药用龙牙百合中微量元素含量测定

采用原子吸收法和原子荧光法测定了隆回药用龙牙百合中的微量元素,结果表明隆回药用龙牙百合含有丰富的微量元素铜、锌、镁、钙等,为进一步利用和综合开发药用龙牙百合提供了参考。     

液相色谱特征图谱用于草乌成分定量

测定不同产地草乌的液相色谱指纹图谱,构建草乌的特征图谱,对不同草乌样品进行相似性对比分析,考察不同产地草乌的生物碱总量含量差异.采用色谱柱为WelchromC18柱(250 mm×4.6 mm,5μL),流动相为甲醇–0.1％三乙胺(体积比为75:25),流量为1 mL/min,检测波长为235 nm,柱温为30℃,进样体积为20μL.对10个批次样品进行相似度分析和含量测定,确定草乌的特征图谱共有模式,标定10个特征峰,指认了新乌头碱、乌头碱、次乌头碱的特征峰.10批不同产地草乌的相似度均大于0.90,相似度较好.产地1的草乌总生物碱含量为3.4046 mg/g,在10个产地中含量最高.其它产地草乌总生物碱含量相近.     

HPLC-MS结合多元统计分析区分人参产地及筛选皂苷类标志物

利用高效液相色谱-质谱联用(HPLC-MS)技术结合多元统计分析方法, 区分中国人参主产区5个不同产地的45个人参样本, 筛选出差异性皂苷类标志物. 根据人参总皂苷在反相C₁₈色谱柱中的洗脱顺序, 结合串联质谱分析和标准品比对, 在提取的人参总皂苷中鉴定出15种原人参三醇型、 24种原人参二醇型和2种齐墩果酸型共41种皂苷. 对人参总皂苷的HPLC-MS全扫描数据进行了多元统计分析. 正交偏最小二乘-判别分析(OPLS-DA)结果表明, 所建立的分析模型具有良好的数据描述能力和预测能力. 所有人参样本能够根据产地被区分, 并筛选得到同时区分5个产地的差异性皂苷类组分18种; 能够区分任意2个产地人参样本的差异性组分主要为在人参中含量较高的人参皂苷Rb1, Rg1, Re, Rc, Rd, Ro和m-Rb1等. 分层聚类分析(HCA)结果显示, 黑龙江和吉林两省的样本能够独自聚类, 但是绥化市的样本更接近于吉林省. 初步推断原因为绥化市地理位置较接近吉林省, 两地人参生长环境相似并可能存在种质资源交换.     

不同产地三七的~1H NMR指纹图谱对比分析

通过提取方法和检测方法的探讨,选用体积分数90%的甲醇水溶液,对三七主根样品进行超声提取,并用noesypr1d脉冲序列预饱和压制水峰实验,获取了8种不同产地三七的1H NM R指纹图谱,对三七主要成分特征信号进行了初步指认。通过图谱分析看出,不同产地三七的三萜皂苷含量和各种三萜皂苷组成比例不同,黄酮、糖类含量比重也不一样。由于1H NM R具有提供信息丰富、简便、快速和重现性好的特点,可以作为中药指纹图谱研究的方法。     

ICP-AES法测定百合中的微量元素

用ICP-AES法对兰州百合和湖南百合、药用百合中的Fe、Mn、Cu、Zn等18种元素进行了分析研究。结果表明,百合中含有丰富的人体必需微量元素;湖南食用百合比兰州百合的微量元素含量高,Fe含量高于兰州百合的5倍之多,Zn含量几乎是兰州百合的10倍之多。加标回收率为83%~106%,该法具有操作简便、快速和准确度高等优点。说明湖南百合具有较高的保健价值,为进一步开发百合提供了科学依据。     

