复方丹参提取物高效液相色谱-紫外-蒸发光散射检测指纹图谱的建立

采用紫外/蒸发光散射检测器(UV和ELSD)串联检测技术,建立了复方丹参提取物HPLC/UV/ELSD指纹图谱。运用指纹图谱相似度评价软件,对14批复方丹参提取物HPLC/UV/ELSD指纹图谱进行相似度计算,结果相似度良好。该指纹图谱能同时反映复方丹参提取物中丹参和三七的主要化学组分特征,可有效评价复方丹参提取物的质量稳定性。     

复方丹参片生产中丹酚酸B的快速测定

为建立制药企业在生产复方丹参片时的快速质量控制方法,用TLC及反相HPLC法,对在不同处理条件下的复方丹参片样品中丹酚酸B进行了定性、定量分析,同时优化了色谱条件,提高了测定的准确性。结果表明,甲醇超声处理复方丹参片粉末20 min(1次),再用高纯水超声处理20 min(2次);流动相V(甲醇) V(乙腈) (V甲酸) V(水)=25 10 1 64,波长286 nm。本法线性好,准确度高,简便快捷经济,可用于生产该药的内在质量监测。     

复方板蓝根颗粒抗病毒成分HPLC-UV指纹图谱及LC-ESI-MSn研究

建立了复方板蓝根颗粒提取物高效液相色谱(HPLC-UV)指纹图谱分析方法. 确定了10批不同来源复方板蓝根颗粒提取物的19个共有峰. 各提取物的HPLC-UV指纹图谱与对照指纹图谱比较, 相似度均在93%以上. 利用液相色谱与质谱联用(LC-ESI-MSⁿ)技术对主要共有峰的结构进行了鉴定. 药效学研究表明, 复方板蓝根颗粒提取物有抗病毒活性. 该指纹图谱精密度、稳定性和重现性良好, 可作为复方板蓝根颗粒的质量评价方法.     

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。     

RP-HPLC法测定复方丹参片中的隐丹参酮、丹参酮Ⅰ和丹参酮ⅡA

建立了反相高效液相色谱法测定复方丹参片(丹参、三七、冰片)中的隐丹参酮、丹参酮Ⅰ和丹参酮ⅡA。采用DiamonsilTMC18(250×4.6 mm,5μm)色谱柱,以V(甲醇)∶V(水)=75∶25为流动相,流速为0.8 mL/min,检测波长270nm。隐丹参酮、丹参酮Ⅰ和丹参酮ⅡA分别在1.456~10.19μg/mL、2.160~15.12μg/mL和3.152~22.06μg/mL的范围内呈良好线性关系,平均回收率分别为99.21%(RSD=0.63%)、100.3%(RSD=1.0%)、99.87%(RSD=0.63%)。可用于复方丹参片的质量控制。     

丹参水溶性成分的电喷雾质谱行为及其特征图谱的初步研究

应用电喷雾-质谱(ESI-MS)技术研究了原儿茶醛和丹参素的ESI-MS规律,结合ESI-MS技术,对9种丹参水溶性成分的质谱行为进行了研究,并对其中5种成分进行了定性分析。同时利用选择性离子检测质谱技术,初步建立了丹参水溶性成分SIM-MS特征图谱,该图谱简单、易于解析,重现性与特征性较好,可以用于丹参药材及复方丹参的快速指纹鉴别。     

复方丹参片中四种成分的高效液相色谱-电化学检测-紫外检测法分析

建立了电化学检测器与二极管阵列检测器联用的液相色谱(HPLC-ECD-DAD)同时分离和测定复方丹参片中原儿茶酸、原儿茶醛、咖啡酸和丹参酮ⅡA 等4种成分的分析方法。采用Zorbax SB-C18柱(150 mm×4.6 mm i.d.,5.0 μm),以甲醇和0.4%磷酸为流动相(流速1.0 mL/min)进行梯度洗脱;ECD检测电压0.7 V,DAD检测波长270 nm,柱温30 ℃。实验结果表明,原儿茶酸、原儿茶醛、咖啡酸和丹参酮ⅡA质量浓度分别为0.3～9.0 mg/L,1.1～54.0 mg/L,1.1～11.1 mg/L和5.2～52.0 mg/L时与其峰面积呈良好的线性关系(线性相关系数均高于0.999),原儿茶酸、原儿茶醛、咖啡酸和丹参酮ⅡA的平均回收率(n=6)分别为97.8%(相对标准偏差(RSD)为2.15%),98.2%(RSD为2.07%),97.6%(RSD为2.18%)和97.2%(RSD为2.07%)。该法同时利用了ECD和DAD的优点,是一种快速、灵敏、准确的分析方法,可以为复方丹参片的质量控制提供科学依据。     

