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31.
An analytical method has been developed for the determination of residues of ethephon (2-chloroethyl phosphonic acid) in drinking and surface water. The procedure is based on de-ionisation with an anion/cation-exchange resin, solid phase extraction by means of anion-exchange polystyrene-divinylbenzene extraction disks, elution with a mixture of methanol and 10 M hydrochloric acid (98/2, v/v), redisolution into acetonitrile after evaporation and silylation with N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA). Quantification is performed by gas chromatography with ion-trap cubic mass spectrometric detection in the electron impact mode (GC-EI-MS3). Method validation was conducted using samples of mineral, tap, and river water that were fortified with ethephon at concentration levels ranging from 0.1 to 1.0 microg/L. The mean recovery from all the fortified samples (n = 36) amounted to 88% with a relative standard deviation of 17%. The method, therefore, was shown to allow accurate determination of ethephon residues in drinking and surface water with a limit of quantification of 0.1 microg/L. 相似文献
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Renard PY Schwebel H Vayron P Josien L Valleix A Mioskowski C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(13):2910-2916
A new and particularly mild method for the formation of phosphorus-sulfur bonds has been achieved through base-catalyzed addition of thiocyanate to the corresponding H-phosphine oxide, phosphinate, or phosphonate. This reaction procedure offers many advantages: the use as starting material of a stable and not oxygen-sensitive phosphorus(v) species, particularly mild and nonaqueous reaction conditions and workup (a pivotal point for these sensitive phosphonothioates), and, through optimized access to thiocyanates, a wider scope of substrates. This method has been applied to achieve the synthesis of substrate analogues for the study of antibody-catalyzed hydrolysis of acetylcholinesterase inhibitor PhX (11). 相似文献
34.
Langer F Schwink L Devasagayaraj A Chavant PY Knochel P 《The Journal of organic chemistry》1996,61(23):8229-8243
The hydroboration of olefins with Et(2)BH provides diethyl(alkyl)boranes 2 which readily undergo a boron-zinc exchange with Et(2)Zn providing a range of polyfunctional primary, secondary, and benzylic diorganozincs. The resulting diorganozincs 3 have been reacted with various electrophiles (allylic halides, acid chlorides, alkylidenemalonates, ethyl propiolate, nitroolefins) in the presence of CuCN.2LiCl with excellent yields. With secondary dialkylzincs prepared from diastereomerically pure diethyl(alkyl)boranes, the boron-zinc exchange occurs with loss of stereochemistry. The asymmetric addition of 3 to aldehydes in the presence of the chiral catalyst 55 furnishes optically active polyfunctional secondary alcohols (50 to over 96% ee). 相似文献
35.
Stereospecific intermediate nitrite formation occurs in the title reaction. 相似文献
36.
Sabelle S Renard PY Pecorella K de Suzzoni-Dézard S Créminon C Grassi J Mioskowski C 《Journal of the American Chemical Society》2002,124(17):4874-4880
Acetylcholinesterase is one of the most widely used and studied enzymes. Not only does this enzyme regulate neurotransmission (and thus play a key role in neurodegenerative processes) but it is also a prime target for pest control agents and warfare agents. Above all, due to its particularly high turnover rate, acetylcholinesterase is among the most efficient reporter enzymes yet described (for use as enzymatic tracer in immunoassays, for instance). However, its activity is detected through a colorimetric reagent, the Ellman reagent, which displays low detection limits and is often subject to background perturbations. In the course of our search for a more sensitive detection assay, we describe here a first-generation 1,2-dioxetane chemiluminescent probe, based on chemically induced electron exchange luminescence, which has an approximately 10 times lower detection limit than the Ellman colorimetric assay (2.5 x 10(-19) mol for Electrophorus electricus AChE in its tetrameric form). 相似文献
37.
Zhen-Yu Yin Ching S. Chang Pierre-Yves Hicher Minna Karstunen 《International Journal of Plasticity》2009
This paper presents a micromechanical analysis of the macroscopic behaviour of natural clay. A microstructural stress–strain model for clayey material has been developed which considers clay as a collection of clusters. The deformation of a representative volume of the material is generated by mobilizing and compressing all the clusters along their contact planes. Numerical simulations of multistage drained triaxial stress paths on Otaniemi clay have been performed and compared the numerical results to the experimental ones in order to validate the modelling approach. Then, the numerical results obtained at the microscopic level were analysed in order to explain the induced anisotropy observed in the clay behaviour at the macroscopic level. The evolution of the state variables at each contact plane during loading can explain the changes in shape and position in the stress space of the yield surface at the macroscopic level, as well as the rotation of the axes of anisotropy of the material. 相似文献
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An air-coupled ultrasonic transducer is created by bonding a bulk piezoelectric element onto the surface of a thick plate with a wedge of power-law profile. The wedge is used to improve the ultrasonic radiation efficiency. The power-law profile provides a smooth, impedance-matching transition for the mechanical energy to be transferred from the thick plate to the air, through the large-amplitude flexural waves observed in the thinnest region of the wedge. The performance of the proposed transducer is examined numerically and compared to that of a design where the piezoelectric element is isolated and where it is affixed to a thin plate of uniform thickness. The numerical analysis is first focused on the free-field radiation of the transducers. Then, time-reversal experiments are simulated by placing the transducers inside a cavity of arbitrary shape with some perfectly reflecting boundaries. In addition to time-reversal mirrors, the proposed concept could be integrated in the design of phased arrays and parametric arrays. 相似文献
40.
Sacré PY Deconinck E Daszykowski M Courselle P Vancauwenberghe R Chiap P Crommen J De Beer JO 《Analytica chimica acta》2011,(2):224-231
Most of the counterfeit medicines are manufactured in non good manufacturing practices (GMP) conditions by uncontrolled or street laboratories. Their chemical composition and purity of raw materials may, therefore, change in the course of time. The public health problem of counterfeit drugs is mostly due to this qualitative and quantitative variability in their formulation and impurity profiles.In this study, impurity profiles were treated like fingerprints representing the quality of the samples. A total of 73 samples of counterfeit and imitations of Viagra® and 44 samples of counterfeit and imitations of Cialis® were analysed on a HPLC-UV system. A clear distinction has been obtained between genuine and illegal tablets by the mean of a discriminant partial least squares analysis of the log transformed chromatograms. Following exploratory analysis of the data, two classification algorithms were applied and compared. In our study, the k-nearest neighbour classifier offered the best performance in terms of correct classification rate obtained with cross-validation and during external validation. For Viagra®, both cross-validation and external validation sets returned a 100% correct classification rate. For Cialis® 92.3% and 100% correct classification rates were obtained from cross-validation and external validation, respectively. 相似文献