9种人参皂苷同时测定方法及在人参质量鉴别中的应用

建立可同时测定人参皂苷Rg1、Re、Rf、Rg2、Rb1、Re、Rb2、Rb3和Rd含量的反相高效液相色谱（RP—HPLC）方法。采用Agilent Zorbax SB-C18柱,以乙腈-水-0．05％磷酸为流动相,流速1．5mlMmin,柱温35℃,检测波长203nm。在此色谱条件下,各组分在60min内均得到较好分离,回收率符合含量测定要求。运用该方法对不同产地人参进行含量测定,道地药材主根中9种人参皂苷总含量为1．19—1．45％,须根为5．47—6．90％,3个非道地药材主根分别为1．03％、1．04％、1．85％。聚类分析结果表明,根据测定的9种皂苷含量能准确区分人参的主根与须根,并判断其道地性。     

穿龙薯蓣化学成分的液相色谱-质谱联用分析

穿龙薯蓣(DiosoreanipponicaMakino)为薯蓣科薯芋属植物,产于内蒙古,黑龙江等省区,其根茎俗称穿山龙,既是生产治疗心血管疾病药物地奥心血康的原料药材,又是用于合成多种甾体激素类药物的原料薯蓣皂苷元的重要来源之一。临床报道穿龙薯蓣总皂苷对治疗冠心病、抗动脉粥样硬化、降血脂、平喘、抗炎和抗肿瘤有一定疗效,其有效部位为穿龙薯蓣甾体皂苷.我们采用高效液相与电喷雾串联质谱联用方法分析穿龙薯蓣中主要的皂苷成分,并发现一种未见报道的甾体皂苷元。     

高效液相色谱法测定竹节参中多种人参皂苷含量

建立了高效液相色谱法(HPLC)测定竹节参中人参皂苷Rg1、Re、Rb1、Rb2、Rg2、Rd含量的方法.运用二极管阵列检测器(DAD)峰纯度和光谱检索功能,结合保留时间定性,外标峰面积法定量.采用C18反相柱,以乙腈-水梯度洗脱测定了同一批竹节参总皂苷中人参皂苷Rg1、Re、Rd的含量分别为0.81%、0.15%、2.99%,回收率为93.46%~94.02%,含量及回收率的RSD均小于5%,该方法简便、灵敏,精密度及准确度在允许范围内,可作为竹节参皂苷提取物中多种人参皂苷的同时测定方法.     

液相色谱-质谱联用定量分析威灵仙及其同属植物中4种三萜皂苷

建立了4种三萜皂苷类成分威灵仙皂苷B、虎掌草皂苷D、威灵仙皂苷C和虎掌草皂苷B的液相色谱-质谱联用定量分析方法.采用Agilent Zorbax SB-Cl8柱,以乙腈-0.05%甲酸为流动相,流速0.6 mL/min,柱温25 ℃,各组分在负离子模式下用选择性离子监测方式检测,在25 min内均得到较好分离.运用本方法对威灵仙及铁线莲属药材中的4种三萜皂苷含量进行测定,各样品中4种三萜皂苷的含量总和达0.0652～41.7 mg/g, 含量差异较大,浙江天目山的威灵仙中4种皂苷的总含量最高,达41.7 mg/g,约为商品威灵仙(5.80 mg/g)的7倍,可能是由于采集时间和地点不同造成的.本方法快速、灵敏、重复性好,适用于威灵仙及铁线莲属药材中三萜皂苷类成分的含量测定及其植物来源的鉴别.     

β-环糊精对燃煤焦油和烟气中环芳烃的清除作用

采用三维荧光法测定了7处产地煤样燃烧的焦油和烟气中多环芳烃（PAHs）的含量,焦油中PAHs含量为0.201～0.419 mg/g,烟气中PAHs含量为1.1～3.2 μg/g;测试了β-环糊精（β-CD）溶液对煤烟气中多环芳烃的清除作用,最高去除率可达65.6%。 结果表明：不同产地煤的烟气中PAHs含量不同, 煤焦油中PAHs浓度(mol/L)在10-5数量级,远高于烟气中的浓度(mol/L,10-7数量级)。 用β-CD去除不同产地煤燃烧烟气中多环芳烃的去除率不同。 所选7种煤平均清除率为38.4%。 β-CD溶液有希望成为煤烟气中多环芳烃的清除剂。     

