不同产地龙葵药材的高效液相色谱-蒸发光散射检测指纹图谱

采用高效液相色谱-蒸发光散射检测器(HPLC-ELSD)来研究不同产地龙葵药材品质的差异,为龙葵药材质量标准的制定提供参考依据。使用Phenomenex C₁₈色谱柱,流动相为乙腈-20%(v/v)甲醇水溶液(含0.03%(v/v)三乙胺),梯度洗脱,蒸发管温度为40 ℃。利用"中药色谱指纹图谱相似度评价系统"对所采集的色谱图进行相似度比对,选择相似度在0.9~1.0之间的色谱图归一化拟合成龙葵的标准指纹图谱,并利用对照品进行色谱峰指认。研究结果表明,不同产地来源的龙葵药材之间具有显著的差异,依据HPLC-ELSD采集到的非挥发类成分可对中药材进行区分。该方法为龙葵药材的真实性、优良性和稳定性评价提供了一种新的、具有广阔应用前景的技术手段。     

五加生化胶囊的高效液相色谱指纹图谱研究

应用高效液相色谱(HPLC)法建立五加生化胶囊的指纹图谱。采用ANGLAVenusil XBP-C18色谱柱(250×4.6mm,5μm),以甲醇-0.1%磷酸溶液为流动相,梯度洗脱,检测波长为327nm,五加生化胶囊多数峰达到基线分离。采用2004A中药色谱指纹图谱相似度评价系统对11批样品的指纹图谱进行峰匹配,确定12个共有峰,11批五加生化胶囊指纹图谱的相似度均在0.90以上。结果表明:五加生化胶囊的HPLC指纹图谱特征性和专属性强,可较系统地用于五加生化胶囊的质量控制。     

基于香气成分气相色谱-质谱指纹图谱的判别分析和相似度评价用于绿茶等级差异研究

该文以研究指纹图谱在绿茶等级判别方面应用的可行性为目的。以信阳毛尖茶为研究对象，以茶汤香气成分为研究目标，采用顶空固相微萃取与气相色谱-质谱联用技术，筛选其香气特征成分，建立不同等级信阳毛尖茶香气成分GC-MS指纹图谱。发现运用判别分析法可以对2个系列7个等级41个信阳毛尖茶样进行很好的等级区分；通过不同等级色谱指纹图谱的相似度计算发现，相似度与茶样等级之间具有较好的相关性，尤其是对于品质较好的茶样，这种相关性更好。表明运用判别分析法和相似度计算方法能够反映绿茶等级之间的差异性，且基于相似度评价的方法具有客观量化的特征。     

中药色谱指纹图谱的小波变换及分形表达方法

提出一种基于小波变换的色谱指纹图谱分形表达方法。该法运用小波变换将色谱谱线分解至不同分辨尺度，然后计算各尺度分量的分形维数，用色谱的小波基分形参量替代色谱指纹图谱的采样值。仿真实验结果表明，色谱小波基分形参量对谱峰保留时间漂移具有较好的抗干扰能力。以当归和川芎两种中药材的品种及道地性鉴别分类问题为实例，比较研究色谱采样值与小波基分形参量，k-近邻法的交叉验证计算结果表明，小波基分形参量的分类效果优于色谱采样值。     

邓老凉茶颗粒的超高效液相色谱质谱联用指纹图谱研究

建立了适用于邓老凉茶颗粒质量控制的超高效液相色谱质谱联用指纹图谱分析方法。样品采用甲醇索氏萃取60 min,萃取液采用超高效液相色谱质谱法进行指纹图谱分析。色谱柱采用Waters ACQUITY HSST3 C18(150 mm×3.0 mm,1.8μm),以0.5%甲酸-乙腈为流动相进行梯度洗脱,流速为0.8 mL/min,柱温35℃。质谱采用负离子ESI模式,选择基峰离子流质量色谱图进行指纹图谱研究。32个共有峰在15 min内得到良好分离,其中15个共有峰通过对照品进行了确证。通过《中药色谱指纹图谱相似度评价系统2004A版》对邓老凉茶颗粒样品进行相似度分析,15个批次样品的相似度均达到0.960以上,表明邓老凉茶颗粒的产品质量稳定性很好。以32个共有峰的相对峰面积进行主成分分析,邓老凉茶颗粒样品之间的细微质量差异得到明显区分。该方法快速、高效、可靠,可有效地用于邓老凉茶颗粒的质量控制。     

基于核苷类化合物HILIC-ESI-TOF/MS分析的海洋动物药指纹图谱方法

探讨了核苷类化合物指纹图谱用于不同海洋动物药真伪鉴别的可行性, 为贵重动物药的鉴别提供了一种新方法. 采用亲水色谱-电喷雾飞行时间质谱(HILIC-ESI-TOF/MS)对不同海洋动物药中的16种核苷类化合物进行分析, 构建了基于16种核苷类化合物的特征指纹图谱, 结合相似度分析和聚类分析, 用于不同海洋动物药的鉴别. 结果表明, 基于核苷类化合物HILIC-ESI-TOF/MS分析的指纹图谱能反映不同海洋动物药各自的固有特征, 结合相似度分析和聚类分析可实现对不同海洋动物药的正确区分. 说明核苷类化合物指纹图谱有望成为动物药鉴别的新方法.     

