大黄属3种大黄植物不同部分蒽醌含量的测定与比较

采用C18反相柱高效液相色谱方法分离、外标法定量对大黄属掌叶组唐古特大黄、波叶组波叶大黄、穗序组穗序大黄的根（及根茎）、叶片、叶柄、主茎四部分的芦荟大黄素、大黄酸、大黄素、大黄酚4种游离和结合蒽醌的含量进行了测定和比较。结果表明：唐古特大黄中,叶片中的游离蒽醌含量高于其它部分,游离蒽醌总量地上部分远高于地下部分;结合蒽醌则根中最高,蒽醌总量地下部分远高于地上部分。波叶大黄和穗序大黄中,游离和结合蒽醌均为根中最高,穗序大黄蒽醌总量地下部分远高于地上部分,而波叶大黄中,游离蒽醌总量地上部分高于地下部分,结合蒽醌总量地上部分与地下部分相差不大,地上部分略高于地下部分。     

毛脉酸模内生真菌蒽醌类次生代谢产物的筛选及含量分析

本文通过对毛脉酸模内生真菌的发酵培养得到其次生代谢产物,采用HPLC法对内生真菌中蒽醌类成分进行筛选。以大黄素、大黄酸、大黄酚、大黄素甲醚、芦荟大黄素五种蒽醌类成分为参照,筛选出3株真菌含大黄素、3株真菌含大黄酸、5株真菌含芦荟大黄素,其中含量最高为683μg/g、最低为8μg/g。将各菌株所含成分与各菌株分离部位的相应成分进行比较,相对宿主植物而言各菌株均有较高的含量。本实验分析方法准确、快捷,适用于毛脉酸模内生真菌的代谢产物研究。     

栽培唐古特大黄蒽醌含量的季节动态变化

采用高效液相色谱法,测定3、4年生生长季节内不同月份的青海栽培唐古特大黄中芦荟大黄素、大黄酸、大黄素、大黄酚、大黄素甲醚等5种蒽醌类化合物的含量。结果表明,3年、4年生大黄总蒽醌含量在5~6月份生长初期增加,并于6月初达到最大值,6~9月份生长旺盛期间明显降低,10月份又略有回升;3年和4年生大黄总蒽醌含量分别在0.8%~2.5%和1.3%~2.1%范围内波动。     

青海栽培和野生唐古特大黄蒽醌类成分的HPLC对比分析

采用HPLC法测定青海栽培唐古特大黄中的5种蒽醌含量,并和野生唐古特大黄药材进行了比较.结果表明,二、三、四年龄栽培唐古特大黄中芦荟大黄素、大黄酸、大黄素、大黄酚、大黄素甲醚5种蒽醌总量分别为1.21%,2.01%,1.62%,其中三、四年龄栽培唐古特大黄已达到<药典>规定的药用标准;野生大黄的总蒽醌含量远高于栽培大黄为3.64%.     

高速逆流色谱对大黄蒽醌类成分的分离研究

利用高速逆流色谱对大黄中的5个蒽醌活性成分进行了分离,当两相溶剂系统的组成是石油醚∶乙酸乙酯∶甲醇∶水=8∶2∶8∶1时,分离出大黄素;当两相溶剂比为3∶4∶3∶2时,分离出大黄酸和芦荟大黄素;当溶剂比为12∶2∶12∶1时,分离出大黄酚和大黄素甲醚;经高压液相色谱检测大黄素、大黄酸和芦荟大黄素、大黄酚和大黄素甲醚的含量分别为98.81%9、9.15%、98.51%9、8.89%和98.16%。     

HPLC-DAD和LC-MS/MS法对各种芦荟样品中蒽醌类成分的分析研究

采用HPLC-DAD和LC-MS／MS对各种芦荟样品中蒽醌类成分进行鉴定,在此基础上建立了同时测定各种芦荟样品中芦荟苷与芦荟大黄素含量的方法。采用Nucleodur-silica色谱柱（250mm＊4．6mm,5μm）,流动相A为甲醇-醋酸（500：1．70）,B为水．醋酸（500：1．70）,梯度洗脱,流速1．0mL／min,DAD扫描波长范围为190～370nm,紫外检测波长为254和356nm。质谱离子源为ESI,采用全扫描一级质谱和选择离子全扫描二级质谱两种方式同时测定。结果表明：各种芦荟样品中主要的蒽醌类成分为芦荟苷A、B与芦荟大黄素,未检测到大黄素、大黄酸、大黄素甲醚、大黄酚;芦荟干粉中所含的芦荟苷含量最高。该法准确、可靠、重现性好,可行性高。     

