each sample batch using at least one lithium tetraborate fused geological reference material. This resulting Li concentration in the beads was then used for all subsequent samples in a run. Limits of detection, reproducibility, deviation from reference values indicate the potential of LA-ICP-MS for such bulk analysis without matrix matched calibration standards.     

Three-dimensional microfabrication by two-photon-initiated polymerization with a low-cost microlaser

Fabrication of submicrometer structures by two-photon-initiated polymerization is performed with an inexpensive and low-power microlaser. This is made possible by the design of photoinitiators with strong two-photon absorption cross sections. We analyze the influence of both material properties and irradiation conditions on the two-photon polymerization rate and show that resins based on our highly sensitive two-photon photoinitiator can be solidified with microlaser excitation, whereas commercial UV photoresins require ultrashort and intense laser pulses.     

Géométrie diophantienne et variétés toriques

We present some results on projective toric varieties which are relevant in diophantine geometry. We interpret and study several invariants attached to these varieties by geometrical and combinatorial terms. We also give a Bézout theorem for Chow weights of projective varieties and an application to the theorem of successive algebraic minima. These results are extracted from the two texts of Philippon and Sombra mentioned in the references at the end of this Note (both downloadable from http://fr.arxiv.org). To cite this article: P. Philippon, M. Sombra, C. R. Acad. Sci. Paris, Ser. I 340 (2005).     

Ensembles invariants non enlacés des difféomorphismes du tore et de l’anneau

We introduce the notion of unlinked invariant set for a diffeomorphism of the 2-torus or the closed annulus and we look at the properties of these sets which generalize the Aubry-Mather sets. We prove that for any irrational number in the rotation set of an area-preserving diffeomorphism of the annulus, there exists an unliked invariant set whose rotation set is reduced to . In the same way we prove that any minimal diffeomorphism of the 2-torus homotopic to the identity may be approximated in the C⁰-topology by a periodic diffeomorphism.

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Mathematics Subject Classification (2000) 37E30, 37E45, 37J10     

Practical guide for improving performance

Research has established that health care is not error free. The question facing perioperative units, as well as all health care services, is how to minimize the human factors that impact quality and safety. This two-part series on performance improvement in perioperative services was intended to help answer this question. Achieving performance excellence starts with a supportive work culture. The human issues of teamwork, communication, and leadership are crucial to achieving performance excellence. Next, perioperative caregivers must accept that all people make mistakes so systems and processes can be designed to be more "forgiving" of errors. Last, a planned and systematic approach must be used to measure, analyze, and improve performance. Successful implementation of performance improvement calls for strong partnerships between physicians, managers, and staff members. Performance excellence requires that everyone work together to ensure that perioperative care is safe, effective, appropriate, customer focused, and efficient.     

Theoretical and experimental study of differential group delay and polarization dependent loss of Bragg gratings written in birefringent fiber

In this paper, we completely study the wavelength dependency of differential group delay (DGD) and polarization dependent loss (PDL) for Bragg gratings written in birefringent fibers. Based on the coupled mode theory, we present analytical expressions for the evolution with wavelength of the transmission coefficient, the DGD and the PDL. The wavelength dependencies of these evolutions on the birefringence are then discussed. Experimental results are finally presented for an apodized FBG written in a bow-tie fiber. A very good agreement between theory and experience is reported, confirming the validity of the theoretical analysis.     

Design of the spatial filter window for digital holographic convolution reconstruction of object beam field

In the convolution reconstruction process of digital holographic object beam field, the object beam fields with different magnifications can be obtained when the reconstructing beams are spherical waves with different wave curvature radii. This paper presents a theoretical and experimental discussion on the useful spatial frequency spectrum of the hologram numerically illuminated by the spherical wave. The result shows that there would be an image in the spatial frequency spectrum of digital hologram, which is completely the same as the object, if the wave surface radius of the spherical wave is equal to the distance from the object to the CCD sensor. Taking this image as a reference and designing a filter, the position of the reconstructed images with different magnifications can be predicted correctly in the reconstructed plane. Additionally, since the spectrum distribution of zero-order diffraction can be forecasted accurately in theory, its contribution can be effectively eliminated through changing the spatial filter shape; then a reconstructed object field containing more high-frequency information can be obtained.