高效液相色谱指纹图谱及随机森林应用于湖南安化黑茶水溶性成分的研究

建立了适用于湖南安化黑茶的高效液相色谱指纹图谱分析方法。样品用水在90℃恒温水浴中浸提20min,以C18色谱柱(250 mm×4.6 mm,5μm)分离,甲醇-0.1%磷酸溶液为流动相梯度洗脱,检测波长为270nm,流速为1.0 m L/min,黑茶的各种组分得到较好分离,共确定18个色谱峰作为安化黑茶的特征指纹峰,并通过对照品分析对其中12个峰进行确证。运用相似度评价、主成分分析、正交偏最小方差判别分析(Orthogonal partial least squares discriminant analysis,OPLS-DA)和随机森林法对78个黑茶样品指纹图谱进行了化学模式识别研究和变量重要性判定。结果表明联合指纹图谱分析法和随机森林法可有效区分湖南安化黑茶和其他产地的黑茶。该方法操作简单,精密度、稳定性和重现性良好,为安化黑茶的鉴别和质量控制提供了实验依据。     

内燃机油高效液相指纹图谱的建立

建立了内燃机油指纹图谱的高效液相色谱(HPLC)分析方法。采用反相C18柱,以乙腈-水为流动相梯度洗脱,检测波长280 nm,柱温30℃,进样体积10μL进行试验。考察结果表明,指纹图谱中各共有色谱峰的相对保留时间α和相对峰面积Sr的相对标准偏差(RSD)均小于2.4%,满足小于3%的指纹图谱研究技术要求。通过共有特征峰分析以及色谱峰重叠率、相似度的计算,可进一步鉴别和评价内燃机油的质量。该法与传统的内燃机油品质评价方法相比,节约了试验成本和时间,为内燃机油的快速鉴别和质量控制开拓了新领域。     

基于牛舌草指纹图谱的多指标成分相对定量与鉴别方法

色谱指纹图谱法在中草药产地鉴别或中成药鉴别中发挥着重要作用,然而色谱峰强度和位置易受目标物提取和分离条件的影响,发展更加准确的指纹图谱具有重要意义。该文以色谱峰中某一个常见组分（芦丁）作为内标,分析其他组分的相对含量,以相对含量作为指纹图谱信息,结合化学模式识别可以精确给出产地的相似度。以牛舌草的液相色谱指纹图谱指纹峰为例,以其中芦丁的组分峰作为基准峰,其他指纹峰以芦丁为参照,计算每个指纹峰以芦丁计的含量,建立了牛舌草的指纹图谱。将获得的相对含量指纹图谱采用系统聚类分析和主成分分析进行化学模式识别研究,实现了不同产地牛舌草的区分。该方法建立了牛舌草多指标成分的相对定量与鉴别方法,既节省资源,又具有可操作性,对于其他中药或中成药的质量控制具有一定的借鉴意义。     

银黄口服液的质量控制及其高效液相色谱指纹图谱的研究

利用高效液相色谱方法,建立了复方银黄口服液及其原料药材黄芩和金银花的指纹图谱,测定了银黄口服液中黄芩苷 和绿原酸的含量。以Lichrospher C18色谱柱(250 mm×4.6 mm i.d.,5 μm)为分离柱,以甲醇和0.1%磷酸水溶液为流动 相进行二元梯度洗脱,流速0. 6 mL/min,在254 nm波长下检测。采用夹角余弦和相关系数的方法,计算6批银黄口服液指 纹图谱的相似度均在0.99以上,表明银黄口服液的质量未见显著差异。将银黄口服液指纹图谱中的共有峰与原料药材黄芩 和金银花的指纹图谱中的共有峰相比较,对其归属进行确认,大部分共有峰可以匹配。     

