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111.
Zhang H Mitsumori S Utsumi N Imai M Garcia-Delgado N Mifsud M Albertshofer K Cheong PH Houk KN Tanaka F Barbas CF 《Journal of the American Chemical Society》2008,130(3):875-886
The development of enantioselective anti-selective Mannich-type reactions of aldehydes and ketones with imines catalyzed by 3-pyrrolidinecarboxylic acid and related pyrrolidine derivatives is reported in detail. Both (3R,5R)-5-methyl-3-pyrrolidinecarboxylic acid and (R)-3-pyrrolidinecarboxylic acid efficiently catalyzed the reactions of aldehydes with alpha-imino esters under mild conditions and afforded anti-Mannich products with high diastereo- and enantioselectivities (anti/syn up to 99:1, up to >99% ee). For the reactions of ketones with alpha-imino esters, (R)-3-pyrrolidinecarboxylic acid was an efficient catalyst (anti/syn up to >99:1, up to 99% ee). Evaluation of a series of pyrrolidine-based catalysts indicated that the acid group at the beta-position of the pyrrolidine ring of the catalyst played an important role in forwarding the carbon-carbon bond formation and in directing anti-selectivity and enantioselectivity. 相似文献
112.
A stochastic model is developed describing a service system subject to inhomogeneous Poisson interruptions with age dependent interruption periods. By studying the probabilistic flow of the underlying multivariate Markov process, the Laplace transform of the effective service time is explicitly obtained. For general renewal interruptions, only the expected effective service time is derived. As an application, an optimal checkpoint policy is examined for database management. It is shown that an optimal policy maximizing the ergodic availability of the database is to implement a checkpoint as soon as the cumulative uptime of the database reaches a prespecified constantk
*. A computational procedure is then developed for findingk
* and numerical results are exhibited.This work was supported in part by the National Science Foundation under Grant No. ECS-8600992 and by the IBM Program of Support for Education in the Management of Information Systems. 相似文献
113.
Yuji Sano Kotaro Shirai Naoto Takahata Takafumi Hirata Neil C Sturchio 《Analytical sciences》2005,21(9):1091-1097
Concentrations of minor (Mg and Sr) and trace (Ba and U) elements in four natural calcium carbonate samples were first analyzed by inductively coupled plasma mass spectrometry (ICP-MS) after chemical dissolution and calibrated against a standard dolomite. Their homogeneities were checked by in situ laser ablation (LA) ICP-MS with 10-20 spots. The carbonate samples were measured by using a high lateral resolution secondary ion mass spectrometer (Nano-SIMS NS50). A approximately 4 nA O- primary beam was used to sputter a 5-6-microm diameter crater on the sample surface, and secondary positive ions were extracted for mass analysis using an accelerating voltage of 8 kV and a Mattauch-Herzog geometry. A multi-collector system was adjusted to detect 26Mg+, 43Ca+, 88Sr+, 138Ba+, 238U16O+ and 238U16O2+ ions at the same time. A resolving power of 2500-5000 at 10% peak height was attained by an entrance slit set at 40 microm, and each exit slit at 50 microm with adequate flat-topped peaks. The observed 26Mg/43Ca, 88Sr/43Ca, 138Ba/43Ca and 238U16O2/43Ca ratios agreed well with those measured by LA-ICP-MS. Foraminifera shells were analyzed at 5-6 microm scale by Nano-SIMS. There was a large variation of the Mg/Ca ratios, up to +/- 38%, even in a single fragment of the shell, suggesting that although the ratios provide a useful paleoceanographic proxy at bulk scale, they may reflect a more complex pattern at < 10 microm scale. 相似文献
114.
