Using multiple short-end injections to develop fast electrophoretic separations--applications in iodide analysis

The aim of this study was to develop a fast CE separation method by using multiple short-end injections in a capillary coated with quaternary ammonium chitosan (HACC), in order to determine the iodide content of pharmaceutical formulations. The BGE was composed of 20 mM tris(hydroxymethyl)aminomethane and 11 mM hydrochloric acid, at pH 8. The internal standard used was thiocyanate. Separations were performed in a fused silica capillary (32 cm total length, 8.5 cm effective length and 50 μm i.d.) coated with HACC and direct UV detection at 220 nm. EOF was modified by flushing the capillary with polymeric solution, resulting in a semi-permanent coating of controlled and stable EOF. The EOF was anodic at pH 8. Different strategies, using single and multiple injection short-end configurations, were studied to develop a CE method that resulted in a maximum number of iodide samples analyzed per hour: one plug and flush (Sflush) 35 samples/h, one plug without flush (SWflush) 76 samples/h, four plugs and flush (Mflush) 61 samples/h, and four plugs without flush (MWflush) 80 samples/h. Using the multiple injection configuration, it was possible to inject up to four plugs using spacer electrolytes with good separation efficiency and selectivity. The voltage application time needed to separate the eight peaks (iodide and thiocyanate) with MWflush was only 12s. The method was validated and samples were analyzed using MWflush. Good linearity (R(2)>0.999); a limit of detection 0.4 mg L(-1); intermediate precision better than 3.8% (peak area) and recovery in the range of 99-102% were obtained.     

Asymmetric Total Synthesis of Hasubanan Alkaloids: Periglaucines A–C,N,O-Dimethyloxostephine and Oxostephabenine

We report herein the asymmetric total synthesis of periglaucines A–C, N,O-dimethyloxostephine and oxostephabenine. The key strategies used include: 1) a Rh^I-catalyzed regio- and diastereoselective Hayashi-Miyaura reaction to connect two necessary fragments; 2) an intramolecular photoenolization/Diels–Alder (PEDA) reaction to construct the highly functionalized tricyclic core skeleton bearing a quaternary center; 3) a bio-inspired intramolecular Michael addition and transannular acetalization to generate the aza[4.4.3]propellane and the tetrahydrofuran ring.     

Enantioselective Rhodium-Catalyzed Pauson–Khand Reactions of 1,6-Chloroenynes with 1,1-Disubstituted Olefins

An enantioselective rhodium(I)-catalyzed Pauson–Khand reaction (PKR) using 1,6-chloroenynes that contain challenging 1,1-disubstituted olefins is described. In contrast to the previous studies with these types of substrates, which are only suitable for a single type of tether and alkyne substituent, the new approach results in a more expansive substrate scope, including carbon and heteroatom tethers with polar and non-polar substituents on the alkene. DFT calculations provide critical insight into the role of the halide, which pre-polarizes the alkyne to lower the barrier for metallacycle formation and provides the proper steric profile to promote a favorable enantiodetermining interaction between substrate and chiral diphosphine ligand. Hence, the chloroalkyne enables the efficient and enantioselective PKR with 1,6-enynes that contain challenging 1,1-disubstituted olefins, thereby representing a new paradigm for enantioselective reactions involving 1,6-enynes.     

闽江口晚第四纪海侵地层的研究

大量钴孔岩芯的岩性特征,微体古生物硅藻和有孔虫化石组合,以及~(14)C测年结果揭示,闽江河口区发育两期海侵地层。表明本区在晚第四纪期间至少经历了两次海侵事件,发生于距今44000～22000a的玉木亚间冰期海侵相对较弱,其范围仅达福州市区一带,另一次海侵发生于距今12000a以来的冰后期,该次海侵较为广泛,其范围可达闽侯的甘蔗一带。     

南京地区第四系主要地层类型及分层探讨

南京地区地形地貌复杂,第四系分布变化大,在归纳南京地区第四纪沉积环境的基础上,总结了不同地貌和地质单元的地层层序特征。根据地层的成因和工程性质,结合国家规范中的地层分类原则,提出了统一分层的方法和统一的地层代号,将该地区第四系划分为填土、新近沉积土、一般沉积土和老沉积土等4个大层和若干亚层,同时提供了各层土的基本物理力学性质、典型剖面。对今后的勘察研究提出了建议。     

Synthesis of quaternary succinimides promoted by Ferric Nitrate

An efficient protocol has been accomplished for the synthesis of quaternary α-aminosuccinimides in toluene medium involving 2-phenylimidazo[1, 2-a]pyridine in a one-pot reaction promoted by Ferric Nitrate at 120?°C. The protocol presented herein, is for the first time, via a novel transformation where Ferric Nitrate promotes imidazo[1,2-a]pyridine structural metamorphosis to the title compound quaternary succinimides. High compatibility, easy work-up, and excellent yields are the advantages of this protocol. The quaternary α-aminosuccinimides are expected to have great potential in synthesizing quaternary α-amino acids and applications in medicinal chemistry.     

Ti（Ⅳ）—Tar—PF—CTMAB体系显色反应的研究及应用

研究了Ti(Ⅳ ) 酒石酸盐 (Tar) 苯基荧光酮 (PF) CTMAB四元配合物的显色条件及其应用。该配合物的λmax=5 5 8nm ,钛在 0～ 4 μg/ 2 5ml范围内遵守比耳定律。方法灵敏度高 ,其表观摩尔吸光系数达 1.74× 10 5,且选择性较高。用此法测定合金钢中的钛 ,结果满意