Purete radiochimique du complexe technetium-99m-etain-acide diethylene-triamino-pentaacetique

The radiochemical purity of technetium-99m-tin-diethylene-triamino-pentaacetic acid (DTPA) complex is checked by ascending paper chromatography. The percentage of uncomplexed technetium is lower than 5%. The technetium valency state is determined by visible absorption spectrometry.      

Medium-sized rings versus macrocycles through rhodium-catalyzed ring-expansion reactions of cyclic acetals

α-Diazo β-ketoesters and diketones react with cyclic acetals under Rh(II) catalysis to yield unprecedented polyoxygenated 8- and 9-membered rings in one pot. The reactions occur under mild conditions with yields up to 90%. A perfect regioselectivity is obtained, which can be rationalized through a mechanistic hypothesis that considers 1) the formation of an oxonium ylide, 2) its transformation into an unsaturated acyclic oxocarbenium electrophilic intermediate, and 3) an intramolecular nucleophilic attack in a direct application of Baldwin's rules.     

Synchronization between optically injected semiconductor lasers on undamped relaxation oscillations

Seeding light from a laser into the cavity of a second one is a simple experiment largely encountered in optical domain (Stover, H.L., Steier, W.H.: Appl. Phys. Lett. 8, 91–93 (1966); Lang, R.: IEEE J. Quant. Elect. 18(6), 976–983 (1982)). With an unidirectional coupling, optical injection is a basic tool to study synchronization process between oscillators. The dynamics induced in this experiment have been extensively described, theoretically and experimentally (Simpson, T.B. et al.: Quant. Semiclassical Opt. 9(5), 765–784 (1997); Wieczorek S.: Opt. Commun. 172, 279–295 (1999); Blin, S.: Comptes Rendus de la Phys. 4(6), 687–699 (2003)) but mainly when the seeded light is a continuous wave (CW). In this paper, we describe the synchronization on an undamped relaxation regime. In order to study the degree of correlation between the two synchronized lasers (TL and RL), we use a cascade of two optical injections (Guignard, C.: Conference on Lasers and Electro Optics—the Europeen Quant. Electronics Conference (CLEO-EQEC), Munich (Germany), EC1M (2003)) thus three lasers: Master-transmitter laser (TL)-receiver laser (RL). The seeding by a field showing undamped relaxations can be directly compared with the optical injection by a CW signal, especially when the injected power and the detuning between the TL and RL frequencies are varied. Synchronization on undamped relaxation are shown to occur at values of the optical injected power and detuning, for which the RL is in the locked or wave-mixing regime when it is seeded by a CW. However, additional tongues of synchronization also exist at detuning equal to the relaxation oscillation frequency (ROF).     

Kinematic Field Measurements During Orthogonal Cutting Tests via DIC with Double-frame Camera and Pulsed Laser Lighting

The measurement of machined-part strain fields induced by the cutting process remains a challenge because of the presence of highly intensive and localised strains. In this study, a high-speed double-frame imaging device with pulsed laser lighting is used in order to obtain sharp and highly resolved images during orthogonal cutting tests performed in an aluminium alloy. The displacement fields are then measured using a global Q4–digital-image-correlation (DIC) method and several strategies, facilitating calculation of the total displacements due to the cut, along with the residual strains in the machined part. Numerical procedures are developed to manage the removed material that disturbs the DIC. An automatic primary shear angle detection procedure using DIC is also proposed. Five different markings, which are produced via chemical etching and micro blasting, are applied to the observed surfaces. Their effects on the kinematic fields and the uncertainties are then studied. Three surface parameters are proposed as indicators for determining the surface preparation suitability for the DIC. The repeatability of the kinematic fields induced during the cutting process is studied, because of the ease with which testing can be performed. Finally, the plastically deformed layer engendered by the cutting process is measured using the calculated residual strains.     

Study of a XVIII century hand-painted Chinese wallpaper by multianalytical non-destructive techniques

In this work, hand-painted wallpaper belonging to a private Portuguese collection was analyzed in order to identify the pigments used. The analyzed artwork was an extraordinary XVIII century Chinese wallpaper that depicts exotic birds and flowers, which was painted with considerable accuracy and expertise. Thorough, in situ, X-ray fluorescence analyses were performed on nearly all the wallpaper. Since the elemental content of several colors was consistent for the four papered walls, strategic micro-samples were taken and analyzed by confocal Raman spectroscopy to further identify the pigments used. Pigments such as yellow ochre, lead white and barium white, vermilion, carmine, azurite and malachite were identified. Optical microscopy was used to analyze the fibers in the paper support, and fibers such as kozo, ramie and hemp or linen were identified.     

N-Heterocyclic tridentate aromatic ligands bound to [Ln(hexafluoroacetylacetonate)3] units: thermodynamic, structural, and luminescent properties

Herein, we discuss how, why, and when cascade complexation reactions produce stable, mononuclear, luminescent ternary complexes, by considering the binding of hexafluoroacetylacetonate anions (hfac(-)) and neutral, semi-rigid, tridentate 2,6-bis(benzimidazol-2-yl)pyridine ligands (Lk) to trivalent lanthanide atoms (Ln(III)). The solid-state structures of [Ln(Lk)(hfac)(3)] (Ln=La, Eu, Lu) showed that [Ln(hfac)(3)] behaved as a neutral six-coordinate lanthanide carrier with remarkable properties: 1) the strong cohesion between the trivalent cation and the didentate hfac anions prevented salt dissociation; 2) the electron-withdrawing trifluoromethyl substituents limited charge-neutralization and favored cascade complexation with Lk; 3) nine-coordination was preserved for [Ln(Lk)(hfac)(3)] for the complete lanthanide series, whilst a counterintuitive trend showed that the complexes formed with the smaller lanthanide elements were destabilized. Thermodynamic and NMR spectroscopic studies in solution confirmed that these characteristics were retained for solvated molecules, but the operation of concerted anion/ligand transfers with the larger cations induced subtle structural variations. Combined with the strong red photoluminescence of [Eu(Lk)(hfac)(3)], the ternary system Ln(III)/hfac(-)/Lk is a promising candidate for the planned metal-loading of preformed multi-tridentate polymers.     

Re4As6S3, a thio-spinel-related cluster system

We have synthesized a new compound with formula Re₄As₆S₃ and characterized its crystal structure by Rietveld powder diffraction methods. Re₄As₆S₃ crystallizes in an face-centered cubic unit cell, space group (no. 216), with lattice constant a=9.8608(1) Å and Z=4. The rhenium atoms form tetrahedral clusters linked via tetrahedral arsenic clusters to produce an NaCl-type arrangement. The oxidation state of rhenium is IV and the number of electrons shared by the rhenium atoms in the cluster is 12. The structure is based on an ordered defect thio-spinel A_(1−x)B₂X₄ where the B-type atoms form tetrahedral clusters.     

Polycyclic Indoline‐Benzodiazepines through Electrophilic Additions of α‐Imino Carbenes to Tröger Bases

Polycyclic indoline‐benzodiazepines can be accessed through the intermolecular reaction of Tröger bases with N‐sulfonyl‐1,2,3‐triazoles. Under Rh^II catalysis, α‐imino carbenes are generated and a subsequent cascade of [1,2]‐Stevens, Friedel–Crafts, Grob, and aminal formation reactions yield the polycyclic heterocycles as single isomers (d.r.>49:1, four stereocenters including two bridgehead N atoms). Further ring expansion by insertion of a second α‐imino carbene leads to elaborated polycyclic 9‐membered‐ring triazonanes.