液相色谱-电喷雾电离质谱与电子轰击质谱联用筛选百合中的甾体皂甙

 利用高效液相色谱 电喷雾电离质谱联用仪 (HPLC/ESI MS)、电子轰击质谱 (EI MS)和半制备型高效液相色谱 ,从卷丹百合中筛选出了两种甾体皂甙 ,其中一种为含有 3个糖基与提果皂甙元的甾体皂甙 ,另一种为含有 3个糖基和薯蓣皂甙元的甾体皂甙。结果表明 :在线的HPLC/ESI MS能够准确快速地提供糖甙类化合物的分子质量和糖链部分的有益信息 ,但对甙元部分提供的信息极少 ;离线的EI MS只需极少量 (1mg～ 2mg)的纯品就能准确地提供甙元部分的有益信息 ,但很难获得糖甙的分子离子峰与糖链部分的信息 ,两者有机地结合起来能快速地从植物中筛选甾体皂甙。     

Steroidal saponins and alkaloids from the bulbs of Lilium brownii var. colchesteri

The fresh bulbs of Lilium brownii var. colchesteri were found to contain five steroidal saponins: 26-O-beta-D-glucopyranosylnuatigenin 3-O-alpha-L-rhamnopyranosyl-(1----2)-beta-D-glucopyranoside (6), 26-O-beta-D-glucopyranosylnuatigenin 3-O-alpha-L-rhamnopyranosyl-(1----2)-O-[beta-D-glucopyranosyl-(1----4)]- beta-D-glucopyranoside (7), brownioside (8), deacylbrownioside (9) and 27-O-(3-hydroxy-3-methylglutaroyl)isonarthogenin 3-O-alpha-L-rhamnopyranosyl-(1----2)-O-[beta-D-glucopyranosyl-(1----4)- beta-D-glucopyranoside (10); and two steroidal alkaloids: beta 1-solamargine (11) and solasodine 3-O-alpha-L-rhamnopyranosyl-(1----2)-O-[beta-D-glucopyranosyl-(1----4)- beta-D-glucopyranoside (12); along with several phenolic constituents. Compounds 7, 10 and 12 are new naturally-occurring compounds.     

Quantitative determination and evaluation of Paris polyphylla var. yunnanensis with different harvesting times using UPLC‐UV‐MS and FT‐IR spectroscopy in combination with partial least squares discriminant analysis

A rapid method was developed and validated by ultra‐performance liquid chromatography–triple quadrupole mass spectroscopy with ultraviolet detection (UPLC‐UV‐MS) for simultaneous determination of paris saponin I, paris saponin II, paris saponin VI and paris saponin VII. Partial least squares discriminant analysis (PLS‐DA) based on UPLC and Fourier transform infrared (FT‐IR) spectroscopy was employed to evaluate Paris polyphylla var. yunnanensis (PPY) at different harvesting times. Quantitative determination implied that the various contents of bioactive compounds with different harvesting times may lead to different pharmacological effects; the average content of total saponins for PPY harvested at 8 years was higher than that from other samples. The PLS‐DA of FT‐IR spectra had a better performance than that of UPLC for discrimination of PPY from different harvesting times.     

Determination of Saponins in Leaf of Panax Ginseng C. A. Mey. by High Performance Liquid Chromatography

A high performance liquid chromatography(HPLC) with UV detection was established for simultaneous determination of saponins in the leaf of Panax ginseng C. A. Mey. Nine ginsenosides(Rb1,Rb2,Rb3,Rc,Rd,F1,F2,F3,F5) and notoginsenoside Fe(NFe) were studied. Among the saponins,the ginsenosides F1,F2,F3,F5 and NFe were determined by HPLC-UV method for the first time. The determination of the ginsenosides via the HPLC-UV method was performed on a reversed-phase C18 column with gradient elution in 40 min. The line...     

