Stereoselective Synthesis of Highly Functionalized Nitrocyclopropanes through the Organocatalyic Michael‐Addition‐Initiated Cyclization of Bromonitromethane and β,γ‐Unsaturated α‐Ketoesters

A highly diastereo‐ and enantioselective cyclopropanation of β,γ‐unsaturated α‐ketoesters with bromonitromethane has been successfully developed through a domino Michael‐addition/intramolecular‐alkylation strategy. Acceptable yields (up to 89 %) and enantioselectivities (up to 96 % ee) have been obtained.     

Stabilization of zeylenone in rat plasma by the presence of esterase inhibitors and its LC‐MS/MS assay for pharmacokinetic study

Six esterase inhibitors, namely EDTA·2Na⁺, NaF, phenylmethanesulfonyl fluoride, dichlorvos, bis‐nitrophenyl phosphate (BNPP) and thenoyltrifluoroacetone, and the mixture of NaF and BNPP, were evaluated for the stabilization of labile benzoate containing zeylenone in rat plasma. The mixture appeared to exhibit the most effectively stabilizing effect with the degraded content of zeylenone decreasing from >60% (in the absence of inhibitors) to <6%. Following the stabilization by the addition of NaF (5 mm ) and BNPP (5 mm ), the analytes in rat plasma were acidified by formic acid and extracted into ethyl acetate at 0°C. After chromatographic separation, the detection of zeylenone was performed on a 3200 Q‐Trap with positive ion electrospray mode, monitoring the ion transition m/z 383.2 → 105.0. The method was validated over the range from 2.68 to 1340 ng/mL with inter‐ and intra‐run precision for the quality control samples being less than 6.8%. The assay accuracy was within 100 ± 7.0%. The validated method was successfully applied to a pharmacokinetic study in rats after the intratracheal administration of zeylenone in free drug or polymeric micellar solutions. The results showed that the pulmonary absorption of zeylenone loaded in micelles was significantly retarded compared with that of free drug solutions. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis of Imides by Palladium‐Catalyzed C?H Functionalization of Aldehydes with Secondary Amides

An efficient palladium‐catalyzed C? H functionalization of aldehydes with various N‐substituted N‐heteroarene‐2‐carboxamides has been developed for the synthesis of secondary imides. The reaction tolerates various functionalities, such as methoxy, fluoro, chloro, and bromo groups. A tentative radical mechanism for a Pd^II/Pd^IV catalytic cycle is proposed.     

固相微萃取-气相色谱-质谱法检测30种农药残留

建立使用一种萃取头同时检测蔬菜中30种农药的GC-MS分析方法。采用了SPME-GC/MS自动进样技术,比较聚二甲基硅氧烷(PDMS)、聚丙烯酸酯(PA)、聚二甲基硅氧烷-二乙烯基苯(PDMS/DVB)、聚乙二醇-二乙烯基苯(CW/DVB)4种固定相涂层的分析效果,选择了目标物萃取效率较高、干扰物萃取较少的PDMS。通过正交实验设计,选择不同的萃取温度、萃取时间、振荡速度进行试验,最终确定振荡速度250 r/min,萃取温度70℃,萃取时间60 min作为萃取条件。对不同的无机盐浓度对标准品溶液和加入基质标准品溶液的提取效率的影响分别进行了试验,确定用10%(w/V)NaCl溶液增加提取液离子强度。试验过程中优化分析的色谱条件和质谱条件,进样到分析结束时间可控制在40 min。该方法检测蔬菜样品中混合标准溶液的回收率为43%～119%,相对标准偏差在3.4%～19%之间。     

Effects of High Salt Concentration and Residue on Copper and Aluminum Corrosion

Traditional researches on metal corrosion under salt solutions deposit conditions are usually carried out by visual, electron microscopic observations and simple electrochemical measurement via a traditional one-piece electrode. These techniques have difficulties in measuring localized corrosion that frequently occur in inhomogeneous media. This paper reports the results from the experiments using specially shaped coupons and a relatively new method of measuring heterogeneous electrochemical processes, namely, the wire beam electrode(WBE). Preliminary results from copper and aluminum corrosion in highly concentrated sodium chloride solutions with and without solid deposits show that the method is useful in simulating and studying corrosion especially localized corrosion in pipelines.     

谷氨酸甲基化修饰的基质辅助激光解吸电离-串联飞行时间质谱分析

利用基质辅助激光解吸电离-串联飞行时间质谱(MALDI-TOF/TOF)高置信度地鉴定了枯草芽孢杆菌中的蛋白酶抑制剂和杆菌肽F两种蛋白及其翻译后修饰,发现在这两种蛋白质中共有5个肽段发生谷氨酸甲基化,其中肽段FELVVYDSEHK存在FE(Methylation)LVVYDSEHK和FELVVYDSE(Methylation)HK两种形式。结果表明,MALDI-TOF/TOF高能CID所提供的丰富断裂信息和全质量范围扫描对提高分析结果的确定性具有重要作用。此外,这5个甲基化肽段都可以检测到相对含量更高的非甲基化肽段,这为降低分析结果的假阳性提供了辅助判据。在低质量区检测到甲基化赖氨酸的亚胺相关离子m/z 98和143,说明发生了赖氨酸的甲基化;检测到m/z 116则提示发生了谷氨酸甲基化。