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1.
The binding of heterobidentate P∧S ligands introduces metal-centered chirality to the planar chiral parent complex Ru(η6:η1-NMe2C6H4C6H4PCy2)Cl2. Observed diastereomeric ratios for the kinetic product vary dramatically depending upon ring size of the chelate formed with the P∧S ligand. The complexes epimerize very slowly to thermodynamic product ratios that are substantially different from the kinetic product ratios. 相似文献
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Fabien Fontaine Evan Bolton Yulia Borodina Stephen H Bryant 《Chemistry Central journal》2007,1(1):12-14
Background
Large chemical databases require fast, efficient, and simple ways of looking for similar structures. Although such tasks are now fairly well resolved for graph-based similarity queries, they remain an issue for 3D approaches, particularly for those based on 3D shape overlays. Inspired by a recent technique developed to compare molecular shapes, we designed a hybrid methodology, alignment-recycling, that enables efficient retrieval and alignment of structures with similar 3D shapes. 相似文献4.
Vanderperren H Van Wouwe N Behets S Windal I Van Overmeire I Fontaine A 《Talanta》2004,63(5):1277-1280
Polyhalogenated aromatic hydrocarbons, such as polychlorinated dibenzo-p-dioxins are a large and diverse group of environmental pollutants. Their tendency to accumulate in the food chain and their toxicity make monitoring necessary. The reference analysis method is laborious and very expensive, therefore cheap and rapid bioassays have been developed. The chemical-activated luciferase bioassay (CALUX) bioassay uses a recombinant cell line, which responds to dioxins and dioxin-like molecules with Ah receptor (AhR)-dependent induction of firefly luciferase in a dose related response. The CALUX was tested for its use in the screening of feed. Aliquots of 20 g of enriched feed were extracted with a toluene:methanol mixture (20:4 v/v) and extracts were defatted on 33% H2SO4 silica columns and purified on carbon columns. Only the dioxin and furan fraction was analysed, the PCB fraction was discarded. The precision of the method is acceptable and in compliance with an R.S.D. <30% as suggested for cell-based bioassays in the Commission Directive 2002/70/EC of July 2002. The results evidence good agreement between TEQ-values obtained by either CALUX or GC–HRMS. The method is now routinely in use for a feed screening programme designed by the Federal Agency for the Safety of the Food chain. Approximately, 25 samples are analysed weekly. From the obtained results approximately 10% was confirmed by GC–HRMS. The false positive ratio is 1% and no false negatives were found, making the use of the CALUX technology advantageous. 相似文献
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Vincent Lapinte Laurent Fontaine Vronique Montembault Irne Campistron Danile Reyx 《Journal of molecular catalysis. A, Chemical》2002,190(1-2):117-129
ROMP and retro-acyclic diene metathesis (ADMET) were used for the synthesis of new functional polymers and functional oligomers, respectively. Purely exo and enantiomerically pure norbornene and 7-oxanorbornene derivatives were prepared using stereospecific synthesis, effective fractionation and high yield condensation reactions. Successful ROMPs of those monomers were performed using either the new carbenic Schrock’s or Grubb’s catalysts or in some cases a classical bicomponent catalyst. New functional polymers such as optically active poly(norbornene-2-carboxylic acid), reactive poly(norbornene-2-azlactone), and side-chain liquid crystal polyoxanorbornenes were fully characterized. On the other hand, successful depolymerizations of 1,4-polyisoprene and of epoxidized 1,4-polybutadiene via cross-metathesis with 4-octene were performed using a stabilized bicomponent catalyst and the Grubb’s catalyst, respectively. Conditions for the controlled synthesis of epoxidized oligobutadienes and of epoxydienic monomers via retro-ADMET were clearly defined. 相似文献
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The quantum yields of thecis trans andtrans cis Hg 6(3P1) photosensitized isomerizations of 1,3-pentadiene at 100 Torr and 22°C are 0.54±0.02 and 0.42±0.02, respectively. The steady state ratio ([trans]/[cis])ss is 1.27±0.05 which is almost identical with the ratio of the quantum yields, (ct)/(tc)=1.29±0.10. Thecistrans isomerization is suggested as a useful actinometer for mercury sensitized reactions.
Hg 6(3P1) 1,3- 100 22°C 0,54±0,02 0,42±0,02, . ([]/[]) 1,27±0,05, ( )/( )=1,29±0,10. , .相似文献
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Evert J. Ditzel Xavier L. R. Fontaine Norman N. Greenwood John D. Kennedy Mark Thornton-Pett 《无机化学与普通化学杂志》1992,616(10):79-85
The action of SMe2 on the ten-vertex nido-ruthenaborane [6-(η6-C6Me6)RuB9Hl3] ( 1 ) provides a high-yield route to the unsubstituted isocloso-ruthenaborane [1-(η6-C6Me6)RuB9H9] (2). The benzene analogue [1-(η6-C6Me6)RuB9H9] is prepared similarly. By contrast, reaction of (1) with PhNH2 gives a variety of B-phenylamino isocloso derivatives, including orange crystals of [1-(η6-C6Me6)-2-(PhNH)-isocloso-1-RuB 9 H8] ( 3 ), red-orange [1-(η6-C6Me6)-2,3-(PhNH)2-isocloso-1-RuB9H7] ( 4 ) and dark-red [1-(η6-C6Me6)-5,6,7-(PhNH)3-isocloso-1-RuB9H6] ( 5 ). Detailed 1H and 11B nmr properties of these various compounds are described. The structure of ( 3 ) has been established by a single-crystal X-ray diffraction study of the solvate [1-(η6-C6Me6)-2-(PhNH)-isocloso-1-RuB9H8] · 1/2 CH2Cl2; the crystals were monoclinic, space group C2/c, with a = 1895.1(3), b = 1556.6(3), c = 1716.4(3) pm, β = 104.37(1)° and z = 8. 相似文献