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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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The effect of variation of the integral length scale on the accuracy of Taylor’s hypothesis and the assumption of local isotropy
when a mean strain is applied to a nearly homogeneous and isotropic, heated turbulent flow is investigated. The mean strain
is produced by placing one of two cylinders downstream of the heated wire mesh. Results show, the mean strain rate where the
directly measured variance of the streamwise spatial gradient differs by less than ten percent from the corresponding value
computed using Taylor’s hypothesis and temporal derivative decreases with increasing the ratio of the integral length scale
to the cylinder diameter.
Received: 13 November 1997 / Accepted: 23 April 1998 相似文献
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搭建了一套研究金属和金属氧化物表面的超快激发态电子动力学和光化学动力学的飞秒双光子光电子能谱仪. 该装置将半球形电子能量分析仪和成像技术相结合,同时测量光电子的能量和角度分布.通过Mach-Zehnder干涉仪测量时间分辨的双光子光电子能谱获得超快激发电子态的动力学信息. 这一功能在Cu(111)上得到了证实. 另外还发展了一个通过实时测量双光子光电子能谱来研究表面光化学的方法,并成功应用到CH3CH2OH/TiO2(110)体系. 研究表明,只有将两种方法结合起来才能正确地研究光诱导的表面激发共振的动力学. 相似文献
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A Surface Femtosecond Two-Photon Photoemission Spectrometer for Excited Electron Dynamics and Time-Dependent Photochemical Kinetics
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Ze-feng Ren Chuan-yao Zhou Zhi-bo Ma Chun-lei Xiao Xin-chun Mao Dong-xu Dai Jerry LaRue Russell Cooper Alec M. Wodtke Xue-ming Yang 《化学物理学报(中文版)》2010,23(3):255-261
A surface femtosecond two-photon photoemission (2PPE) spectrometer devoted to the study of ultrafast excited electron dynamics and photochemical kinetics on metal and metal oxide surfaces has been constructed. Low energy photoelectrons are measured using a hemispheri-cal electron energy analyzer with an imaging detector that allows us to detect the energy and the angular distributions of the photoelectrons simultaneously. A Mach-Zehnder interferom-eter was built for the time-resolved 2PPE (TR-2PPE) measurement to study ultrafast surface excited electron dynamics, which was demonstrated on the Cu(111) surface. A scheme for measuring time-dependent 2PPE (TD-2PPE) spectra has also been developed for studies of surface photochemistry. This technique has been applied to a preliminary study on the photochemical kinetics on ethanol/TiO2(110). We have also shown that the ultrafast dy-namics of photoinduced surface excited resonances can be investigated in a reliable way by combining the TR-2PPE and TD-2PPE techniques. 相似文献
10.
This study compares the shedding behavior around and downstream of a single plate positioned in a flow field alone with the
shedding behavior around and downstream of the same plate positioned in an array of identical plates. The shedding frequencies
and corresponding Strouhal numbers based on chord [S
r
(c)] and based on thickness [S
r
(t)] are obtained using a hot-wire anemometer. In comparison with the plate positioned as a single plate, the same plate placed
in a plate array shows increases in S
r
(c) of up to 55.5% and produces a dominant peak in the power spectra that is wider by a factor of 3.5. In contrast to the
single-plate results, which exhibit step changes in S
r
(c) of about 0.6 at c/t ≈ 6, 8 and 11, the plate positioned in an array shows only one abrupt transition at c/t ≈ 4.
Received: 26 January 1999/Accepted: 7 February 2000 相似文献