Etude par Résonance Magnétique Nucléaire de dioxaphosphorinanes-1,3,2 à liaison P?N extracyclique. Exemple de changement d'orientation de la liaison P?N

The ¹H NMR spectra of several 1,3,2-dioxaphosphorinanes bearing an extracyclic P? N bond have been analysed. The ³J(POCH) couplings are strongly dependent upon the orientation of the bond around the phosphorus atom. Depending upon the nature of the bonds attached to the nitrogen atom, the dioxaphosphorinane ring may adopt either a fixed chair conformation with the P? N bond in the axial or equatorial orientation, or it may be in equilibrium between two chair conformations where the P? N bond is alternately axial or equatorial. The equilibrium is fast on the NMR time scale.     

The Road to Deterministic Matrices with the Restricted Isometry Property

The restricted isometry property (RIP) is a well-known matrix condition that provides state-of-the-art reconstruction guarantees for compressed sensing. While random matrices are known to satisfy this property with high probability, deterministic constructions have found less success. In this paper, we consider various techniques for demonstrating RIP deterministically, some popular and some novel, and we evaluate their performance. In evaluating some techniques, we apply random matrix theory and inadvertently find a simple alternative proof that certain random matrices are RIP. Later, we propose a particular class of matrices as candidates for being RIP, namely, equiangular tight frames (ETFs). Using the known correspondence between real ETFs and strongly regular graphs, we investigate certain combinatorial implications of a real ETF being RIP. Specifically, we give probabilistic intuition for a new bound on the clique number of Paley graphs of prime order, and we conjecture that the corresponding ETFs are RIP in a manner similar to random matrices.     

Ionic liquids versus ionic liquid-based surfactants in dispersive liquid–liquid microextraction for determining copper in water by flame atomic absorption spectrometry

This work compares the performance of dispersive liquid–liquid method (DLLME) as a prior step for determining copper by flame atomic absorption spectrometry (FAAS), when using the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate (C₄MIm-PF₆) or the IL-based surfactant 1-hexadecyl-3-butylimidazolium bromide (C₁₆C₄Im-Br) as extractant solvents. For the water-insoluble C₄MIm-PF₆, the most conventional DLLME mode using acetonitrile as dispersive solvent was employed. For the water-soluble C₁₆C₄Im-Br, the in situ DLLME mode with lithium bis[(trifluoromethane)sulfonyl]imide (Li-NTf₂) as metathesis reagent was employed. In both approaches, some effective parameters such as volumes of extractant and dispersive solvents, concentration of complexing agent, pH of sample solution, salting-out effect and final diluting solvent to ensure compatibility with FAAS, were properly optimised. The optimum conditions for the IL-DLLME method using C₄MIm-PF₆ were: 100 μL of neat C₄MIm-PF₆, 1 mL of acetonitrile, 10 mL of water, no control of pH for environmental waters, NaCl content of 23 g L^?1, diethyl dithiocarbamate (DDTC) as complexing agent at 10 mg L^?1 and final dilution of the micro-droplet with acetonitrile up to 70 µL. The optimum conditions for the in situ IL-DLLME method using C₁₆C₄Im-Br were: 0.8 mL of acetonitrile, 10 mL of water containing C₁₆C₄Im-Br at 25.2 mmol L^?1, final dilution step of the micro-droplet with 200 µL of acetonitrile and remaining conditions as those of C₄MIm-PF₆. The analytical performance of both methods was similar, being slightly better for the IL-DLLME method using C₄MIm-PF₆, with limits of detection (LOD) of 3.3 µg L^?1 (versus 5.1 µg L^?1 when using C₁₆C₄Im-Br), precision values as intraday relative standard deviation (RSD in %) lower than 8.8% (being of 10% for the C₁₆C₄Im-Br method) and an enrichment factor of 54 (being 27 when using C₁₆C₄Im-Br). The DLLME-FAAS method with C₄MIm-PF₆ was used in the analysis of environmental waters with successful performance, with relative recoveries of 110% and 105%, and interday precision with RSD values of 21% and 7.4% for spiked levels of 60 and 160 µg L^?1, respectively. The results obtained when analysing an urban wastewater sample coming from an inter-laboratory exercise was comparable to those obtained for other 93 laboratories. The method was also valid for the determination of Cu²⁺ in presence of foreign ions commonly found in natural waters.     

