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71.
A series of new polyfluorinated dienes 3, containing the novel -CFCHCHCF-, pattern has been synthesized (50–70% yields) by reacting perfluoroalkyl iodides with perfluoroalkyl-ethylenes in the presence of copper. The monoalkenes RfCFCHCH2CF2R′f and the saturated compounds RfCF2CH2CH2CF2R′f were obtained by varying the experimental conditions. The 1H and 19F NMR spectra are analysed and the reaction mechanism is discussed. 相似文献
72.
Bernaus A Gaona X Ivask A Kahru A Valiente M 《Analytical and bioanalytical chemistry》2005,382(7):1541-1548
The present work studies the adsorption behaviour of mercury species on different soil components (montmorillonite, kaolinite and humic acid) spiked with CH3HgCl and CH3HgOH at different pH values, by using XAS techniques and bacterial mercury sensors in order to evaluate the availability of methyl mercury on soil components. The study details and discusses different aspects of the adsorption process, including sample preparation (with analysis of adsorbed methyl mercury by ICP-OES), the various adsorption conditions, and the characterization of spiked samples by XAS techniques performed at two synchrotron facilities (ESRF in Grenoble, France and HASYLAB in Hamburg, Germany), as well as bioavailability studies using mercury-specific sensor bacteria. Results show that XAS is a valuable qualitative technique that can be used to identify the bonding character of the Hg in mercury environment. The amount of methyl in mercury adsorbed to montmorillonite was pH-dependent while for all soil components studied, the bond character was not affected by pH. On the other hand, clays exhibited more ionic bonding character than humic acids did with methyl mercury. This interaction has a higher covalent character and so it is more stable for CH3HgOH than for CH3HgCl, due to the higher reactivity of the hydroxyl group arising from the possible formation of hydrogen bonds.The bioavailability of methyl mercury adsorbed to montmorillonite, kaolinite and humic acids was measured using recombinant luminescent sensor bacterium Escherichia coli MC1061 (pmerBRBSluc). In case of contact exposure (suspension assays), the results showed that the bioavailability was higher than it was for exposure to particle-free extracts prepared from these suspensions. The highest bioavailability of methyl mercury was found in suspensions of montmorillonite (about 50% of the total amount), while the bioavailabilities of kaolinite and humic acids were five times lower (about 10%). The behaviour of methyl mercury in the presence of montmorillonite could be explained by the more ionic bonding character of this system, in contrast to the more covalent bonding character observed for humic acids. Thus, XAS techniques seem to provide promising tools for investigating the mechanisms behind the observed bioavailabilities of metals in various environmental matrices, an important topic in environmental toxicology. 相似文献
73.
Factor Xa is a serine protease which activates thrombin and plays a key regulatory role in the blood-coagulation cascade. Factor Xa is at the crossroads of the extrinsic and intrinsic pathways of coagulation and, hence, has become an important target for the design of anti-thrombotics (inhibitors). It is not known to be involved in other processes than hemostasis and its binding site is different to that of other serine proteases, thus facilitating selective inhibition. The design of high-affinity selective inhibitors of factor Xa requires knowledge of the structural and dynamical characteristics of its active site. The three-dimensional structure of factor Xa was resolved by X-ray crystallography and refined at 2.2 Å resolution by Padmanabhan and collaborators. In this article we present results from molecular dynamics simulations of the catalytic domain of factor Xa in aqueous solution. The simulations were performed to characterise the mobility and flexibility of the residues delimiting the unoccupied binding site of the enzyme, and to determine hydrogen bonding propensities (with protein and with solvent atoms) of those residues in the active site that could interact with a substrate or a potential inhibitor. The simulation data is aimed at facilitating the design of high-affinity selective inhibitors of factor Xa. 相似文献
74.
75.
Gabriela Flores-Ramírez Manuel Rivera Alfredo Morales-Pablos Joel Osuna Xavier Soberón Paul Gaytán 《BMC chemical biology》2007,7(1):1
Background
The effect of single and multiple amino acid substitutions in the green fluorescent protein (GFP) from Aequorea victoria has been extensively explored, yielding several proteins of diverse spectral properties. However, the role of amino acid deletions in this protein -as with most proteins- is still unknown, due to the technical difficulties involved in generating combinatorial in-phase amino acid deletions on a target region. 相似文献76.
Xavier Verdaguer Iolanda Marchueta Jordi Tormo Albert Moyano Miquel A. Perics Antoni Riera 《Helvetica chimica acta》1998,81(1):78-84
A convenient preparation of (1R,2S,3R,4S)-3-(neopentyloxy)isoborneol (= (1R,2S,3R,4S)-3-(2,2-dimethyl-propoxy)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol; 1a ), a valuable chiral auxiliary, is described. The synthesis involves six steps starting from the readily available camphorquinone ( 5 ) and gives 1a in 48% overall yield. The key step is the chemoselective hydrolysis of the less hindered 1,3-dioxolane moiety in the camphorquinone di-acetal 4 . 相似文献
77.
78.
Nicolas P. Cheval Barbara Hoffmann Anna Dikova Fatih Sirindil Philippe Bertus Aurélien Blanc Jean-Marc Weibel Patrick Pale 《Tetrahedron》2018,74(50):7111-7119
Vinyl nosylates, readily obtained from β-dicarbonyl derivatives, could be efficiently engaged in Sonogashira cross-coupling reactions, either cocatalyzed by copper or silver salts. The para-nitrobenzenesulfonate (nosylate) group allows this coupling to be performed under very mild conditions (room temperature). These new leaving group and mild conditions could be applied to the synthesis of acetylenic coumarinyl derivatives and to the total synthesis of an acetylenic monoterpene natural product, named cleviolide. 相似文献
79.
80.
Adrian M. Tomuta Xavier Fernández‐Francos Francesc Ferrando Xavier Ramis Àngels Serra 《先进技术聚合物》2013,24(11):962-970
A hyperbranched aromatic polyester (HBPOH) has been synthesized, and poly(ε‐caprolactone) arms have been grown on some of its end hydroxyl groups (HBPCL). These modifiers have been used in cationic diglycidyl ether of bisphenol A formulations cured with ytterbium triflate as cationic initiator. The effect of HBPOH and HBPCL on the curing kinetics has been studied using differential scanning calorimetry (DSC). The obtained materials have been characterized by dynamomechanical analysis, DSC, thermogravimetric analysis and mechanical tests. The modifiers are incorporated into the thermosetting network because of the participation of the end hydroxyl groups in the cationic curing of epoxides by the activated monomer mechanism. Homogeneous thermosets have been obtained with a remarkable increase in impact strength without sacrificing elastic modulus or hardness. A compromise between the rigid structure of the aromatic hyperbranched core and the flexibilizing effect of the poly(ε‐caprolactone) arms is believed to be responsible for the overall thermal and mechanical properties of the materials. The use of these polymeric modifiers increases the thermal stability of the resulting materials because of the low degradability of the aromatic ester groups in the hyperbranched core and the incorporation of the modifier into the network structure. However, the presence of such ester groups makes them reworkable by hydrolysis or alcoholysis in an alkaline medium, thus opening a way for recovery of valuable substrates. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献