Quality evaluation of Radix Astragali through a simultaneous determination of six major active isoflavonoids and four main saponins by high-performance liquid chromatography coupled with diode array and evaporative light scattering detectors

A method, high-performance liquid chromatography coupled with diode array and evaporative light scattering detectors (HPLC-DAD-ELSD), was developed to evaluate the quality of Radix Astragali through a simultaneous determination of six major active isoflavonoids and four main saponins. The wavelength at 280 nm was chosen to determine six isoflavonoids: calycosin-7-O-beta-D-glucoside (1), ononin (2), (6alphaR, 11alphaR)-9,10-dimethoxypterocarpan-3-O-beta-D-glucoside (3), (3R)-2'-hydroxy-3',4'-dimethoxyisoflavan-7-O-beta-D-glucoside (4), calycosin (5), and formononetin (6); and ELSD connected after DAD was employed to determine four saponins: astragaloside IV (7), astragaloside II (8), astragaloside I (9), and acetylastragaloside I (10). This assay was fully validated with respect to precision, repeatability and accuracy. The proposed method was successfully applied to quantify the ten components in eleven samples from different localities in China; significant variations were demonstrated in the content of these compounds in the samples from different areas. This simple, rapid, low-cost and reliable HPLC-DAD-ELSD method is suitable for routine quantitative analysis and quality control of traditional Chinese medicines (TCMs) consisting of bioactive multi-components with different structures such as Radix Astragali.     

Simultaneous determination of saponins and fatty acids in Ziziphus jujuba (Suanzaoren) by high performance liquid chromatography-evaporative light scattering detection and pressurized liquid extraction

The seed of Ziziphus jujube Mill. var. spinosa (Bunge) Hu ex H. F. Chou, Suanzaoren in Chinese, is one of commonly used Chinese medicines. Saponins and fatty oil contains several fatty acids in Suanzaoren are responsible for its therapeutic activities. In this study, a new HPLC coupled with evaporative light scattering detection (ELSD) and pressurized liquid extraction (PLE) method was developed for the simultaneous quantitative determination of 11 major components of 2 saponins and 9 fatty acids, namely jujuboside A, jujuboside B, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, arachidic acid and docosanoic acid in Suanzaoren. Simultaneous separation of these eleven compounds was achieved on a C18 analytical column. The mobile phase consisted of (A) 0.1% aqueous acetic acid and (B) methanol with 0.1% acetic acid using a gradient elution. The drift tube temperature of ELSD was set at 75 degrees C, and nitrogen flow-rate was 1.8l/min. All calibration curves showed good linearity (r(2)>0.9955) within test ranges. This method showed good reproducibility for the quantification of these eleven components in Suanzaoren with intra- and inter-day variations of less than 3.41 and 4.37%, respectively. The validated method was successfully applied to quantify 11 investigated components in nine commercial samples of Suanzaoren.     

Determination and Fingerprint Analysis of Steroidal Saponins in roots of Liriope muscari (Decne.) L. H. Bailey by ultra high performance liquid chromatography coupled with ion trap time‐of‐flight mass spectrometry

Liriope muscari (Decne.) L. H. Bailey is a well‐known traditional Chinese medicine used for treating cough and insomnia. There are few reports on the quality evaluation of this herb partly because the major steroid saponins are not readily identified by UV detectors and are not easily isolated due to the existence of many similar isomers. In this study, a qualitative and quantitative method was developed to analyze the major components in L. muscari (Decne.) L. H. Bailey roots. Sixteen components were deduced and identified primarily by the information obtained from ultra high performance liquid chromatography with ion‐trap time‐of‐flight mass spectrometry. The method demonstrated the desired specificity, linearity, stability, precision, and accuracy for simultaneous determination of 15 constituents (13 steroidal glycosides, 25(R)‐ruscogenin, and pentylbenzoate) in 26 samples from different origins. The fingerprint was established, and the evaluation was achieved using similarity analysis and principal component analysis of 15 fingerprint peaks from 26 samples by ultra high performance liquid chromatography. The results from similarity analysis were consistent with those of principal component analysis. All results suggest that the established method could be applied effectively to the determination of multi‐ingredients and fingerprint analysis of steroid saponins for quality assessment and control of L. muscari (Decne.) L. H. Bailey.     

