固相萃取/超高效液相色谱法测定龙胆泻肝丸中栀子苷、龙胆苦苷与黄芩苷

建立了一种快速测定龙胆泻肝丸中栀子苷、龙胆苦苷和黄芩苷3种有效成分的超高效液相色谱方法。样品经50%甲醇提取,C18固相萃取(SPE)小柱净化后,采用Ultimate XB-C18色谱柱(4.6 mm×50 mm,1.8μm)进行分离,以乙腈-0.1%磷酸溶液为流动相进行梯度洗脱。考察了不同规格色谱柱、流动相梯度比例、进样体积、柱温和流速对分离效果的影响,并对SPE柱流出液的平衡体积进一步考察,在最佳分析条件下进行液相色谱分析,该方法显示了良好的线性关系(r≥0.999 8),其定量下限(LOQ)为0.24～0.44 mg/L,加标回收率为95%～99%。该方法快速、准确,可满足实际检测需要。     

柴胡舒肝丸的毛细管电泳指纹图谱及其黄芩苷含量的测定

建立了柴胡舒肝丸(Chaihu Shugan Pill, CHSGP)的毛细管区带电泳指纹图谱(capillary electrophoresis fingerprint, CEFP),并采用内标法测定了黄芩苷的含量。以50 mmol/L硼砂-150 mmol/L磷酸二氢钠-50 mmol/L磷酸氢二钠(1:1:1, v/v/v)(含5 mmol/L庚烷磺酸钠)为背景电解质(BGE)溶液,采用未涂层石英毛细管(总长度75 cm,有效分离长度63 cm,内径75 μm),以色谱指纹图谱分离量指数(RF)为目标函数优化实验条件,在紫外检测波长265 nm、运行电压11 kV条件下,以黄芩苷峰为参照物峰,确定了22个共有指纹峰,建立了CHSGP的CEFP,通过对20批样品聚类分析确定用其中13批生成对照CEFP(RCEFP),以此RCEFP为标准用系统指纹定量法鉴别20批柴胡舒肝丸质量。结果其中的4批化学成分数量和分布比例不合格,4批含量明显偏低,其他12批完全合格。采用内标法测定黄芩苷的含量,在5～200 mg/L范围内线性良好(r=0.9999),平均回收率(n=9)为98.2%。该法具有较好的精密度和重现性,为柴胡舒肝丸的质量控制提供了一种新的参考。     

The effectiveness of borneol on pharmacokinetics changes of four ginsenosides in Shexiang Baoxin Pill in vivo

Shexiang Baoxin Pill (SBP) is a traditional Chinese medicine, widely used for cardiovascular diseases in the clinic. Ginsenosides are important effective components in SBP, but their pharmacokinetic characteristics are still not known. In this paper, we studied the pharmacokinetics of ginsenoside Rb1, Rc, Re and Rg1 in SBP and investigated the effect of borneol on the pharmacokinetic characteristic of ginsenosides based on an Agilent G6410A triple quadrupole LC/MS system. Results showed that the pharmacokinetic parameters of ginsenoside Rb1, Rc, Re and Rg1 in rat plasma after oral administration of SBP are significantly different with oral administration of SBP without Borneolum Syntheticum. Plasma pharmacokinetic profiles after oral administration of ginsenoside Rb1, Rc, Re, Rg1 and co‐administration with borneol at three different ratios (10:1, 1:1 and 1:10 ginsenoside vs borneol, w/w) were also determined. It was demonstrated that borneol can elevate the plasma concentration of ginsenosides after co‐admininstration. Copyright © 2013 John Wiley & Sons, Ltd.     

Discovery of quality markers for Mailuoshutong Pill based on “spider web” mode of “Content-Pharmacokinetics-Pharmacology” network

Mailuoshutong pill (MLSTP) is a traditional Chinese medicine compound preparation used for the treatment of thromboangiitis obliterans. However, component responsible for those effects are not yet identified, nor with their accurate contents and in-vivo movement, which means the quality markers of MLSTP are still unknown. The aim of this study was to discovery quality markers of MLSTP by developing a new multi-dimensional network strategy based on “Content-Pharmacokinetics-Pharmacology”. 40 analytes were determined by UHPLC-MS/MS in 8 min and the average contents in 11 batches of commercial MLSTP samples were used as the content dimension, the pharmacokinetics and pharmacology dimension were evaluated by five variables based on ADME Prediction and Prediction of Activity Spectra. Each dimension of the characteristic network was quantified by multivariate statistical analysis, and a three-dimensional network was constructed. Finally, Liquiritin, Calycosin-7-glucoside and Albiflorin with larger regression area were preferred as quality markers of MLSTP, which had satisfactory comprehensive properties of content, pharmacokinetic properties and pharmacological activity. In summary, the potential quality markers of MLSTP were identified by multi-dimensional characteristic network of content, pharmacokinetics and pharmacology. Also, the new strategy established in this work provided a valuable perspective for the selection of quality control indicators from compound formula.     

