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131.
Leduc AM Salameh A Soulivong D Chabanas M Basset JM Copéret C Solans-Monfort X Clot E Eisenstein O Böhm VP Röper M 《Journal of the American Chemical Society》2008,130(19):6288-6297
The surface complex [([triple bond]SiO)Re([triple bond]CtBu)(=CHtBu)(CH2tBu)] (1) is a highly efficient propene metathesis catalyst with high initial activities and a good productivity. However, it undergoes a fast deactivation process with time on stream, which is first order in active sites and ethene. Noteworthy, 1-butene and pentenes, unexpected products in the metathesis of propene, are formed as primary products, in large amount relative to Re (>1 equiv/Re), showing that their formation is not associated with the formation of inactive species. DFT calculations on molecular model systems show that byproduct formation and deactivation start by a beta-H transfer trans to the weak sigma-donor ligand (siloxy) at the metallacyclobutane intermediate having a square-based pyramid geometry. This key step has an energy barrier slightly higher than that calculated for olefin metathesis. After beta-H transfer, the most accessible pathway is the insertion of ethene in the Re-H bond. The resulting pentacoordinated trisperhydrocarbyl complex rearranges via either (1) alpha-H abstraction yielding the unexpected 1-butene byproduct and the regeneration of the catalyst or (2) beta-H abstraction leading to degrafting. These deactivation and byproduct formation pathways are in full agreement with the experimental data. 相似文献
132.
Souhir Boujday Romain Briandet Michèle Salmain Jean-Marie Herry Pierre-Guy Marnet Michel Gautier Claire-Marie Pradier 《Mikrochimica acta》2008,163(3-4):203-209
We describe the elaboration of ultra-sensitive immunosensors, to detect the bacterial pathogen Staphylococcus aureus. We utilized commercially available polyclonal anti-S. aureus antibody as receptor. Immunosensors were elaborated by building a self-assembled monolayer (SAM) of thiolamine onto planar gold-coated sensor chips. Then, Protein A was covalently linked to the thiolated SAM using glutaraldehyde as cross-linking agent. After a blocking step by Bovine Serum Albumin (BSA), the antibody was immobilized by affinity to Protein A. This step-by-step construction was monitored by Polarization Modulation Reflection Absorption Infrared Spectroscopy (PM-RAIRS) and Quartz Crystal Microbalance with Dissipation (QCM-D). In a first stage, the parameters of immunosensor elaboration were optimized using a model rabbit IgG. The accessibility of receptors and the homogeneity of their distribution were checked by PM-RAIRS, QCM-D, and by immuno-gold scanning electron microscopy. Then, the specific rabbit anti-S. aureus antibody was immobilized and the resulting sensing layer was applied to the detection of the pathogen target. Independent detection of bacteria immobilized on the sensors by fluorescent imaging allowed validation of the specificity of recognition toward the pathogen as well as a quantitative response of the sensor. Using PM-RAIRS as transducing technique allowed us to enhance sensitivity and reach a very competitive detection level (105 CFU mL?1). 相似文献
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Dynamic polymers (dynamers) based on reversible imine interactions were generated and found to respond to changes in neat/solution environment, thus displaying adaptive behavior through modification of their constitution in order to maximize the stability of their mesoscopic state as a function of conditions. 相似文献
138.
The long oligopyridinedicarboxamide strand 9, containing 15 heterocyclic rings has been synthesized and its helical structure determined by X-ray crystallography. It was shown that the shorter analogue 6 displays induced circular dichroism and amplification of induced chirality upon dissolution in an optically active solvent, diethyl-L-tartrate. A novel class of helical foldamers was prepared, strands 14-16, based on two oligopyridine carboxamide segments linked through a L-tartaric acid derived spacer. These tartro strands display internal chirality induction as well as chirality amplification. NMR spectroscopy (on 8 and 9) and circular dichroism (on 16) studies show that the oligopyridine carboxamide strands undergo reversible unfolding/folding upon protonation. The protonation-induced unfolding has been confirmed by X-ray crystallographic determination of the molecular structure of the extended protonated heptameric form 8(+). The molecular-scale mechano-chemical motions of the protonation-induced structural switching consist of a change of the length of the molecule, from 6 angstroms (6, coiled form) to 29 angstroms (8(+), uncoiled form) for the heptamer and from 12.5 angstroms (9, coiled form, X-ray structure) to 57 angstroms (9(+), uncoiled form, from modeling) for the pentadecamer. Similar unfolding/folding motional processes take place in the L-tartro strands 15 and 16 upon protonation/deprotonation, with loss of helicity-induced circular dichroism on unfolding as shown for the protonated form 16(+). 相似文献
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Guillemot G Thieuleux C Copéret C Soulivong D Spitzmesser S Basset JM 《Dalton transactions (Cambridge, England : 2003)》2007,(40):4589-4593
Grafting the well-defined molecular complexes [(ArO)Zr(CH2tBu)3], , and [(ArO)2Zr(CH2tBu)2], , on SiO2-(700) (ArO=2,6-Ph2C6H3O) gives the corresponding monosiloxy surface complexes [([TRIPLE BOND]SiO)Zr(CH2tBu)2(OAr)] and [([TRIPLE BOND]SiO)Zr(CH2tBu)(OAr)2] as major surface species as evidenced by mass balance analysis, IR and NMR spectroscopies. In both cases, minor cyclometallated species (ca. 20%) are also probably formed during the grafting process. While /SiO2-(700) catalytically transforms propane into its lower and higher homologues, /SiO2-(700) remains inactive. Moreover, the formation of butane as the major higher homologues is consistent with the formation of metallocarbene intermediates in this system in contrast to what was observed for the corresponding homologation reaction on silica supported zirconium hydrides. 相似文献