Qualitative and quantitative analyses of Epimedium wushanense by high-performance liquid chromatography coupled with diode array detection and electrospray ionization tandem mass spectrometry

A new HPLC-DAD-ESI-MS(n) method was developed for rapid separation, characterization and quantitation of flavonoids in Epimedium wushanense, a popular Chinese herbal medicine. For qualitative identification, a total of 37 compounds were characterized from the underground and aerial parts of E. wushanense. Among them, 28 compounds were prenylated flavonoids, and 23 were confirmed by comparing with reference standards. For quantitative analysis, 12 major flavonoids including kaempferol glycosides, desmethylicaritin glycosides, and icaritin glycosides were simultaneously determined by HPLC/UV. Samples were separated on a Waters Symmetry C(18) column at 35 °C eluted with a gradient three-component mobile phase of acetonitrile, methanol, and water containing 0.03% v/v formic acid. All the flavonoids showed good linearity (r(2) ≥0.9997). The recoveries varied from 92.6 to 106.1% at three concentration levels. This method was applied to the determination of 20 samples of different geographical sources, harvesting time, and plant parts. Contents of the predominant flavonoid, epimedin C, ranged from 1.4 to 5.1% in aerial parts and 1.0 to 2.8% in underground parts. The methods established in this paper were simple and reliable and could be used for the quality control of E. wushanense.     

Determination of four active saponins of Panax notoginseng in rat feces by high-performance liquid chromatography

A method is developed for the determination of ginsenoside Rg1, Rb1, Rd, and notoginsenoside R1 of Panax notoginseng (PNS) in rat feces after oral and intravenous administration of total saponins of PNS. The fecal samples are treated with organic extraction and solid-phase extraction prior to high-performance liquid chromatography. The calibration curves for the four saponins are linear in the given concentration ranges. The precision of the method is in the range of 1.0-10.0% (relative standard deviation), and the accuracy is between 80.0% and 110%. The recoveries of this method are all over 75%. This method is successfully applied to the analyses of fecal samples of rats treated with PNS.     

Simultaneous quantitative and qualitative analysis of bioactive phenols in Dendrobium aurantiacum var. denneanum by high-performance liquid chromatography coupled with mass spectrometry and diode array detection

A novel high-performance liquid chromatographic method with mass spectrometry and diode array detection method for the simultaneous qualitative and quantitative analysis of bioactive phenols was developed. In total, nine chemically diverse phenols including five bibenzyls, three phenanthrenes and a coumarin were unambiguously identified in Dendrobium aurantiacum var. denneanum by comparison with the available references or reported data according to their retention behaviors, UV spectra and fragmentations of ESI-MS. The contents of the four main phenolic compounds, moscatilin, gigantol, moscatin and coumarin, in D. aurantiacum var. denneanum from the wild and various cultivated populations were determined by HPLC-UV. The sample preparation involved a rapid and simple procedure based on solid-phase extraction using a C(18) reversed-phase cartridge. The quantitative analysis was performed on a Beckman Coulter ODS column (5 microm, 250 x 4.6 mm) using a linear gradient elution system of acetonitrile-0.5% formic acid. The method was validated for linearity, limits of detection (LOD) and quantification (LOQ), precision and accuracy. Good results were obtained with respect to the overall intra- and inter-day variations (RSD less than 3.22%) and the percentage recoveries (ranging from 90.50 to 99.22%). Notable differences in the contents of phenols were observed among different cultivated populations. The samples colleted in April and May (spring), or October and November (autumn) accumulated much higher contents of phenols than those collected in other seasons.