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821.
Labouille S Escalle-Lewis A Jean Y Mézailles N Le Floch P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(7):2256-2265
The catalytic activity both of cationic [(XDPP)Au][X] (XDPP = bis-2,5-diphenylphosphole xantphos X = BF(4)) and of the isolated gold hydride complex [(XDPP)(2)Au(2)H][OTf] in the dehydrogenative silylation process is presented. A parallel theoretical study using density functional theory revealed a mechanism involving the counter anion as a co-catalyst, which was experimentally confirmed by testing various counterions (X = OTf, NTf(2), PF(6)). Finally, a "Au(2)H(+)" species was determined as the intermediate during the catalytic cycle, which correlates well with the experimental findings on the first example of catalytic activity of an isolated "Au-H" complex. 相似文献
822.
Cosquer G Pointillart F Le Gal Y Golhen S Cador O Ouahab L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(44):12502-12511
(TTF-salphen)M compounds (TTF-salphen(2-)=4,5-bis(propylthio)tetrathiafulvalene-N,N'-phenylenebis(salicylideneimine) dianion; M=Cu(II) and Ni(II)) have been treated with Ln(hfac)(3)·2H(2)O precursors (hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate anion; Ln=Gd(III), Tb(III), and Dy(III)) to elaborate unprecedented 3d/4f TTF-based heterobimetallic complexes of formula [(TTF-salphen)MLn(hfac)(3)]. All the structures of these compounds have been resolved by X-ray diffraction on single crystals. The structures of these complexes are formed by a TTF-salphen(2-) ligand coordinated to the 3d metal ions in the inert tetradentate N(2)O(2) site. The Ln(hfac)(3) fragment is coordinated to the (TTF-salphen)M one through the two phenolate bridges. Even if the complexes are similar in both Cu(II) and Ni(II) families, the crystal packing is different. In the first case, dimers of TTF-salphen(2-) donors constitute the organic network. In the other case, a reminiscent organic network is observed with S···S contacts. The photophysical properties of [(TTF-salphen)CuDy(hfac)(3)] (3) in chloroform solution highlight the redshift of the TTF→salphen charge transfer (400 cm(-1)) relative to the analogue excitations in (TTF-salphen)Cu, which attest to the stability of these structures in solution. Static magnetic measurements have allowed us to quantify the ferromagnetic interactions (J=+1.29 cm(-1)) between Cu(II) and Gd(III) in the [(TTF-salphen)CuGd(hfac)(3)] complex. Finally, an empirical method that consists of the comparisons of the magnetic properties of [(TTF-salphen)CuTb(hfac)(3)] with [(TTF-salphen)NiTb(hfac)(3)] and [(TTF-salphen)CuDy(hfac)(3)] with [(TTF-salphen)NiDy(hfac)(3)] has established that ferromagnetic interactions take place between Cu(II) and Tb(III) ions, whereas unusual antiferromagnetic interactions have been identified between Cu(II) and Dy(III) ions. 相似文献
823.
Bouchonnet S Kinani S Souissi Y Bourcier S Sablier M Roche P Boireau V Ingrand V 《Rapid communications in mass spectrometry : RCM》2011,25(1):93-103
With the future aim of using gas chromatography coupled with mass spectrometry to characterize the transformation products of ozonated herbicides: metolachlor, acetochlor and alachlor, an interpretation of their electron ionization mass spectra is presented. Fragmentation mechanisms are proposed on the basis of isotopic labelling and multiple-stage mass spectrometry experiments carried out on an ion trap mass spectrometer. We also give examples in order to demonstrate how the elucidation of such fragmentation mechanisms for herbicides may simplify the characterization of their ozonation products. 相似文献
824.
Knyazev A Louise L Veber M Langevin D Filoramo A Prina-Mello A Campidelli S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(51):14663-14671
The dispersion of highly hydrophobic carbon materials such as carbon nanotubes in biological media is a challenging issue. Indeed, the nonspecific adsorption of proteins occurs readily when the nanotubes are introduced in biological media; therefore, a methodology to control adsorption is in high demand. To address this issue, we developed a bifunctional linker derived from pyrene that selectively enables or prevents the adsorption of proteins on single-wall carbon nanotubes (SWNTs). We demonstrated that it is possible to decrease or completely suppress the adsorption of proteins on the nanotube sidewall by using proper functionalization (either covalent or noncovalent). By subsequently activating the functional groups on the nanotube derivatives, protein adsorption can be recovered and, therefore, controlled. Our approach is simple, straightforward, and potentially suitable for other biomolecules that contain thio or amino groups available for coupling. 相似文献
825.
Geagea R Ladeira S Mazières S Destarac M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(13):3718-3725
Molybdenum and chromium pentacarbonyldiphenylphosphinocarbodithioate complexes have been prepared in a one‐pot reaction from the corresponding metallocarbonyldiphenylphosphine. The complexes have been characterised by IR, 1H, 31P and 13C NMR spectroscopies and by mass spectrometry. The solid‐state structures of [Cr(CO)5{PPh2CS2CH(Ph)CH3}] ( 1 ) and [Mo(CO)5{PPh2CS2CH(Ph)CH3}] ( 2 ) are reported. Compounds 1 and 2 are isostructural and crystallise in the triclinic P$\bar 1Molybdenum and chromium pentacarbonyldiphenylphosphinocarbodithioate complexes have been prepared in a one-pot reaction from the corresponding metallocarbonyldiphenylphosphine. The complexes have been characterised by IR, (1)H, (31)P and (13)C?NMR spectroscopies and by mass spectrometry. The solid-state structures of [Cr(CO)(5){PPh(2)CS(2)CH(Ph)CH(3)}] (1) and [Mo(CO)(5){PPh(2)CS(2)CH(Ph)CH(3)}] (2) are reported. Compounds 1 and 2 are isostructural and crystallise in the triclinic P1 space group. These new organometallic compounds are highly efficient reversible chain-transfer agents for reversible addition-fragmentation chain-transfer (RAFT) polymerisation of styrene (St) and n-butyl acrylate (nBA), with controlled number-average molar mass values and narrow dispersities (<1.2). The controlled character of the polymerisation was further exemplified by the synthesis of St and nBA diblock copolymers. 相似文献
826.
