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1.
Garcia Ruano JL Alcudia A del Prado M Barros D Maestro MC Fernandez I 《The Journal of organic chemistry》2000,65(10):2856-2862
The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported. 相似文献
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Garcia Ruano JL Alemparte C Martin Castro AM Adams H Rodriguez Ramos JH 《The Journal of organic chemistry》2000,65(23):7938-7943
The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles. 相似文献
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The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton. 相似文献
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Acoustic performance in ultrasonic transmitters can be improved by means of a suitable electrical driving response and matching/tuning networks. It is important to predict this electrical response, but doing so is not easy because it departs notably from the nominal pattern with the loading probes. In practice, the analysis of HV pulser spikes in NDE applications requires fairly complex models in the transient regime and, in addition, non-linear problems could arise, especially in the case of tuned transmitters. In this paper, the most relevant influences of loading characteristics of NDT ultrasonic probes on the pulser electrical driving responses are evaluated in time and frequency domains. Conventional pulse generators and typical NDE pulsers are considered. Driving responses are analysed across commercial ultrasonic probes and, alternatively, across similar purely electrical loads. Distinct influences on pulser responses from electrical and motional sections of the probes are identified. All these aspects are studied on the basis of experimental and computer results. 相似文献
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Mazerolles G Preys S Bouchut C Meudec E Fulcrand H Souquet JM Cheynier V 《Analytica chimica acta》2010,678(2):195-202
In the present study, direct flow injection mass spectrometry was investigated for rapid characterization of the polyphenolic composition of red wines. Atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) (in both positive and negative ion modes) have been simultaneously used for a more comprehensive analysis of the samples studied. In this way, four mass spectra have been recorded for each wine. Each spectrum was considered as a fingerprint related to the chemical composition. This methodology was applied to a large number of Beaujolais wines from different grades and different vintages.This data set was processed using a chemometrical multiblock analysis, which allowed to synthesize the whole information collected. The results obtained showed that the wine fingerprints address the composition of the main polyphenolic compounds present in the red wines and can discriminate groups of wines showing different polyphenolic compositions. Multiblock analysis appears as a very promising tool to deal with several data tables of multivariate signals in order to define, by combining the whole information, the best operating protocol according to the desired analytical objectives. 相似文献
7.
Rodrigues AC Nascimento ML Bragatto CB Souquet JL 《The Journal of chemical physics》2011,135(23):234504
Conductivity data of the xAgI(1 - x)AgPO(3) system (0 ≤ x ≤ 0.5) were collected in the liquid and glassy states. The difference in the dependence of ionic conductivity on temperature below and above their glass transition temperatures (T(g)) is interpreted by a discontinuity in the charge carrier's mobility mechanisms. Charge carrier displacement occurs through an activated mechanism below T(g) and through a Vogel-Fulcher-Tammann-Hesse mechanism above this temperature. Fitting conductivity data with the proposed model allows one to determine separately the enthalpies of charge carrier formation and migration. For the five investigated compositions, the enthalpy of charge carrier formation is found to decrease, with x, from 0.86 to 0.2 eV, while the migration enthalpy remains constant at ≈0.14 eV. Based on these values, the charge carrier mobility and concentration in the glassy state can then be calculated. Mobility values at room temperature (≈10(-4) cm(2) V(-1) s(-1)) do not vary significantly with the AgI content and are in good agreement with those previously measured by the Hall-effect technique. The observed increase in ionic conductivity with x would thus only be due to an increase in the effective charge carrier concentration. Considering AgI as a weak electrolyte, the change in the effective charge carrier concentration is justified and is correlated to the partial free energy of silver iodide forming a regular solution with AgPO(3). 相似文献
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The performance of transducers used for medical diagnosis depends to a great extent on matching layer, backing impedance and geometry of the active surface. In this paper special attention is given to the element vibrational modes, the optimum matching, the grating lobe and change of the real acoustic impedance into an imaginary impedance as a function of the product of the width and wavelength. Grating lobes on the echo image and the effect of a mismatch of the matching layer are illustrated. Suggestions are made for the design of linear and phased array transducers considering the above-mentioned aspects. 相似文献
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A wide variety of transducer shapes and applications exists in the field of diagnostic ultrasound. As a basic material ferro-electric ceramics are used almost exclusively, but polymer piezoelectric material seems a new alternative. By comparing in a qualitative way the most relevant parameters of these materials, a state of the art judgement may be made about their applicability in diagnostic ultrasound. 相似文献
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Glasses in the binary system xAg2P2O6 − (1 − x)Ag2Te2O5 have been prepared for 0 x 1. For each composition only one glass transition temperature is observed in the temperature range of 180–220 °C. All glasses appear homogeneous considering their optical and electrical properties. Nevertheless, in SEM observations, some glass compositions appear to be heterogeneous after decoration following short nitric acid etching. For each composition, conductivity data obtained in the temperature range of 25–200 °C using impedance techniques obey an Arrhenius relationship with a composition independent pre-exponential term. Variation of the conductivity activation energy with x induces correlative variations of isothermal conductivity curves leading to an increase of the ionic conductivity of about one order of magnitude compared with linearity at 25 °C. This behaviour is discussed with respect to the thermodynamic properties of the glassy solutions. 相似文献