HPLC指纹图谱结合灰色关联度分析综合评价云南丽江秦艽资源

对采自云南丽江17个不同产区秦艽样品建立其HPLC指纹图谱,测定了药材中9大质量指标并进行灰色关联度分析,建立一种新型秦艽质量综合评价方法。采用甲醇-0.1%磷酸为流动相体系,梯度洗脱,建立17批秦艽药材的高效液相色谱指纹图谱;采用HPLC法测定马钱苷酸,龙胆苦苷和獐牙菜苦苷含量;按药典方法测秦艽中醇溶性浸出物、总灰分、酸不溶性灰分含量;分光光度法测定多糖含量。建立的丽江秦艽药材的HPLC指纹图谱的相似度极高,通过对多项指标的灰色关联度分析遴选出X2和X12两个优级药材资源。指纹图谱结合多指标成分的灰色关联度分析,能全面评价秦艽药材质量,亦可从中筛选优质秦艽资源和为秦艽道地适宜产区的规划确定提供依据。     

化学模式识别技术评价中药厚朴质量的研究

本文对不同产地和市售的二十四种厚朴药材及饮片的萃取液进行了高效液相色谱、气相色谱及紫外光谱分析;对所得数据用主成分分析进行分类,概括出不同样品化学成分的异同,认为大叶木兰可做为厚朴的代用品,而在陕西安康购得的样品不应做厚朴使用,后者经生药学鉴定为厚朴伪品凹叶木兰。化学模式识别技术可为寻找药材的代用品、评价中药质量及鉴定伪劣药材提供依据。     

不同产地地龙质量分析研究

采用原子吸收光谱法测定了地龙中的砷、铅含量,并与我国食品中重金属的限量规定总量、东南亚国家的限量规定进行了比较。采用药典方法分别测定浸出物、总灰分和酸不溶性灰分和进行重金属检查,综合考察不同产地地龙的内在质量。     

基于无机元素特征的不同产地鳖甲药材质量分析

为研究中药鳌甲中元素的分布规律及其与药材产地之间的关系,探讨鳌甲中无机元素的特征,采用电感耦合等离子体质谱法(ICP-MS)测定了10批鳖甲样本中10种无机元素含量,根据元素含量的高低分布状态建立了鳌甲药材相关的无机元素指纹图谱,运用"总体特征分布分析-主成分与系统聚类分析结合-因子分析"的三级分析方法,对选取的特征元...     

基于高效液相色谱指纹图谱的不同产地不同采摘期昆仑雪菊的化学模式识别及抗氧化谱效关系探究

干燥、粉碎10批不同产地、不同采摘期的昆仑雪菊样品,分取0.2 g,用60%(体积分数)甲醇溶液50 mL超声提取30 min,过0.45μm滤膜,所得溶液(质量浓度为4 000 mg·L^-1)进入高效液相色谱仪,其中各组分在Agilent HC-C₁₈色谱柱上用不同体积比的0.4%(体积分数)乙酸溶液和乙腈的混合溶液进行梯度洗脱分离,在285 nm波长下检测。以中药色谱指纹图谱相似度评价系统建立指纹图谱,筛选共有组分并进行相似度评价。对绿原酸进行方法学考察,并以绿原酸为参照计算各共有组分的含量。以聚类分析和主成分分析等化学模式识别法对不同产地、不同采摘期的样品进行分类。分别采用1,1-二苯基-2-三硝基苯肼(DPPH)、2,2-联氮-二(3-乙基-苯并噻唑-6-磺酸)二铵盐(ABTS)自由基清除法测定10批样品的抗氧化活性,以灰色关联分析法建立共有组分峰面积数据和抗氧化活性的谱效关系。结果显示：10批样品指纹图谱以及它们与对照指纹图谱之间的相似度均大于0.900,共有组分有24个;两种化学模式识别法均将样品分为4类,推测分类结果和产地、采摘...     