斑马鱼模型评价何首乌中18种成分的肝脏毒性

首次用斑马鱼模型探索何首乌中18种成分的肝脏毒性作用,为何首乌的肝毒性物质基础研究提供依据。对肝脏荧光转基因斑马鱼给以高、中、低剂量的18种何首乌主要成分72 h,并分别于给药后24、48、72 h用荧光显微镜对其进行拍照。拍好的图片通过Image J软件进行肝脏面积和荧光强度分析。大黄素组、大黄酸组、芦荟大黄素组、大黄素-1-O-葡萄糖苷组、大黄素甲醚-8-O-葡萄糖苷组、芦荟大黄素-8-O-葡萄糖苷组及阳性对照组(对乙酰氨基酚)的肝脏面积和肝脏荧光强度与空白组相比显著降低;而大黄酚组、大黄素甲醚组、大黄素-8-O-葡萄糖苷组、大黄酸-8-O-葡萄糖苷组、大黄酚-1-O-葡萄糖苷组、大黄酚-8-O-葡萄糖苷组、芦荟大黄素-3-羟甲基葡萄糖苷组、白藜芦醇组、没食子酸组、儿茶素组、表儿茶素组的肝脏面积和肝脏荧光强度与空白组相比无显著差异;此外,二苯乙烯苷组的肝脏荧光强度与空白组相比显著增高。由此可见大黄素、大黄酸、芦荟大黄素、大黄素-1-O-葡萄糖苷、大黄素甲醚-8-O-葡萄糖苷、芦荟大黄素-8-O-葡萄糖苷对斑马鱼幼鱼肝脏具有一定毒性作用。何首乌的肝毒性作用可能还是由蒽醌类化合物介导,其物质基础与上述6种蒽醌成分有关,并以结合蒽醌为主。     

切片厚度和烘干温度对唐古特大黄蒽醌含量影响的研究

采用HPLC-DAD法测定了不同切片厚度在不同烘干温度下唐古特大黄中芦荟大黄素、大黄酸、大黄素、大黄素甲醚、大黄酚的含量,探究切片厚度和烘干温度对唐古特大黄药材质量的影响。色谱柱采用的是Agilent Eclipse plus C18(4. 6×250 mm,5μm);流动相A相为色谱级别甲醇,B相为0. 1%冰乙酸溶液;柱温25℃;检测波长254 nm。结果表明:75℃烘干,切片厚度以0. 4～2 cm或6～7 cm; 25、50℃时烘干,切片0. 4～3 cm或6～8 cm,药材总蒽醌含量较高,其他厚度含量较低,芦荟大黄素、大黄酸、大黄素、大黄素甲醚、大黄酚的含量也符合上述规律。结论唐古特大黄产地初加工时,75℃烘干,切片厚度以0. 4～2 cm或6～7 cm为宜; 25和50℃时烘干,切片0. 4～3 cm或6～8cm为宜,从而保证唐古特大黄药材的质量。     

中药大黄的综合研究XXXI．大黄蒽醌衍生物系统分离的改进方法

西宁大黄小碎片加到20％硫酸溶液和氯仿的混合液中,在水浴中回流以水解,提取,氯仿提取液相继以5％碳酸氢钾溶液,5％氢氧化钾溶液振荡提取,提取液分别以盐酸酸化,即分离得大黄酸,大黄素,芦荟大黄素及大黄酚和大黄素甲醚混合物等黄色沉淀物,后者再以硅胶柱层析分离,可得大黄酚和大黄素甲醚单体,上述五种蒽醌衍生物再经结晶即得纯品。     

大黄药材、浸膏及其清胃颗粒剂质量的RP—HPLC分析

建立适合大黄药材、大黄浸膏及清胃颗粒剂过程分析与质量控制的反相高效液相色谱方法.采用YWG-ODS 10μm(200×4.0mm ID)色谱柱,流动相组成为甲醇-水-高氯酸(75250.1V/V),检测波长254nm,流速1.0ml/min,柱温控制20℃.以芦荟大黄素、大黄素、大黄酸、大黄酚和大黄素甲醚的峰面积作为定量信息,标准曲线外标法测定样品含量.结果表明,清胃颗粒剂中五种游离蒽醌成分的平均加样回收率分别为芦荟大黄素95.61%(RSD3.05%)、大黄素98.03%(RSD2.77%)、大黄酸100.1%(RSD2.21%)、大黄酚97.49%(RSD3.64%)和大黄素甲醚96.79%(RSD4.12%).本法操作简便、检测灵敏,适合于大黄药材、大黄浸膏及清胃颗粒剂过程分析与质量控制.     

Microbial glycosylation of four free anthraquinones by Absidia coerulea

Absidia coerulea transformed four anthraquinones from rhubarb, chrysophanol, physcion, emodin and aloe-emodin to their corresponding glycosylated metabolites. The structures of the products were characterized as chrysophanol 8-O-beta-D-glucoside, physcion 8-O-beta-D-glucoside, emodin 6-O-beta-D-glucoside, and aloe-emodin 1-O-beta-D-glucoside, respectively.     