Soares SF Galvão RK Araújo MC da Silva EC Pereira CF de Andrade SI Leite FC 《Analytica chimica acta》2011,(1):30-28
This work proposes a modification to the successive projections algorithm (SPA) aimed at selecting spectral variables for multiple linear regression (MLR) in the presence of unknown interferents not included in the calibration data set. The modified algorithm favours the selection of variables in which the effect of the interferent is less pronounced. The proposed procedure can be regarded as an adaptive modelling technique, because the spectral features of the samples to be analyzed are considered in the variable selection process. The advantages of this new approach are demonstrated in two analytical problems, namely (1) ultraviolet–visible spectrometric determination of tartrazine, allure red and sunset yellow in aqueous solutions under the interference of erythrosine, and (2) near-infrared spectrometric determination of ethanol in gasoline under the interference of toluene. In these case studies, the performance of conventional MLR-SPA models is substantially degraded by the presence of the interferent. This problem is circumvented by applying the proposed Adaptive MLR-SPA approach, which results in prediction errors smaller than those obtained by three other multivariate calibration techniques, namely stepwise regression, full-spectrum partial-least-squares (PLS) and PLS with variables selected by a genetic algorithm. An inspection of the variable selection results reveals that the Adaptive approach successfully avoids spectral regions in which the interference is more intense. 相似文献
827.
828.
Wallace IM Urbanus ML Luciani GM Burns AR Han MK Wang H Arora K Heisler LE Proctor M St Onge RP Roemer T Roy PJ Cummins CL Bader GD Nislow C Giaever G 《Chemistry & biology》2011,18(10):1273-1283
Preselection of compounds that are more likely to induce a phenotype can increase the efficiency and reduce the costs for model organism screening. To identify such molecules, we screened ~81,000 compounds in Saccharomyces cerevisiae and identified ~7500 that inhibit cell growth. Screening these growth-inhibitory molecules across a diverse panel of model organisms resulted in an increased phenotypic hit-rate. These data were used to build a model to predict compounds that inhibit yeast growth. Empirical and in silico application of the model enriched the discovery of bioactive compounds in diverse model organisms. To demonstrate the potential of these molecules as lead chemical probes, we used chemogenomic profiling in yeast and identified specific inhibitors of lanosterol synthase and of stearoyl-CoA 9-desaturase. As community resources, the ~7500 growth-inhibitory molecules have been made commercially available and the computational model and filter used are provided. 相似文献
829.
Mukherjee P Shade CM Yingling AM Lamont DN Waldeck DH Petoud S 《The journal of physical chemistry. A》2011,115(16):4031-4041
This work explores the sensitization of luminescent lanthanide Tb(3+) and Eu(3+) cations by the electronic structure of zinc sulfide (ZnS) semiconductor nanoparticles. Excitation spectra collected while monitoring the lanthanide emission bands reveal that the ZnS nanoparticles act as an antenna for the sensitization of Tb(3+) and Eu(3+). The mechanism of lanthanide ion luminescence sensitization is rationalized in terms of an energy and charge transfer between trap sites and is based on a semiempirical model, proposed by Dorenbos and co-workers (Dorenbos, P. J. Phys.: Condens. Matter 2003, 15, 8417-8434; J. Lumin. 2004, 108, 301-305; J. Lumin. 2005, 111, 89-104. Dorenbos, P.; van der Kolk, E. Appl. Phys. Lett. 2006, 89, 061122-1-061122-3; Opt. Mater. 2008, 30, 1052-1057. Dorenbos, P. J. Alloys Compd. 2009, 488, 568-573; references 1-6.) to describe the energy level scheme. This model implies that the mechanisms of luminescence sensitization of Tb(3+) and Eu(3+) in ZnS nanoparticles are different; namely, Tb(3+) acts as a hole trap, whereas Eu(3+) acts as an electron trap. Further testing of this model is made by extending the studies from ZnS nanoparticles to other II-VI semiconductor materials; namely, CdSe, CdS, and ZnSe. 相似文献
830.
In this work, a microfluidic free-flow electrophoresis device with a novel approach for preventing gas bubbles from entering the separation area is presented. This is achieved by integrating partitioning bars to reduce the channel depth between electrode channels and separation chamber in order to obtain electrical contact and simultaneously prevent bubbles from entering the separation area. The three-layer sandwich chip features a reusable carrier plate with integrated ports for fluidic connection combined with a softlithographically cast microfluidic PDMS layer and a sealing glass slide. This design allows for a straightforward and rapid chip prototyping process. The performance of the device is demonstrated by free-flow zone electrophoretic separations of fluorescent dye mixtures as well as by the separation of labeled amines and amino acids with separation voltages up to 297 V. 相似文献