清开灵注射液HPLC/ELSD指纹图谱建立及质量相关性研究

运用高效液相色谱／蒸发光散射检测器(HPLC／ELSD)建立了复方清开灵注射液的指纹图谱。对其中7种有效成分进行了定量测定,方法学考察结果良好;通过指纹图谱相似度评价软件,对10批清开灵注射液的HPLC／ELSD指纹图谱进行了相似度计算,结果表明：10批样品相似度很好。该方法为中药质量控制提供了一种可以同时实现整体定性、指标成分定量且简便易行的方法模式。     

利用三级质谱与二级质谱匹配策略鉴定丹参中酚酸类成分

多级质谱信息(MS/MS information)可提供鉴定化合物结构的关键线索,多级质谱(MS/MS)图谱到结构的转换(MS/MS spectrum to structure)是精准鉴定化合物结构的重要过程。本研究提出了化合物的三级质谱(MS³)图谱与其结构单元的二级质谱(MS²)图谱匹配策略,实现了化合物结构的精准鉴定。首先,利用三重四极杆复合线性离子阱质谱仪(Qtrap-MS)的双碰撞池,采集酯类化合物酯基质谱裂解产生的特征碎片离子(c^–和y^–)在线性离子阱(LIT)内经第二次碰撞诱导解离(Collision-induced dissociation, CID)后的MS³图谱,并同步采集其结构单元化合物([M–H]^–)在LIT中经碰撞诱导解离后的MS²图谱,结果表明,酯类化合物特征碎片离子的MS³图谱与结构单元化合物的MS²图谱匹配。最后,采用HR-MS/MS对丹参总酚酸(Total ...     

生姜精油的超高效合相色谱特征图谱研究

应用超高效合相色谱(UPC~2)技术研究了生姜精油的特征图谱。生姜精油经正庚烷稀释,以超临界CO_2为流动相,乙腈为助溶剂,采用超高效合相色谱梯度洗脱分离,流速为0.8 mL/min,二极管阵列(PDA)检测器测定,建立了特征峰PDA光谱谱图库及安徽产生姜精油的标准对照特征图谱。通过特征峰PDA光谱图检索识别及色谱图相似度评价,10份安徽产生姜精油的样品谱图与标准对照特征图谱的相似度均大于0.9。各共有指纹峰相对保留时间和相对峰面积的相对标准偏差(RSD)均小于3.0%,方法精密度、重现性、稳定性良好,符合特征图谱评价要求。通过超高效合相色谱特征图谱采集,结合聚类分析、主成分分析,对20批不同来源的生姜精油样品成功进行了区分。该研究为生姜精油的质量控制及产地溯源提供了一种简便、快速的新方法。     

Quality Assessment of Cardiotonic Pills by HPLC Fingerprinting

An HPLC method has been developed for the fingerprinting and quantitative analysis of cardiotonic pills. A standard fingerprint containing 11 common peaks at three wavelengths was constructed from ten batches of pills to evaluate batch-to-batch consistency. In addition, the amounts of three marker compounds were also determined to evaluate the quality of the quantitative analysis. Chromatographic fingerprints at three wavelengths, along with the content of three marker compounds were found to be suitable for quality assessment. Fufang Danshen Pian (cardiotonic tablets), a traditional dosage form is produced from three kinds of Chinese medicinal herbs for the prevention and treatment of angina pectoris and coronary heart disease. Fufang Danshen Pian mainly contained an additional group of liposoluble components besides salvianolic acid B from Salvia miltiorrhiza Bunge while cardiotonic pills only contained water-soluble components. Therefore, the fingerprint accompanied with marker compounds can be used to assess the quality of the cardiotonic pills.     

Electrospray ionization mass spectrometry fingerprinting of perfumes: Rapid classification and counterfeit detection

A fast procedure to classify perfumes and identify counterfeit samples is described. Dilution of a few microL of the sample in a 1:1 methanol/water solution is followed by detection of its major polar components via direct infusion electrospray ionization mass spectrometry (ESI-MS) in the positive ion mode. As proof-of-principle cases, three famous brands of perfumes were used. The ESI+-MS fingerprints of authentic samples were very characteristic, showing distinctive sets of polar markers for each sample. Principal component analysis (PCA) placed samples of the three perfume brands in well-defined groups. Counterfeit samples were also clearly detected owing to contrasting ESI-MS fingerprints, with PCA placing these samples far away from the authentic samples.     