平行五波长高效液相色谱指纹图谱全息整合法定量鉴定杞菊地黄丸的整体质量

建立了杞菊地黄丸(Qijudihuang Pill, QJDHP)平行五波长(PFW)高效液相色谱(HPLC)指纹图谱,并依据系统指纹定量法结合全息整合法定量鉴定了杞菊地黄丸的整体质量。采用反相HPLC法,以丹皮酚(POL)为参照物峰,分别于203、228、265、280和326 nm下检测,分别确定了51、49、52、49和47个共有指纹峰,建立了QJDHP的PFW-HPLC指纹图谱。分别以权重法、均值法和投影参数法整合5个波长下各样品的定性定量全信息,结果基于5个波长综合信息用系统指纹定量法鉴定11批QJDHP样品,其中有8批质量为好,1批为较好,质量一般为2批。评价时以均值法最为简捷和准确。本实验结果表明,平行多波长指纹图谱整合法是基于从全信息角度整体定性和定量鉴定中药质量的有效可信方法,是对HPLC-二极管阵列检测（DAD）三维指纹图谱的简化定量处理,其整体综合定量鉴定结果具有可靠性。     

HPLC同时测定清胃黄连丸中的4种有效成分

建立同时测定清胃黄连丸中栀子苷、黄芩苷、小檗碱和巴马汀含量的HPLC方法。结果表明,栀子苷、黄芩苷、小檗碱和巴马汀分别在2.07—66.2μg/mL（r=0.9997）、2.72—86.9μg/mL（r=0.9998）、2.23—71.3μg/mL（r=0.9998）、2.13—68.1μg/mL（r=0.9998）范围内与峰面积呈良好的线性关系;平均回收率分别为103.2%（RSD=3.27%）、106.7%（RSD=2.46%）、103.5%（RSD=2.13%）、95.7%（RSD=2.68%）。该方法简便可行、重现性好、能更好的控制清胃黄连丸的质量。     

测定心灵丸中痕量铅的喷涂石英管原子吸收光谱法

采用火焰原子吸收光谱法测定中成药心灵丸中的铅。以混合酸消化待分析物，以氘灯扣除背景吸收，采用经钒酸盐溶液喷涂的石英缝管进行测定，考察了样品的预处理方法及提高测定灵敏度和高温下喷涂石英管的抗腐蚀性的机理。结果表明该消化方法可获得澄明的样品溶液而铅没有损失。灵敏度提高了近３倍，检出限为８３７μｇ／Ｌ（σ＝３），ＲＳＤ为０９％～１２％，其回收率为９７９％～１０２３％。     

Metabolomics approach based on ultra‐high‐performance liquid chromatography coupled with quadrupole‐time‐of‐flight mass spectrometry to identify the chemical constituents of the Traditional Chinese Er‐Zhi‐Pill

Er‐Zhi‐Pill, which consists of Ligustri lucidi fructus and Ecliptae prostratae herba , is a classical traditional Chinese medicinal formulation widely used as a liver‐nourishing and kidney‐enriching tonic. To identify the bioactive ingredients of Er‐Zhi‐Pill and characterize the variation of chemical constituents between co‐decoction and mix of individually decocted L. lucidi fructus and E. prostratae herba , a novel metabolomics approach based on ultra high performance liquid chromatography coupled with quadrupole time‐of‐flight mass spectrometry in both positive and negative ion modes, was established to comprehensively analyze chemical constituents and probe distinguishable chemical markers. In total, 68 constituents were unambiguously or tentatively identified through alignment of accurate molecular weights within an error margin of 5 ppm, elemental composition and fragmentation characteristics, including eight constituents, which were confirmed by comparing to reference standards. Furthermore, principal component analysis and partial least squares discriminant analysis using Simca‐p+ 12.0 software were applied to investigate chemical differences between formulations obtained by co‐decoction and a mixture of individual decoctions. Global chemical differences were found in samples of two different decoction methods, and 16 components, including salidroside, specneuzhenide and wedelolactone, contributed most to the observed differences. This study provides a basic chemical profile for the quality control and further mechanism research of Er‐Zhi‐Pill.     

桂附地黄丸金匮肾气丸指纹图谱双指标等级序列二次聚类分析及质量评价

建立了两种组成相似的中药桂附地黄丸和金匮肾气丸的鉴别和质量定量评价分级方法。采用数理统计方法分析桂附地黄丸和金匮肾气丸的水提物的红外指纹图谱共有峰率和变异峰率双指标序列,确定其中的等级序列并进行二次聚类分析, 构建了各种样品的最相似样品组。利用确定的每种中药样品的最相似样品组,可以准确鉴别18种桂附地黄丸和金匮肾气丸样品。文章提出的方法可以对桂附地黄丸和金匮肾气丸样品进行准确鉴别及质量定量评价。