Vacuum versus gas environment for the synthesis of nanocomposite films by pulsed-laser deposition

Nanocomposite films formed by Cu nanocrystals (NCs) with sizes <10 nm embedded in an amorphous Al₂O₃ host have been grown by alternate pulsed-laser deposition both in vacuum and in a buffer gas (Ar) up to pressures of 0.1 Torr. The dimensions, dimension distributions, and shape of the NC produced in vacuum and in Ar up to pressures of 5᎒^-3 Torr follow a similar trend as a function of the Cu areal density. This allows us to conclude that the nucleation and growth of the NC are dominated by processes occurring at the substrate surface rather than in the gas phase. For Ar pressures ̓᎒^-2 Torr, the anisotropy of the NC is enhanced, the deposition rate decreases abruptly and a significant amount of the buffer gas is incorporated into the host, thus leading to the formation of a porous material.     

Spectrofluorimetric determination of carbaryl and 1-naphthol in micellar media

The interaction of 1-naphthol-N-methyl-carbamate (carbaryl) and its degradation product, 1-naphthol, with the surfactant hexadecyl-trimethylammonium bromide has been studied. The micellar medium allows the direct spectrofluorimetric determination of carbaryl, with 6.2 ng/ml as detection limit in acidic medium, or indirectly, after hydrolysis, as 1-naphthol at pH 11.0 or pH 3.0 with detection limits of 0.4 and 1.6 ng/ml, respectively. The recoveries of carbaryl and 1-naphthol from natural waters are acceptable.     

Solid-phase microextraction coupled with high-performance liquid chromatography for the analysis of heterocyclic aromatic amines

Solid-phase microextraction (SPME) coupled with high-performance liquid chromatography (HPLC) with UV diode array detection (DAD) for the analysis of heterocyclic aromatic amines (HAs) is described. Four kinds of fiber coatings: Carbowax-templated resin (CW-TPR), Carbowax-divinylbenzene (CW-DVB), poly(dimethylsiloxane)-divinylbenzene (PDMS-DVB) and polyacrylate (PA) were evaluated for extraction of nine most biologically active heterocyclic aromatic amines. Different parameters affecting to the microextraction and determination of HAs were studied, such as absorption and desorption time, desorption mode, composition of the solvent for desorption, pH, ionic strength, and percentage of methanol in the sample. To determine these amines in food samples a new simplified procedure is proposed, consisting of treatment of the sample with methanolic NaOH prior microextraction by CW-TPR fiber coating and HPLC-DAD determination. The advantages of this new method are the reduced amounts of time and organic solvents required.     

Imide--amide rearangement of cylic phosphorimidates: a mechanistic study

Studies aimed at the development of new synthetic pathways for the preparation of chiral cyclic oxaza and diaza phosphoramides suitable for use in asymmetric chemistry led us to the investigation of the imide -amide rearrangement of cyclic phosphorimidates. As a result of this work new types of oligomeric organophosphorus compounds, formed by a novel 1,4-addition type ring opening polymerisation, were identified. These compounds are the stable intermediates of the imide-amide rearrangement, which upon heating yield the previously reported rearranged product. A detailed study of the mechanism of the Lewis acid catalysed imide-amide rearrangement and stereochemical control of the final products is reported. As a result, the full mechanism was elucidated and evidence of retention of configuration at the rearranged carbon atom is presented. Substituent effects were rationalised based on molecular modelling calculations.     

A model of the annealing and activation of dissolution sites in magnetite exposed to (γ + n) radiation

The influence of gamma and reactor (n + γ) preirradiation on the dissolution of magnetite microcrystals synthetized by a low-temperature wet method was studied. Two opposite effects affect the dissolution rate: the annealing due to the gamma radiation and the generation of new imperfect coordination polyhedra. A model for the kinetic processes was proposed and the kinetic parameters were calculated.