GC - MS法对不同产地大米的快速鉴定

采用GC - MS对4种不同产地大米中的脂溶性成分进行分析,并利用NIST标准质谱库和质谱图搜索程序进行检索.结果表明,大米中主要的脂溶性成分为棕榈酸、亚油酸、油酸、角鲨烯和谷甾醇.不同产地大米中脂溶性化合物的指纹谱图存在显著差异,通过主成分分析和聚类分析,建立了一种对不同产地大米进行快速鉴定的方法.     

UV–化学模式识别不同产地的丹参

建立由UV–化学模式识别法评价丹参质量的方法。分别用正己烷、乙酸乙酯、水、乙醇提取不同产地的丹参,并测绘其紫外光谱。取紫外光谱各波长的吸光度为特征数据,进行主成分分析、聚类分析,对不同产地丹参质量的差异进行了评价。不同溶剂提取液的光谱聚类结果有所差异,可将不同产地丹参聚为3类。UV–化学模式识别技术可以从整体上反应丹参所含成分的差异,可为丹参质量控制与评价提供依据。     

气相色谱结合化学计量学区分大米贮藏时间与产地

香气是衡量大米质量的一个主要因素,对大米的食用品质有重要影响。该文以顶空固相微萃取(SPME)技术为基础,采用气相色谱法分别分析了不同贮藏时间和不同产地大米样本的挥发性成分,通过主成分分析法(PCA)和偏最小二乘判别分析法(PLS-DA)对大米样本进行分类和判别分析。PCA及PLS投影图显示不同储藏时间的大米明显聚为4类,通过留一交叉验证法(LOO)计算PLS预报的准确率为96%,相对标准误差为8.2%。同时,PCA投影图中可将4个不同产地的大米样本进行区分,分类效果显著;所建PLSDA模型可靠,不同产地大米样本均能被准确识别,正确率为100%。以顶空固相微萃取/气相色谱检测大米中挥发性成分,利用主成分分析法和偏最小二乘判别分析法鉴别大米新鲜程度和产地具有可行性。     

虎骨及其类似品微量元素的灰色关联分析

以Na、Mg、K、P、Al、Si、Ti、Cr、Mn、Fe、Zn、Co、Ni、Cu的含量为分析指标．用灰色关联分析研究了熊骨、豹骨、黄牛骨、猪骨、狗骨、猫骨与虎骨在微量元素组成上的相似亲疏关系。结果表明，虎骨、熊骨、豹骨和猫骨的微量元素组成相近似，后3种骨可考虑作为虎骨的代用品。     

Qualitative and Quantitative Analysis for the Quality Control of Rhizoma Coptidis by HPLC-DAD and HPLC-ESI-MS

For quality control purpose, an approach of fingerprinting and simultaneous quantification of five major bioactive constituents of Rhizoma Coptidis was established via a high-performance liquid chromatograph coupled with a photodiode array UV detector(HPLC-DAD) and an electrospray ionization mass spectrometer(HPLC-ESI/MS). The compounds were identified on the basis of the comparison of their mass spectra with literature data and those of standard samples and quantified by the HPLC-DAD method. Baseline separation was achieved on an XTerra C 18 column(5 μm, 250 mm×4.6 mm i. d.) with linear gradient elution of formate buffer(consisting of 0.5% formic acid, adjusted to pH=4.5 with ammonia) and acetonitrile(consisting of 0.2% formic acid and 0.2% triethylamine). The me-thod was validated for linearity(r 2 0.9995), repeatability(RSD3.1%), intra-and inter-day precision(RSD1.8%) with recovery(99.9%―105.1%), limits of detection(0.15―0.35 μg/mL), and limits of quantification(0.53―0.82 μg/mL). The similarities of 32 batches of Rhizoma Coptidis and their classification according to their manufacturers were based on the retention time and peak areas of the characteristic compounds. The five compounds were selected for quality assessment of Rhizoma coptidis via partial least squares analysis(PLS).     

应用电化学指纹图谱优化黄连水提取工艺的研究

以黄连提取液中的总成分为定量指标,应用电化学振荡技术获取不同提取工艺的电化学指纹图谱.根据电化学指纹图谱特征参数诱导时间来考察其水溶性有效成分含量的高低,与高效液相色谱含量测定方法对照,验证了该方法的可靠性,确定黄连提取的最佳工艺为:采用12倍量的水,提取1.5 h,提取2次.结果表明利用电化学指纹图谱的诱导时间优化中药水溶性有效成分的提取工艺是可行的.     