微量元素制剂辅助治疗复发性口疮疗效观察

报道了１０３例ＲＡＵ患者使用微量元素制剂辅助治疗的临床疗效观察。将两个实验组分别与对照组比较。结果显示：应用锌、铁制剂辅助雷公藤、复方丹参等治疗的实验组Ｉ效果优于雷公藤、复方丹参对照组（Ｐ〈０．０１），而仅用锌、铁制剂治疗的实验组Ⅱ临床效果比对照组差（Ｐ〈０．０１），但锌、铁制剂有改善ＲＡＵ临床症状作用，而不能较好地控制其复发。     

Monitoring the quality consistency of Fufang Danshen Pills using micellar electrokinetic chromatography fingerprint coupled with prediction of antioxidant activity and chemometrics

A fast micellar electrokinetic chromatography fingerprint method combined with quantification was developed and validated to evaluate the quality of Fufang Danshen Pills, a traditional Chinese Medicine, which has been used in the treatment of cardiovascular system diseases, in which the tetrahedron optimization method was first used to optimize the background electrolyte solution. Subsequently, the index of the fingerprint information amount of I was performed as an excellent objective indictor to investigate the experimental conditions. In addition, a systematical quantified fingerprint method was constructed for evaluating the quality consistency of 20 batches of test samples obtained from the same drug manufacturer. The fingerprint analysis combined with quantitative determination of two components showed that the quality consistency of the test samples was quite good within the same commercial brand. Furthermore, the partial least squares model analysis was used to explore the fingerprint–efficacy relationship between active components and antioxidant activity in vitro, which can be applied for the assessment of anti‐oxidant activity of Fufang Danshen pills and provide valuable medicinal information for quality control. The result illustrated that the present study provided a reliable and reasonable method for monitoring the quality consistency of Fufang Danshen pills.     

复方丹参配伍比例对丹参化学成分溶出的影响

采用高效液相色谱峰比值法比较了由丹参和三七组成的复方丹参中丹参与三七的比例(以质量比计)从10∶0变化到1∶10的过程中丹参化学成分的变化。结果表明：所有合煎样品中丹参的主要成分含量均比单味药丹参中丹参主要成分的含量高,并且经典方(m(丹参)∶m(三七)＝5∶3)中丹参主要成分的含量最高。因此,丹参与三七以一定的比例(5∶3)配伍并且采用合煎的方法能够增加丹参成分的溶出率, 由此看来中医药中讲究的配伍规律是有其内在的科学道理的。     

Integrated evaluation of HPLC and UV fingerprints for the quality control of Danshen tablet by systematic quantified fingerprint method combined with antioxidant activity

Danshen tablet, which consists of Salviae Miltiorrhizae Radix et Rhizoma, Notoginseng Radix et Rhizoma and Borneolum syntheticum , has been widely used in the therapy of cardiovascular disease. The aim of this study was to develop comprehensive evaluation methods for the quality control of Danshen tablet. First, five‐wavelength fusion fingerprint was established to avoid one‐sidedness of a single wavelength. Then, the ultraviolet spectrum fingerprint was applied to reflect the information of unsaturated bond and conjugated system of chemical substances in Danshen tablet. The similarity analyses of these two fingerprints were performed by systematic quantified fingerprint method in terms of qualitative and quantitative aspects. After that, the evaluation results of high‐performance liquid chromatography and ultraviolet fingerprints were integrated by the mean algorithm, which could reduce the error caused by single method. The integrated evaluation results showed that 30 batches of samples were classified into seven grades. Finally, the fingerprint–efficacy relationship was established using an on‐line antioxidant system and partial least‐squares model to explore the connection between chemical components and antioxidant activities. The methods established in this paper were found suitable for the analysis of Danshen tablet.     

Quantitative analysis combined with chromatographic fingerprint and antioxidant activities for the comprehensive evaluation of Compound Danshen Tablets

The composition of traditional Chinese medicine is extremely complex, so it is difficult to ensure quality consistency. We took Compound Danshen Tablets as the object of the study, by using high‐performance liquid chromatography to establish multiwavelength fusion fingerprints. Characteristic fingerprints of 30 batches of samples were generated at four wavelengths and evaluated by systematic quantified fingerprint method. An on‐line antioxidant determination method was used for the determination of the antioxidant components in Compound Danshen Tablets. The fingerprint analysis of the marker compounds can reflect the content of the marker compounds, which were determined by using the external standard method. This study elucidated that multiwavelength fusion fingerprint profiles and multiple markers compound analysis in conjunction with the assay of antioxidant activity offered a reliable and efficient approach to quantitatively evaluate the quality consistency of the traditional Chinese medicine and herbal preparations.     

高效液相色谱-电喷雾离子阱质谱法鉴定复方丹参方化学及代谢成分

应用高效液相色谱-电喷雾离子阱质谱法鉴定了复方丹参方和其在家兔血浆、尿及粪便中的代谢产物。实验采用ZorbaxC18色谱柱,二元线性梯度洗脱进行色谱分离,并与电喷雾质谱联用,根据正离子和负离子模式下的分子离子峰获得化合物分子量信息,通过与文献数据或部分对照品对照,确定化合物的可能结构。