Synthesis of (R)(E)-3,7-Dimethyl-2-octene-1,8-dioic Acid, a Copulation Released Pheromone Component of Azuki Bean Weevil

Started from 5-hydroxy-2-pentanone, (R)(E)-3,7-dimethyl-2-octene-1,8-dioic acid, callosobruchusic acid, was synthesized via five steps with D-(-)-camphor sultam as the chiral auxiliary. It was of good optical purity and yield.

(E)-3-甲基-2-戊烯酸的合成研究

目的探索一种简洁高效的(E)-3-甲基-2-戊烯酸(D)的适用于工业生产的合成方法。方法以磷酰基乙酸三乙酯(A)和2-丁酮(B)为起始原料,利用Horner-Wadsworth-Emmons反应合成α,β-不饱和酯(C);(C)不经纯化直接进行碱性水解即得(D)。结论此方法具有原料简易可得、操作步骤简单、收率较高的特点,反应过程简单易控,适合工业化生产。

Modulatory Effects of EPA and DHA on Proliferation and Apoptosis of Pancreatic Cancer Cells

In order to investigate the effects of eicosapentaenoic acid （EPA） and docosahexaenoic acid （DHA） on the proliferation, apoptosis of pancreatic cancer cell line SW1990 cells and the expression of cyclin E mRNA, the SW1990 cells were treated with different concentrations of EPA or DHA （20, 40, 60 μg/mL） for 0, 12, 24, 36 and 48 h respectively. By using MTF method, the inhibitory effects of EPA or DHA on the cell growth were assayed. Real time PCR was used to detect the expression changes of cyclin E mRNA after the SW1990 cells were treated with 40μg/mL EPA or DHA for different time. Flow cytometry was used to test the changes of apoptostic rate in the SW1990 cells treated with different concentrations of EPA or DHA for 24 h. The results showed that EPA and DHA could inhibit the growth of SW1990 cells in a time- and concentration-dependent manner （P〈0.01）. EPA or DHA could also significantly inhibit the expression of cyclin E mRNA in a time-dependent manner （P〈0.05）. EPA or DHA could induce the apoptosis of SW1990 cells in a concentration-dependent manner （P〈0.01）. It was concluded that ω-3 fatty acid could inhibit the proliferation of pancreatic cancer cell line SW1990 cells and promote their apoptosis. The down-regulation of the cyclin E expression by ω-3 fatty acid might be one of the mechanisms for its anti-tumor effect on pancreatic cancer.

二妙丸HPLC指纹图谱及UPLC-LTQ-Orbitrap成分分析

目的建立二妙丸的HPLC指纹图谱质量评价方法,并对二妙丸中的化学成分进行UPLC-LTQ-Orbitrap定性分析。方法指纹图谱采用HPLC法,色谱柱为Shiseido C18柱(250 mm×4.6 mm,5μm),乙腈-0.1%甲酸水溶液为流动相进行梯度洗脱,体积流量为1.0 m L/min,检测波长为330 nm,以黄柏、苍术混合对照药材生成的色谱图为标准对照图谱,采用"中国药典委员会相似度评价软件(2012A)"对样品进行相似度评价;采用UPLC-LTQ-Orbitrap技术对二妙丸中化学成分进行定性分析,色谱柱为Thermo Scientific Syncronis C18柱(100 mm×2.1 mm,1.9μm),乙腈-0.1%甲酸水溶液梯度洗脱,经DAD检测器后采用LTQ-Orbitrap Elite质谱正离子模式采集,各成分的一级全扫描离子在离子阱内进行CID多级质谱、FT检测高分辨质谱数据分析。结果所建立的指纹图谱有10个共有色谱峰,20批样品的相似度在0.869~0.992。通过对照品指认、文献比对以及高分辨质谱数据解析,鉴定了21个化学成分,分别为neo-chlorogenic acid、木兰箭毒碱、竹叶椒碱、木兰花碱、3-O-feruloylquinic acid、蝙蝠葛碱、demethyleneberberine、oxyberberine、非洲防己碱、药根碱、小檗红碱、巴马汀、小檗碱、丁香酸、咖啡酸、(E)-4-(3-hydroxyprop-1-en1yl)-2-methoxyphenol、白术内酯II、acetosyringone、白术内酯I、selina-4(14),7(11)-dien-8-one、苍术素。结论建立的二妙丸HPLC指纹图谱专属性强,重现性好,结合液质联用技术的定性分析,可全面评价二妙丸的内在质量。