Structural elucidation and identification of alkaloids in Rhizoma Coptidis by electrospray ionization tandem mass spectrometry

Simple, convenient, sensitive and accurate analytical methods are needed for the structural characterization and identification of alkaloid components in Rhizoma Coptidis in traditional Chinese herbal medicine, which has important bioactivity. In this work, the identification of alkaloid compounds in Rhizoma Coptidis was investigated by obtaining molecular mass information using electrospray ionization mass spectrometry (ESI-MS). Multi-stage tandem mass spectrometric (ESI-MS(n)) data for the alkaloid compounds were used for detailed structural characterization, then structure information was obtained by comparison of the fragmentation mechanisms of both alkaloids in Rhizoma Coptidis and standard samples of berberine, palmatine, coptisine and jatrorrhizine by MS. Based on the results obtained, the structure of a novel compound was elucidated. The results of the experiments demonstrate that ESI-MS(n) is a sensitive, selective and effective tool for the rapid determination of alkaloids in Rhizoma Coptidis.     

非水毛细管电泳测定黄连饮片中5种生物碱

建立了一种非水毛细管电泳(NACE)同时测定黄连饮片生品与炮制品中小檗碱、巴马汀、药根碱、木兰碱和黄连碱含量的方法。分别考察了非水溶剂、缓冲液体系及其浓度和pH、运行电压、运行温度和检测波长等条件对实验结果的影响。在优化的实验条件下,选择非水毛细管电泳分离模式,以40 mmol/L乙酸钠-40 mmol/L乙酸铵的无水甲醇缓冲溶液(pH 5.8)为电泳介质,未涂渍标准熔融石英毛细管(64.5 cm×75 μm,有效长度56 cm)为分离通道,检测波长为254 nm,分离电压为25 kV,压力进样(5 kPa×6 s),柱温为20 ℃。结果显示,5种生物碱在20 min内可实现基线分离,加标回收率为98.37%～101.03%。该方法简单、准确,重现性较好,可用于黄连饮片内在质量的评价和控制。     

基于多指标含量测定结合化学计量学的不同产地丹参品质差异分析

为对比分析产地对丹参中酚酸类和丹参酮类成分的影响,采用超高效液相色谱（UPLC）及超高效液相色谱－三重四极杆质谱联用技术（UPLC－QQQ－MS）同时测定来自山东、河南、陕西、四川、安徽共408份丹参中23种化学成分的含量,并对数据进行多元统计分析。研究发现17种酚酸类及6种丹参酮类成分在不同产地丹参中均存在显著差异。山东的丹参样品中丹参酮类成分含量最高,四川的样品中丹酚酸B含量最高,安徽丹参的紫草酸、丹酚酸Y、丹酚酸A、丹酚酸D和丹酚酸E等的含量最高。多种模式识别方法均可用于不同产地丹参的判别分析,线性判别分析（LDA）为产地溯源的最佳模型。正交偏最小二乘法判别分析（OPLS－DA）表明不同产地丹参的化学成分差异较大,不同来源丹参的质量差异标志物不仅限于丹酚酸B、丹参酮Ⅰ、隐丹参酮、丹参酮ⅡA,其他丹酚酸类及丹参酮类也是重要的质量标志物。该研究对全国不同主产区的栽培丹参进行多指标含量测定及建模分析,所建立的定量方法专属性强、准确高效,可为不同产地丹参的质量控制及产地判别提供参考。     

黄连中小檗碱及其同分异构体的电喷雾质谱研究

利用电喷雾多级串联质谱对黄连经水提、醇沉、薄层色谱分离后，得到的组分进行了详细研究，并对其中小檗碱及其同分异构体表小檗碱的分子离子[M ]进行了源内碰撞诱导解离(CID)，在不同源内CID能量(25％，50％)下碰撞诱解离时存在区别，并提出其碎裂机理方面的解释。     

