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51.
Two original dinuclear (LnYb, 3 and LnEr, 4) and one trinuclear CuIILnIIICuII (LnGd, 5) complexes derived from a polydentate non symmetrical Schiff base ligand H2L have been prepared. The ligand possesses two functions (phenol and oxime) able to coordinate the Ln ions, but structural studies (X-ray diffraction and powder X-ray diffraction) show that the CuII and LnIII ions are only bridged by the oximato (NO) pair. The missing phenoxo bridge is replaced by a surprising pseudo-bridge involving one oxygen atom of the nitrato anion linked to the Cu and Ln ions according to a η2: η1: μ mode. Although this latter contact has no role from the magnetic point of view, it introduces a large deformation of the unique bridging network. The CuYb complex 3 and the trinuclear CuGdCu complex 5 present antiferromagnetic interactions, with a JCuGd interaction equal to ?1.25 cm?1 in 5. The genuine single bridge can be considered as responsible for the antiferromagnetic character of the interaction. 相似文献
52.
Badr Benmansour Ludovic Stephan Jean-Yves Cabon Laure Deschamps Philippe Giamarchi 《Journal of fluorescence》2011,21(3):843-850
This work presents spectroscopic properties of some Endocrine Disrupting Compounds (EDCs), frequently found in food and in
natural water. Studied molecules belong to the groups of phenolic and phthalate EDCs. In a first part, we have examined their
absorption and fluorescence properties. Fluorescence emission wavelengths are about 300 nm for phenolic compounds and 360 nm
for phtalate compounds; main excitation wavelengths being comprised between 210 nm and 230 nm. Fluorescence lifetimes measured
are short (about 4 ns) and the fluorescence quantum yield has been determined. In a second part, to avoid the time consuming
solvent extraction step, an analytical application to evaluate the performance of a direct analysis by laser induced fluorescence
spectroscopy of ECDs traces in tap water and in raw water is presented. Good detection limits have been obtained, i.e.: 0.35 μg.L−1 of chlorophenol in tap water, which are always lower than the reported Predictive Non Efficient Concentration (PNEC). 相似文献
53.
In this Letter, we present a new experimental approach to investigate the effective temperature concept as a generalization of the fluctuation-dissipation theorem (FDT) for nonequilibrium systems. Simultaneous measurements of diffusion coefficient and sedimentation velocity of heavy colloids, embedded in a Laponite clay suspension, are performed with a fluorescence-recovery-based setup. This nonperturbative dual measurement, performed at a single time in a single sample, allows for a direct application of the FDT to the tracer velocity observable. It thus provides a well-defined derivation of the effective temperature in this ageing colloidal gel. For a wide range of concentrations and ageing times, we report no violation of the FDT, with effective temperature agreeing with bath temperature. This result is consistent with recent theoretical predictions on the coupling between the velocity observable and nonequilibrium gels dynamics. 相似文献
54.
My-Loan-Phung Le Fannie Alloin Pierre Strobel Jean-Claude Lepr��tre Laure Cointeaux Carlos P��rez del Valle 《Ionics》2011,18(9):817-827
Ionic liquids, ILs, based on fluorinated pyrrolidinium and piperidinium ammonium cations and imide anion were prepared and characterized. The physicochemical and electrochemical properties of these ILs including melting point, glass transition and degradation temperatures, viscosity, ionic conductivity, and electrochemical stability were determined and compared to alkyl pyrrolidinium and piperidinium ILs. The incorporation of a CF3 group instead of a CH3 induces an increase of the IL viscosity, thus a conductivity decrease. However, good ionic conductivity is obtained with fluorinated pyrrolidinium IL. Cyclic amine ILs with propyl alkyl chain or fluorinated ammonium exhibit very high electrochemical stability toward oxidation. The effect of the addition of LiTFSI on the IL properties was studied with the same methodology. 相似文献
55.