仿刺参中皂苷类成分的高效液相色谱指纹图谱

利用高效液相色谱法建立了仿刺参皂苷类成分的指纹图谱,为仿刺参的质量控制提供了新的方法。采用固相萃取制备供试品溶液,选用Zorbox SB-C18色谱柱(250 mm×4.6 mm, 5 μm),以乙腈-0.1%磷酸水溶液为流动相进行梯度洗脱,检测波长为205 nm,柱温30 ℃。分析了不同产地的10批仿刺参样品,采用国家药典委员会推荐的“中药色谱指纹图谱相似度评价系统(2004 A版)”处理谱图,确定了6个共有峰。计算了10个样本间的指纹图谱相似度,所得相似度计算结果均大于0.97。该方法具有良好的稳定性和重现性,可用于仿刺参的质量控制。     

用高效液相色谱组方指纹图谱智能预测中药质量的新模式

建立大黄、黄芩、黄连的高效液相色谱(HPLC)组方指纹图谱,确定其融合模型,观察组方融合指纹图谱(CSF)与一清片复方样品指纹图谱的一致性,从而以CSF代替复方整体来智能预测复方制剂质量。用二极管阵列检测器(DAD)同时测定黄芩、大黄、黄连和一清片在268 nm波长下的HPLC指纹图谱,并使用系统指纹定量法进行定性、定量评价。结果 CSF涵盖各单味药主要色谱峰信息,即CSF共有峰(55个)涵盖一清片样品共有峰(50个)的主要指纹图谱信息。15批样品的质量除YQT-S01为5级外,其他质量均为3级及以上。各组合模式CSF质量除CSF-2为6级外,其余均为2级或1级。该文探讨了标准指纹图谱和中药组方融合指纹图谱的相关性,可以与相应的计算机评价软件相结合,通过组方融合指纹图谱所代表复方制剂的整体指纹图谱来实现智能预测中药成方制剂质量的新模式。     

北五味子的液相色谱指纹图谱的建立

利用反相高效液相色谱法建立中药材北五味子的指纹图谱,为科学评价及有效控制北五味子质量提供了新方法。实验分析了10个不同产地的北五味子样品,采用国家食品药品监督管理局推荐的“中药色谱指纹图谱相似度评价系统(2004 A版)”计算处理,建立了由26个指纹峰和19个共有峰组成的北五味子指纹图谱,确定了5个主要的指纹峰。通过夹角余弦法和相关系数法计算了北五味子10个样本与指纹图谱间的相似度,得到了满意的结果。所建立的指纹图谱可以用来区别不同产地北五味子药材的优劣,为进一步控制北五味子的质量提供依据。     

Development of a Chromatographic Fingerprint of Tobacco Flavor by Use of GC and GC-MS

A new chromatographic fingerprinting method has been established for quality control of tobacco flavor. Three different extraction techniques, simultaneous distillation extraction (SDE), liquid–liquid extraction, and solid-phase microextraction were evaluated for isolation of the components of interest. After comparison of their performance, a combination of SDE and GC-MS was used for simple, reliable, and reproducible development of a chromatographic fingerprint of tobacco flavor. Twelve samples of the flavor from different batches were used to establish the fingerprint. Thirty-nine volatile components of the tobacco flavor samples, accounting for 86.54% of the total content, were identified and quantified. The 12 samples had 28 peaks in common. The method of fingerprint analysis was then validated on the basis of the relative retention times and relative peak areas of the common peaks, sample stability, and similarity analysis. The similarities of the 12 samples of tobacco flavor were >0.80, showing that samples from different batches were, to some extent, consistent. The chromatographic fingerprint developed was successfully used to differentiate tobacco flavor samples from tobacco extract prepared from tobacco leaf, both by similarity comparison and by principal-components projection analysis. The method can be used for quality control of tobacco flavor.     

Fractal fingerprinting of chromatographic profiles based on wavelet analysis and its application to characterize the quality grade of medicinal herbs

Extracting chemical fingerprints is an important step for representing and interpreting chromatographic data. In this paper, the chromatographic profile is decomposed into components at different resolution levels using wavelet analysis, then the fractal dimensions of these components are computed as the chemical fingerprints. The chromatographic fingerprint is characterized by the vector composed of these chemical fingerprints, which can represent the chemical patterns of different categories of complex samples. Computer simulations reveal that the fractal fingerprints are more stable than the original chromatographic profile data with respect to variations of peak retention time. To demonstrate the validity of this method, the evaluation of the quality of the medicinal herb Angelica sinensis (Oliv.) diels is investigated. Principal component analysis of the fractal fingerprints indicates that samples belonging to the same quality grade are clustered together, while those belonging to different quality grades are separated. Using these fractal fingerprints taken from the chromatographic scans as inputs for an artificial neural network (ANN). The quality grades of two sets of the herbs were verified by cross-validation, indicating that 96.7% of the herbs are correctly identified with respect to their quality grades evaluated by experienced experts, and 100.0% of the herbs are correctly identified with respect to their quality grades determined by pharmacodynamical evaluation.     