Quality Evaluation of Atractylodis Macrocephalae Rhizoma Based on Combinative Method of HPLC Fingerprint,Quantitative Analysis of Multi-Components and Chemical Pattern Recognition Analysis

A method for the quality evaluation of Atractylodis Macrocephalae Rhizoma (AMR) based on high-performance liquid chromatography (HPLC) fingerprint, HPLC quantification, and chemical pattern recognition analysis was developed and validated. The fingerprint similarity of the 27 batches of AMR samples was 0.887–0.999, which indicates there was very limited variance between the batches. The 27 batches of samples were divided into two categories according to cluster analysis (CA) and principal component analysis (PCA). A total of six differential components of AMR were identified in the partial least-squares discriminant analysis (PLS-DA), among which atractylenolide I, II, III, and atractylone counted 0.003–0.045%, 0.006–0.023%, 0.001–0.058%, and 0.307–1.175%, respectively. The results indicate that the quality evaluation method could be used for quality control and authentication of AMR.     

In vitro and in vivo identification of metabolites of magnoflorine by LC LTQ‐Orbitrap MS and its potential pharmacokinetic interaction in Coptidis Rhizoma decoction in rat

Magnoflorine, an important aporphine alkaloid in Coptidis Rhizoma, is increasingly attracting research attention because of its pharmacological activities. The in vivo and in vitro metabolism of magnoflorine was investigated by LC LTQ‐Orbitrap MS. In vivo samples including rat urine, feces, plasma and bile were collected separately after both oral (50 mg kg^?1) and intravenous administration (10 mg kg^?1) of magnoflorine, along with in vitro samples prepared by incubating magnoflorine with rat intestinal flora and liver microsome. As a result, 12 metabolites were found in biological samples. Phase I metabolites were identified in all biological samples, while phase II metabolites were mainly detected in urine, plasma and bile. In a pharmacokinetic study, rats were not only dosed with magnoflorine via oral (15, 30 and 60 mg kg^?1) and intravenous administration (10 mg kg^?1) but also dosed with Coptidis Rhizoma decoction (equivalent to 30 mg kg^?1 of magnoflorine) by intragastric administration to investigate the interaction of magnoflorine with the rest of compounds in Coptidis Rhizoma. Studies showed that magnoflorine possessed lower bioavailability and faster absorption and elimination. However, pharmacokinetic parameters altered significantly (p < 0.05) when magnoflorine was administered in Coptidis Rhizoma decoction. Oral gavage of Coptidis Rhizoma decoction decreased the absorption and elimination rates of magnoflorine, which revealed that there existed pharmacokinetic interactions between magnoflorine and the rest of ingredients in Coptidis Rhizoma. Copyright © 2015 John Wiley & Sons, Ltd.     

Approach based on high‐performance liquid chromatography fingerprint coupled with multivariate statistical analysis for the quality evaluation of Gastrodia Rhizoma

Gastrodia Rhizoma is a Traditional Chinese Medicine applied in the treatment of stroke, numbness of limb, headache and dizziness. However, its clinical effect is threatened by sulfur‐fumigation used in the process of storage. This article employs content determination coupled with high‐performance liquid chromatography fingerprint to investigate the effect of sulfur‐fumigation on Gastrodia Rhizoma so as to evaluate the quality of Gastrodia Rhizoma. The result was that most active ingredient in Gastrodia Rhizoma decreased after sulfur‐fumigation and the fingerprints analyzed by mathematical statistics between sulfur‐fumigated Gastrodia Rhizoma and unfumigated Gastrodia Rhizoma have substantial differences, which reveals that sulfur‐fumigation has a significant influence on the quality of Gastrodia Rhizoma. The conclusion of hierarchical clustering analysis, principal component analysis and partial least squares could validate each other, which implies that the method of mathematical statistics applied for assessing the quality of Gastrodia Rhizoma is effective and stable. The method not only affords a viable strategy for distinguishing Gastrodia Rhizoma whether sulfur‐fumigated or not and assessment of the quality of Gastrodia Rhizoma, but also provides a reference for other herbal medicine that suffers from sulfur‐fumigation.