Soluble Protein Content,Bioactive Compounds and the Antioxidant Activity in Seeds of Ten Rheum tanguticum Lines from Qinghai-Tibet Plateau

Rheum tanguticum (Rh. tanguticum) is a Chinese medicinal plant traditionally used in the treatment of constipation. As a byproduct, the seeds of this plant are rich in nutrients and phytochemicals. This study aimed to determine and assess seed germination ability, seed physical characteristics, soluble protein content, chemical constituents and antioxidant capacity from different breeding lines, to promote the development and utilization of seed resources. Significant differences were observed for the soluble protein content and antioxidant assays among the ten lines. The contents of aloe-emodin, rhein and catechins accumulated in seeds were extremely low and significantly different from those in roots. In contrast, emodin and chrysophanol were abundant in seeds, and significant differences were observed between seeds and roots. It was found that associations between gallic acid and catechins were not significant for either soluble protein or antioxidant capacity. There was a significantly positive correlation between the contents of four anthraquinones (aloe-emodin, rhein, emodin and chrysophanol) and soluble protein. Seeds have potent antioxidative capacity and relatively high levels of soluble protein content. The rich chemical composition of seeds can be widely used in the medical industry for further development.     

Phytoestrogens from the roots of Polygonum cuspidatum (Polygonaceae): structure-requirement of hydroxyanthraquinones for estrogenic activity.

The methanolic extract from the roots of Polygonum (P.) cuspidatum was found to enhance cell proliferation at 30 or 100 microg/mL in MCF-7, an estrogen-sensitive cell line. By bioassay-guided separation from P. cuspidatum with the most potent activity, emodin and emodin 8-O-beta-D-glucopyranoside were isolated as active principles. The methanolic extracts from Polygonum, Cassia, Aloe, and Rheum species, which were known to contain anthraquinones, also showed the MCF-7 proliferation. As a result of the evaluation of various anthraquinones from plant sources and synthetic anthraquinones, aloe-emodin, chrysophanol, chrysophanol 8-O-beta-D-glucopyranoside, and 1,8-dihydroxyanthraquinone showed weak activity. On the other hand, alizalin and 2,6-dihydroxyanthraquinone as well as emodin having the 2- and/or 6-hydroxyl groups showed potent activity. These results show that the unchelated hydroxyl group is essential for strong activity. Emodin and 2,6-dihydroxyanthraquinone also inhibited 17beta-estradiol binding to human estrogen receptors (ERs) with K(i) values of 0.77 and 0.31microM for ERalpha and 1.5 and 0.69 microM for ERbeta. These findings indicate that hydroxyanthraquinones such as emodin are phytoestrogens with an affinity to human estrogen receptors.     

大黄蒽醌衍生物与环核苷酸磷酸二酯酶、钙调素相互作用的研究

大黄蒽醌衍生物是中药大黄的主要成份。该类衍生物与钙调素(calmo-dulin,CaM)依赖的磷酸二酯酶(PDE)的相互作用表明:它们可作用子钙调素。其中,大黄酸结合CaM并抑制CaM依赖的磷酸二酯酶(CaM-PDE);而大黄素、大黄酚和芦荟大黄素既刺激CaM-PDE的活力,又刺激PDE的基础活力,其作用机制尚待阐明;当有Ca~(2+)或无Ca~(2+)条件下测定时,大黄酸对PDE基础活力均无影响。表明:象其它的CaM拮抗剂一样,大黄酸能抑制钙调素依赖的PDE的活力。     

Preparative isolation and purification of hydroxyanthraquinones from Rheum tanguticum Maxim. on normal phase silica gel: using a Flash Master Personal system

A flash chromatography method for preparative separation and purification of five hydroxyanthraquinones from the Chinese medicinal herb Rheum tanguticum Maxim. ex Balf. was developed by using Flash Master Personal(+) systems. The purities of the products, chrysophanol, physcion, emodin, aloe-emodin, and rhein were all over 90%, determined by high performance liquid chromatography (HPLC). Their structures were ascertained by EI-MS, (1)H- and (13)C-NMR data, and by co-TLC and HPLC with the authentic samples available in our laboratory.     

Chemical constituents isolated from Polygala japonica leaves and their inhibitory effect on nitric oxide production in vitro

A methanolic extract of dried leaves of Polygala japonica Houtt (Polygalaceae) significantly attenuated nitric oxide production in lipopolysaccharide-simulated BV2 microglia. Five anthraquinones chrysophanol (1), emodin (2), aloe-emodin (3), emodin 8-O-beta-D-glucopyranoside (4) and trihydroxy anthraquinone (5), and four flavonoids kaempferol (6), chrysoeriol (7), kaempferol 3-gentiobioside (8) and isorhamnetin (9) were isolated from the methanolic extract using bioactivity-guided fractionation. Among them, compounds 1-4, 6 and 7 showed significant inhibitory effect on lipopolysaccharide-induced nitric oxide production in BV2 microglia at the concentrations ranging from 1.0 to 100.0 microM.