基于信息融合的中药多元色谱指纹图谱相似性计算方法

摘要用信息融合算法合并多张色谱指纹图谱, 解决中药多元指纹图谱相似性评价难题, 提出一种多元色谱指纹图谱相似度计算方法. 用该方法先对各单元指纹图谱进行串行或并行象素级信息融合, 再对融合了各指纹峰信息的多元色谱指纹图谱进行相似度评价. 计算机仿真和复方丹参滴丸多元HPLC指纹图谱应用结果表明, 该法能够评价中药多元色谱指纹图谱相似度, 定量表征中成药产品批次间质量波动情况.     

Qualitative and quantitative assessment of the HPLC fingerprints of Ginkgo biloba extract by the involution similarity method.

In this paper, we develop a new method for evaluating chromatographic fingerprints of traditional Chinese medicine (TCM) by the average involution similarity and the quantitative involution similarity. To validate this novel approach, we studied the chromatographic fingerprints of Ginkgo biloba extract by the new similarity parameters. The results were compared with those of the cosine of vectorial angle (S(F)), the correlative coefficient (r) and some other quantitative parameters, such as the apparent quantitative similarity of fingerprint R% and the average mass percentage M%. The approach represented in this paper was proved to well reflect the similarity alteration of each batch of Ginkgo biloba extract and the quantitative differences of the extracted constituents. The S(gxq) and S(gxsq) are the best qualitive and quantitative similarity parameters of all those mentioned in this paper; they can be profitably used for the qualitative and quantitative assessments of TCM chromatographic fingerprints. Through this study, the quality evaluation of TCM can be simplified by using only one parameter of with the qualitive and quantitative functions proposed in this paper.     

固相微萃取-气相色谱/质谱法建立烟用香精指纹图谱

采用固相微萃取法(SPME)对6批次的烟用HMT-4香精成分进行提取,GC/MS对其进行分析,建立了该香精的GC/MS指纹图谱的研究方法。通过参兑实验考察了色谱指纹图谱用于香精质量控制的可行性。结果表明:SPME法具有操作简便、快速、节能、萃取效率高等特点,适合于烟用香精成分的提取。6批次的HMT-4香精的指纹图谱稳定性好,相似度高,具有很强的特征性和唯一性。通过参兑实验发现色谱指纹图谱能全面、综合、准确地反映烟用香精的质量情况,可以成为烟用香精质量控制的有效手段。     

Monitoring quality consistency of Liuwei Dihuang Pill by integrating the ultraviolet spectroscopic fingerprint,a multi‐wavelength fusion fingerprint method,and antioxidant activities

Liuwei Dihuang Pill, a classical traditional Chinese medicine, has been widely used to treat kidney yin deficiency in China for hundreds of years. Little attention, however, has been paid to quality control methods for this formulation. In the present study, we aimed to establish a comprehensive and practical quality evaluation system for Liuwei Dihuang Pill. Thus, ultraviolet spectroscopic fingerprints and multi‐wavelength fusion fingerprints have been proposed for quality consistency evaluation of the popular patent. The similarity analysis of Liuwei Dihuang Pill samples was evaluated by systematic quantitative fingerprint method from qualitative and quantitative perspectives. The results showed that 26 batches of samples were classified into five grades for fusion fingerprints and three grades for ultraviolet spectroscopic fingerprints. Moreover, the fingerprint–efficacy correlation was also established and confirmed through the partial least squares model to visualize the antioxidant activity of Liuwei Dihuang Pill in vitro. In conclusion, these results indicated that integrating ultraviolet spectroscopic fingerprints and multi‐wavelength fusion fingerprints coupled with antioxidant activities provide a rapid and effective approach to monitor the quality consistency of Liuwei Dihuang Pill.     

Fingerprint analysis of Ligusticum chuanxiong using hydrophilic interaction chromatography and reversed-phase liquid chromatography

Fingerprint analysis is considered one of the most powerful approaches to quality control in traditional Chinese medicines (TCMs). In this study, a binary chromatographic fingerprint analysis was developed using hydrophilic interaction chromatography (HILIC) and reversed-phase liquid chromatography (RPLC) to gain more chemical information about polar compounds and weakly polar compounds. This method was used to construct a chromatographic fingerprint of Ligusticum chuanxiong. The two chromatographic methods demonstrated good precision, reproducibility, and stability, with relative standard deviations of <2% for retention time and 7% for peak area for both HILIC and RPLC separations. Data from the analysis of 14 samples by HILIC and RPLC were processed with similarity analysis, with correlation coefficients and congruence coefficients. This binary fingerprint analysis, using two chromatographic modes, is a powerful tool for characterizing the quality of samples, and can be used for the comprehensive quality control of TCMs.