Kazuharu Sugawara Naoto Kamiya George Hirabayashi Hideki Kuramitz 《Analytical sciences》2005,21(8):897-900
Avidin, which is one type of glycoprotein, has a strong affinity with biotin (Ka = 10(15) M(-1)). Iminobiotin also forms a complex with avidin (Ka = 10(8) M(-1) at pH 9.5). The avidin-iminobiotin complex changes to the avidin-biotin complex in the presence of biotin because of the difference of the binding constant to avidin. In this study, the interaction between avidin and iminobiotin labeled with an electroactive compound was investigated by voltammetry. After avidin and the labeled iminobiotin (LI) were incubated in 0.1 M phosphate buffer (pH 7.0), the peak currents of LI were measured in various concentrations of biotin. The peak currents increased with increasing the concentration of biotin. Thus, this observation indicates the formation of avidin-biotin complex. On the other hand, the formation of avidin-iminobiotin complex depended on the pH of the solution. LI combines with the avidin at pH 5.6-8.9 and dissociates at pH 4.6. 相似文献
115.
Nobuyasu Itoh Takamitsu Otake Masahiko Numata Yoshie Aoyagi Mayumi Matsuo Takashi Yarita 《Analytical sciences》2008,24(9):1129-1133
To improve the extraction of polycyclic aromatic hydrocarbons (PAHs) from sediment samples, we optimized the conditions of pressurized liquid extraction (PLE). The yields increased as the extraction temperature increased from 100 to 190 degrees C, but the effect of increasing pressure (from 15 to 20 MPa) was small. Parameters of 190 degrees C and 20 MPa, near the maximum of the equipment, gave the highest yield. Under these conditions, the yields of 17 PAHs were 1.5 - 34 times those obtained by the Japanese official method (shaking and ultrasonic extraction with acetone at room temperature). 相似文献
116.
Nobuyasu Itoh Masahiko Numata Yoshie Aoyagi Takashi Yarita 《Analytical sciences》2008,24(9):1193-1197
For the accurate quantification of polycyclic aromatic hydrocarbons (PAHs) in environmental samples by isotope-dilution mass spectrometry (IDMS) and gas chromatography-mass spectrometry (GC-MS), we used deuterium-labeled PAHs (D-PAHs) as internal standards for microg g(-1)-level certified reference materials and corresponding calibration solutions. Although pressurized liquid extraction (PLE) causes significant biases in the analytical results for ng g(-1)-level samples (2.4 - 15%), biases in the analytical results by PLE (190 degrees C, 20 MPa, 2 cycles) were small (<2.3%) and negligible for microg g(-1)-level samples when expanded uncertainty (coverage factor k = 2) was considered. 相似文献
117.
A manifold is described which permits the analysis of less than 1 ml of sample solution. Water- and air-compensation methods for the introduction of the carrier stream into the nebulizer are effective in obtaining sensitive and reproducible measurements of magnesium, but air-compensation gives higher peak responses. 相似文献
118.
K. Ishibashi Y. Aoyagi S. Namba Y. Ochiai M. Kawabe K. Gamo 《Superlattices and Microstructures》1991,9(4)
Magnetoresistance measurements have been performed in narrow GaAs/AlGaAs wires in order to study the scattering process in mesoscopic wires. Amplitude analysis of the Shubnikov -de Haas oscillations shows that electrons have two scattering times, depending upon the magnetic field range. The critical field which separates these scattering times seems to be determined by the relation between the wire width and the electron cyclotron radius. This effect is discussed in terms of the electron trajectories in a wire under the magnetic field. 相似文献
119.
Masayasu Tasaka Satoshi Tamura Naoto Takemura Keisuke Morimoto 《Journal of membrane science》1982,12(2):169-182
Electroosmosis and streaming potential measurements were carried out across charged membranes made of collodion and sulfonated polystyrene. Experiments were confined to the range where linear flux/force relationships hold. Saxén's relationship holds between electroosmosis and streaming potential; for porous charged membranes these exhibit an approximate inverse proportionality to ionic mobility at the limit of low electrolyte concentration. Both tend towards zero at the limit of high electrolyte concentration. 相似文献
120.
The addition of arylboronic acids 1 to azodicarboxylates 2 in the presence of a catalytic amount of a copper salt under mild reaction conditions gives aryl-substituted hydrazines 3 in high yields. The reaction is tolerant of a wide variety of functional groups. 相似文献