Diaz F Lee MS Rejeaunier X Lehoucq G Goudail F Loiseaux B Bansropun S Rollin J Debes E Mils P 《Optics letters》2011,36(3):418-420
Imaging systems that combine a phase mask in the pupil and digital postprocessing may have better performance than conventional ones. We have built such a system to enhance the depth of field of an uncooled thermal camera. The phase masks are binary, their structures are optimized thanks to an image quality criterion, and they have been realized with three different technologies that give equivalent results. The deconvolution postprocessing is performed in real time with a graphics processing unit. A significant increase of the depth of field of a factor 3 has been obtained. 相似文献
56.
9-Membered rings are readily constructed through a radical addition-cyclisation sequence on a 1,6-dien-3-ol system followed by a Grob-type fragmentation. 相似文献
57.
Remigiusz Zurawinski Christine Lepetit Yves Canac Laure Vendier Marian Mikolajczyk Remi Chauvin 《Tetrahedron: Asymmetry》2010,21(13-14):1777-1787
The synthesis and structure of Rh(I) and Pd(II) complexes of chiral P,C-chelating phosphino-(α-sulfinylalkyl)phosphonium ylide ligands with a trisubstituted asymmetric ylidic center P+–C1R(S1(O)p-Tol)–M (R = alkyl group) have been investigated, and compared to those of the analogous disubstituted ylide complexes (R = H). Reaction of the ethyl onium ylide of o-bis(diphenylphosphino)benzene with (?)-menthyl-(S)-p-tolylsulfinate afforded the corresponding racemic erythro phosphino-(α-sulfinylethyl)phosphonium in 90% de (R = Me). The racemization process is interpreted by a Berry-like pseudorotation mechanism driven by the steric repulsion between the α-methyl substituent and the bulky menthyloxy S-substituent or sulfur lone pair in the intermediate ylide-sulfinyl adduct. The ylide of phosphino-(α-sulfinylethyl)phosphonium reacts with [Rh(cod)2][PF6] and PdCl2(MeCN)2 to afford the corresponding P,C1-chelated threo-Rh(I) and erythro-Pd(II) mononuclear complexes in 70% yield and total diastereoselectivity. These respective complexes act as efficient catalytic precursors for the hydrogenation of (Z)-α-acetamidocinnamic acid and allylic substitution of 3-acetoxy-1,3-diphenyl-1-propene with sodium dimethyl malonate. The bonding features of the erythro-Pd(II) complex exhibiting a sulfinyl O?Pd interaction are studied theoretically at the DFT level using ELF and MESP analyses. The η2-P,C haptomeric form of the ylide ligand is estimated to compete at 19% with the η1-C haptomeric form dominating at 81%. 相似文献
58.
In this paper we show, by using dyadic approximations, the existence of a geometric rough path associated with a fractional
Brownian motion with Hurst parameter greater than 1/4. Using the integral representation of fractional Brownian motions, we
furthermore obtain a Skohorod integral representation of the geometric rough path we constructed. By the results in [Ly1],
a stochastic integration theory may be established for fractional Brownian motions, and strong solutions and a Wong-Zakai
type limit theorem for stochastic differential equations driven by fractional Brownian motions can be deduced accordingly.
The method can actually be applied to a larger class of Gaussian processes with covariance functions satisfying a simple decay
condition.
Received: 11 May 2000 / Revised version: 20 March 2001 / Published online: 11 December 2001 相似文献
59.
Marie‐Laure Louillat‐Habermeyer Rongwei Jin Prof. Dr. Frederic W. Patureau 《Angewandte Chemie (International ed. in English)》2015,54(13):4102-4104
A method was developed for the direct dehydrogenative construction of C? N bonds between unprotected phenols and a series of cyclic anilines without resorting to any kind of metal activation of either substrate and without the use of halides. The resulting process relies on the exclusively organic activation of molecular oxygen and the subsequent oxidation of the aniline substrate. This allows the coupling of ubiquitous phenols, thus furnishing aminophenols through an atom‐economical and most sustainable dehydrogenative amination method. This new reactivity, which relies on the intrinsic organic reactivity of cumene in what can be seen as a modified Hock activation process of oxygen, is expected to have a large impact on the formation of C? N bonds in organic synthesis. 相似文献
60.