Total Synthesis of (+)-Sinefungin

Sinefungin (1) a nucleoside antibiotic isolated from Streptomyces has been synthesized from D-ribose. Both the C-6 and C-9 stereogenic centers were constructed by efficient asymmetric syntheses. The C-6 amine stereochemistry was set by a highly diastereoselective allylation (>99% de) of a (1S,2R)-1-amino-2-indanol-derived oxazolidinone 9 followed by a Curtius rearrangement of 11 to 12. The C-9 amino acid stereochemistry of sinefungin (1) was established by a rhodium chiral bisphosphine-catalyzed asymmetric hydrogenation of an alpha-(acylamino)acrylate derivative. The anomeric adenosylation of the mixture of anomeric acetates 20 in the presence of C-6 urethane NH was found to be extremely difficult. Conversion of the C-6 urethane NH as its N-benzyl derivative 21 was necessary prior to the adenosylation reaction. Successful adenosylation was effectively carried out by Vorbrüggen's protocol utilizing persilylated N(6)-benzoyladenine and trimethylsilyl triflate.     

Preparation of Multitracer Nuclides from 232Th(NO3)4 Irradiated by 40Ar Ion Beam

Nuclear counting statistics at high count rate are assessed on a -ray spectrometer set-up with a Wilkinson analog to digital convertor. The validity of recent theoretical formulas for the standard deviation, before and after pulse-loss compensation, is checked. The experimental counting uncertainty is well reproduced by theory. Without pulse-loss compensation (cf. real-time mode), it is dependent on the size and position of the considered region of interest in the spectrum. With pulse-loss compensation (cf. live-time correction) the relative deviation from Poisson statistics is equal for all regions of interest in the spectrum.     

HPLC Determination and Pharmacokinetic Study of Indapamide in Human Whole Blood

A rapid and sensitive HPLC method for the quantification of indapamide in human whole blood is described. The procedure involves liquid–liquid extraction of human whole blood with methyl tertiarybutyl ether coupled with reversed-phase HPLC and UV detection. Separation was performed on a YMC^® ODS-A reverse column (5 µm particle size, 4.6×150 mm i.d.). The mobile phase was composed of acetonitrile - 2-propanol ?0.1 triethylamine in water (adjusting to pH 3.75 with 85% phosphoric acid) (35:5:60, v/v/v). The linear concentration range for indapamide was 5.0–500 ngmL^?1. The lower limit of quantification (LLOQ) was 5.0 ngmL^?1 for indapamide. Intra- and inter-assay RSD ranged from 2.36% to 4.53% and 1.68% to 8.01%, respectively. The sensitivity and precision were sufficient for determination of whole blood concentrations after therapeutic administration of both drugs and the method can be used for the estimation of pharmacokinetic parameters.     

Sorption and desorption of radioselenium on calcareous soil and its solid components

The effect of different solid soil components of calcareous soils on the retention of SeO₃ has been investigated by a batch technique and selective extraction method. The sorption and desorption isotherms of SeO₃ on the untreated calcareous soil and the three treated soils were determined at 20°C, pH 7.8±0.2 and in the presence of 0.001M CaCl₂. It was found that all isotherms are linear, the sorption-desorption hysteresis for untreated soil and treated soils is obvious and the retention of SeO₃ in calcareous soil is mainly attributed to the oxides.     

过渡金属盐促进的纳米氢化钠对硝基的还原反应

研究了在过渡金属盐促进下，纳米尺寸的活性氢化钠对硝基化合物的还原反应．结果表明，过渡金属盐的存在，使纳米氢化钠（ＮａＨ＊）的还原活性进一步增强，硝基苯的转化率在较短时间内就超过９０％．镍盐对生成苯胺的选择性最好（１００％），其次是锰盐．不同纳米碱金属氢化物对硝基苯还原的活性和生成苯胺的选择性顺序为ＮａＨ＊＞ＫＨ＊＞ＬｉＨ＊．几种硝基化合物的反应结果表明，ＮａＨ＊－镍盐是硝基还原生成芳胺有效的复合还原剂     

A Laboratory Investigation of the Reduction of Chromium Oxide by a Reverse-Polarity DC Plasma-Driven Molten Oxide Electrolysis Process

A method for producing chromium metal/chromium alloys using a reverse-polarity DC plasma-driven molten oxide electrolysis process was investigated. A laboratory-scale 50 kW DC plasma-crucible system was designed and built to investigate the feasibility of this process. Experiments on molten oxide electrolysis were successfully conducted to produce chromium metal from chromic oxide. Two starting slag systems, SiO₂–CaO–Al₂O₃–Cr₂O₃–Na₂O and SiO₂–CaO–Cr₂O₃–Na₂O, were used in this study. It was found that in each case chromic oxide was successfully reduced to metallic chromium. Aluminum was also reduced with the presence of alumina in the starting slag. Small amounts of carbon monoxide gas were introduced to the electrolysis system to study oxygen evolution rates from the plasma/slag interface. For the SiO₂–CaO–Al₂O₃–Cr₂O₃–Na₂O system, the oxygen evolution rate showed a maximum during the electrolysis process. For the SiO₂–CaO–Cr₂O₃–Na₂O system, the oxygen evolution rates displayed a declining trend with processing time. These two reduction behaviors were apparently controlled by different mechanisms. The significance of this process is that it might be used to produce carbon-free chromium metal/chromium alloys without carbon containing reducing agent and since no carbon based reactants are used for heating or reduction there are no carbon dioxide emissions.     

带形上随机环境中随机游动的内蕴分枝结构

揭示了带形上随机环境中随机游动的内蕴分枝结构一带移民的多物种分枝过程.利用内蕴分枝结构,可精确表达游动的首次击中时.给出了内蕴分枝结构的如下两个应用:(1)计算出首次击中时的均值,给出游动大数定律速度的显示表达,(2)得到从粒子角度看环境的马氏链不变测度的密度函数的显示表达,进而可用另一种"站在粒子看环境"的方法直接证明游动的大数定律.     

Suspension assisted synthesis of triblock copolymer-templated ordered mesoporous carbon spheres with controlled particle size

A general strategy in terms of large-scale and shape-controlled synthesis was used to design highly ordered mesoporous carbon spheres with controlled size from 50 to 500 microm by an evaporation induced organic-organic self-assembly inside ethanol-in-oil emulsions.     

One-step synthesis of carbon-supported Pd–Pt alloy electrocatalysts for methanol tolerant oxygen reduction

A facile, one-step reduction route was developed to synthesize Pd-rich carbon-supported Pd–Pt alloy electrocatalysts of different Pd/Pt atomic ratios. As-prepared Pd–Pt/C catalysts exhibit a single phase fcc structure and an expansion lattice parameter. Comparison of the oxygen reduction reaction (ORR) on the Pd–Pt/C alloy catalysts indicates that the Pd₃Pt₁/C bimetallic catalyst exhibits the highest ORR activity among all the Pd–Pt alloy catalysts and shows a comparative ORR activity with the commercial Pt/C catalyst. Moreover, all the Pd–Pt alloy catalysts exhibited much higher methanol tolerance during the ORR than the commercial Pt/C catalyst. High methanol tolerance of the Pd–Pt alloy catalysts could be attributed to the weak adsorption of methanol induced by the composition effect, to the presence of Pd atoms and to the formation of Pd-based alloys.     

Sign-changing saddle point

In this paper, the Saddle-point theorems are generalized to a new version by showing that there exists a “sign-changing” saddle point besides zero. The abstract result is applied to the semilinear elliptic boundary value problem