Simultaneous determination of six index constituents and comparative analysis of four ethnomedicines from genus Gentiana using a UPLC‐UV‐MS method

Many species from genus Gentiana (Gentianaceae) have a long history of applications as folk medicines in the world. A simple rapid UPLC‐UV‐MS/MS method has been developed and validated for the simultaneous determination of six index constituents (gentiopicroside, swertiamarin, loganic acid, sweroside, mangiferin and ferulic acid) from the four ethnomedicines (G. rigescens Franch. ex Hemsl., G. rhodantha Franch. ex Hemsl., G. scabra Bunge and G. farreri Balf. f.). The UPLC analysis was performed on Shim‐Pack XR‐ODS III (150 × 2.0 mm, 2.2 µm). The mobile phase was consisted of acetonitrile–0.1% formic acid water using gradient elution. The wavelength 242 nm was chose for the four iridoids as well as mangiferin and 320 nm was set for ferulic acid. Mass spectrometry was applied for identification and quantification for analytes with low concentration. All the regression equations revealed a good linear relationship (R² > 0.9993). Accuracy and precision were all within the required limits. The chromatogram fingerprints analysis combined with principal component analysis showed the similarity values of the four species were <0.788 while the similarity values of G. scabra Bunge and G. rigescens Franch. ex Hemsl. were >0.993, which provided reasonable foundation for utilization and clinical application of the four ethnomedicines. This developed method appears to be a useful tool for quality control of the four ethnomedicines. Copyright © 2014 John Wiley & Sons, Ltd.     

10-吲哚细胞松弛素chaetoglobosin F的NMR解析

源于真菌的天然产物细胞松弛素类化合物（cytochalasins）是微生物研究的热点领域之一．该类化合物结构复杂多样，核磁共振（NMR）波谱鉴定困难．Chaetoglobosin F是分离自五加科药用植物三七（Panax notoginseng）种子内生真菌Chaetomium globosum中的10-吲哚类细胞松弛素．本文对chaetoglobosin F进行NMR结构解析及数据归属，并总结归纳10-吲哚类细胞松弛素的NMR特征，为该类化合物的深入研究提供参考．     

Serum metabolomics study of patients with allergic rhinitis

Allergic rhinitis (AR) negatively affects the healthy lives of many individuals. Most previous studies on AR focused on the expression of cytokines, with only a few analyzing cytokine expression from a metabolomics viewpoint. Therefore, it is worthwhile to study AR at the metabolic level. Consequently, we aimed to identify differential serum biomarkers by metabolomics. In this study, the orthogonal partial least squares discriminant analysis (OPLS-DA) model was applied to characterize the differences in serum samples collected from patients with AR and healthy volunteers. Ten metabolites (except hexadecanoic acid) were found to be altered significantly (p < .05) in the former group, according to results of principal component analysis and OPLS-DA, indicating that these metabolites could be potential biomarkers. MetaboAnalyst 4.0 and pathway enrichment analysis showed that these changes in metabolites mainly involved three pathways, namely, porphyrin and chlorophyll metabolism, arachidonic acid metabolism, and purine metabolism. Our findings may contribute to a better understanding of the potential pathogenesis mechanisms and provide a metabolic evidence for in-depth studies of AR.     

桃小食心虫性信息素——(Z)-7-二十碳烯-11-酮的简便合成

桃小食心虫是危害最大的果树害虫之一,其性信息素主要成分为(Z)-7-二十碳烯-11-酮.从2,3-二氢呋喃出发,经酸水解得到4-羟基丁醛,与正庚基三苯基溴化磷制备的Wittig试剂反应得到(Z)-4-十一碳烯-1-醇,经氧化得到(Z)-4-十一碳烯醛,再经格氏加成得到(Z)-7-二十碳烯-11-醇,氧化后得到目标产物.     

鬼臼毒素五元氮杂环类衍生物的合成及细胞毒活性研究

从鬼臼毒素出发,通过简洁的合成路线合成了9个新型的鬼臼毒素五元氮杂环类衍生物,其结构经1H NMR,13C NMR,IR,HR-ESI-MS以及X单晶衍射确定.对合成的新化合物进行了体外抗肿瘤活性的筛选,结果表明,化合物10具有较好的细胞毒活性,IC50值为2.63~4.73μmol/L,对4种细胞株的活性均优于顺铂,可以作为先导化合物作进一步的结构修饰和更深入的活性研究.     

稀土配合物抗肿瘤活性研究进展

大量研究表明,稀土具有一定的抗肿瘤活性,稀土与配体形成配合物后其抗肿瘤活性强于配体。目前,国内外研究安全、有效、可控的稀土配合物的抗肿瘤药物已经成为热点,已研究出多种稀土配合物并对其进行抗肿瘤机制分析。本文对已研究出的多种稀土配合物如邻香兰醛缩氨基酸Schiff碱稀土配合物、氧氟沙星稀土配合物、嘧啶类稀土配合物和芦丁素稀土配合物等进行分类,并对其抗肿瘤机制进行归纳、总结。     

Two new eremophilane Sesquiterpenoides from Ligularia dictyoneura

Abstract

Two new eremophilane sesquiterpenoides, 6α,9α-dihydroxyeremophilenolide (1), and 1β,10β-dihydroxyeremophilenolide (2), along with ten known eremophilane sesquiterpenoides (3–12) were isolated from the aerial parts of Ligularia dictyoneura (Franch.) Hand.-Mazz. Their structures were elucidated by means of extensive spectroscopic analysis. Compounds 3–6 were assessed for their cytotoxicity against five human cancer cell lines (HL-60, SMMC-7721, A-549, MCF-7 and SW-480), and the result showed that they had no activity.     

红外光谱结合化学计量学对不同采收期滇重楼的定性定量分析

傅里叶变换红外光谱(FTIR)结合偏最小二乘判别分析(PLS-DA)和偏最小二乘回归(PLSR)对不同采收期滇重楼(Paris polyphylla var. yunnanensis)分别进行定性鉴别与定量分析,以期为滇重楼合理采收和鉴别评价提供科学依据。采集46份不同采收期滇重楼样品的红外光谱,对光谱数据进行自动基线校正+纵坐标归一化+自动平滑+小波去噪(WD)预处理后进行PLS-DA分析;采用超高效液相色谱测定样品中重楼皂苷Ⅰ,Ⅱ,Ⅵ,Ⅶ的含量,将液相测定数据与红外光谱数据进行拟合,经自动基线校正+纵坐标归一化+自动平滑+一阶求导+正交信号校正(OSC)优化处理后,建立滇重楼中重楼皂苷Ⅰ,Ⅱ,Ⅵ,Ⅶ的快速预测模型。结果显示,(1)原始红外光谱中主要吸收区域在950~700,1 200~950,1 800~1 500和2 800~3 500 cm-1附近。(2)PLS-DA得分图可准确区分不同采收期滇重楼样品。(3)液相数据显示重楼总皂苷含量随着年限的增加先成倍增加,再逐渐减少,最后呈现缓慢增加的趋势。(4)重楼总皂苷含量定量模型的预测值与真实值间无显著性差异,表明模型预测效果好。FTIR结合化学计量学可准确区分不同采收期滇重楼并快速预测其皂苷含量,为不同采收期滇重楼的鉴别和皂苷含量预测提供一种新方法,同时为确定滇重楼的最佳采收期提供参考依据。