Objective: To establish an ultra-high performance liquid chromatography-tandem mass spectrometry（UPLC-MS/MS） method for the simultaneous determination of twenty chemical components（arecoline hydrobromide, adenosine cyclophosphate, neochlorogenic acid, chlorogenic acid, cryptochlorogenic acid, caffeic acid, liquiritin, benzoylmesaconine, benzoylaconitine, isoliquiritin, benzoylhypacoitine, liquiritigenin, isoliquiritigenin, glycyrrhizic acid, 6-gingerol, honokiol, costunolide, dehydrocostus lactone, magnolol, betulinic acid）in Shipi powder. Methods: The separation was performed over 40.0 min on a Shim-pack GIST C 18 column（100 mm×2.1 mm, 2.0 μm） with a mobile phase consisting of 0.1% formic acid in water and acetonitrile with gradient elution（0-12 min, 2%B→14%B;12-24 min, 14%B→51%B;24-26 min, 51%B→70%B;26-36 min, 70%B;36-37 min, 70%B→2%B;37-40 min, 2%B） at a flow rate of 0.3 mL·min -1 . The column temperature was 35 ℃ and the injection volume was 1 μL. The detection was carried out by electrospray ionization（ESI）. Positive and negative electrospray ionizations were performed in multiple reaction monitoring（MRM） mode. Results: All of the analytes showed good linearity（r≥0.997 6） in the tested ranges. The precision, repeatability and stability of the method were good for the twenty chemical components. The average recoveries were in the range of 93.4%-108.7% with relative standard deviations RSD≤5.0%. The contents of arecoline, adenosine cyclophosphate, neochlorogenic acid, chlorogenic acid, cryptochlorogenic acid, caffeic acid, liquiritin, benzoylmesaconine, benzoylaconitine, isoliquiritin, benzoylhypacoitine, liquiritigenin, isoliquiritigenin, glycyrrhizic acid, 6-gingerol, honokiol, costunolide, dehydrocostus lactone, magnolol, betulinic acid in 15 bantches of in Shipi powder were 7 190.26-13 726.74, 90.11-301.93, 9.65-71.13, 102.88-710.98, 40.51-179.73, 10.90-71.22, 3 424.43-27 337.63, 508.34-1 276.14, 108.27-192.65, 95.74-378.92, 565.19-1 018.53, 106.23-623.42, 3.53-16.47, 6 104.50-15 933.93, 1 047.58-1 750.15, 537.91-2 582.74, 332.83-581.28, 348.22-760.81, 350.65-2 189.73, 2.06-39.22 μg·g -1 . Conclusion: The established method is accurate, stable and reproducible, and can provide a research method for the quality control of Shipi powder.

目的 建立15批当归建中汤特征图谱及多指标成分含量测定方法,为当归建中汤经典名方的质量控制评价提供参考.方法 色谱柱为 Waters Symmetry C18 色谱柱(4.6 mm×250 mm,5 μm);以乙腈(B)-0.1％磷酸溶液(A)为流动相,梯度洗脱;流速:1 mL·min-1;检测波长为230 nm;柱温35℃;进样量为5 μL,建立15批当归建中汤物质基准特征图谱,并使用HPLC测定5种指标成分含量.结果 对15批当归建中汤物质基准进行研究,其特征图谱相似度处于0.886～0.996之间,标定了 15个共有峰,指认出芍药内酯苷、芍药苷、阿魏酸、甘草苷、肉桂酸、甘草酸6个色谱峰.经方法学考察,5种成分在一定浓度范围内呈良好的线性关系;精密度、稳定性、重复性均符合要求;阿魏酸、肉桂酸、甘草苷、甘草酸、芍药苷的平均加样回收率分别为99.74％、100.28％、100.56％、98.44％、102.25％.以含量测定均值上下浮动30％规定出各指标成分的含量范围,均未出现离散数据(平均值的70％～130％以外).结论 建立的经典名方当归建中汤特征图谱及5个成分的含量测定方法简便、稳定、准确可靠,可用于当归建中汤物质基准的质量控制.

Yangwei decoction, a classical traditional Chinese medicine prescription, has been widely used to treat exogenous cold and internal injury with damp stagnation for many centuries. However, its systematic chemical profiling remains ambiguous, which has hampered the interpretation of pharmacology and the mechanism of its formula. In the present study, ultra-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry method was successfully established for the first time to separate and identify the complicated components of Yangwei decoction. The accurate mass data of the protonated molecules, deprotonated molecules, and fragment ions were detected in positive and negative ion modes. A total of 226 compounds in Yangwei decoction were tentatively identified and unambiguously characterized by comparing their retention times and mass spectrometry data with those of reference standards and literature, including 24 lignans, 18 alkaloids, 9 phenylpropanoid glycosides, 76 flavonoids, 59 triterpenoids, 17 organic acids, 7 gingerols, 8 lactones, and 8 other compounds. The present study provides a novel method of constituents characterization for well-known Chinese medicine prescriptions. The study aims to lay a robust foundation for future research, providing the holistic quality control and pharmacology of Yangwei decoction.

目的:建立UPLC-MS/MS方法同时测定养胃汤中26个成分(厚朴酚、和厚朴酚、木兰花碱、木兰箭毒碱、木兰苷A、木兰苷B、橙皮苷、川陈皮素、橘皮素、甜橙黄酮、芸香柚皮苷、柚皮素、人参皂苷Rb1、6-姜辣素、甘草苷、甘草酸、甘草素、异甘草素、异甘草苷、芹糖异甘草苷、毛蕊花糖苷、异毛蕊花糖苷、绿原酸、新绿原酸、咖啡酸、芦丁)的含量.方法:采用Shim-pack GIST C18色谱柱(2.1 mm ×100 mm,2.0μm),以乙腈-0.1％乙酸-1 mmol·L-1乙酸铵水为流动相,进行梯度洗脱,柱温为30℃,流速为0.3 mL·min-1,进样量为1μL,分析时间为18 min.采用电喷雾电离源(ESI源),以多重反应监测(MRM)模式正负离子检测.结果:所测26个化学成分在测定浓度范围内线性关系良好,相关系数均大于0.9969;精密度、重复性和稳定性良好;平均加样回收率为96.5％～104.2％,RSD≤4.0％.6批样品中厚朴酚、和厚朴酚、木兰花碱、木兰箭毒碱、木兰苷A、木兰苷B、橙皮苷、川陈皮素、橘皮素、甜橙黄酮、芸香柚皮苷、柚皮素、人参皂苷Rb1、6-姜辣素、甘草苷、甘草酸、甘草素、异甘草素、异甘草苷、芹糖异甘草苷、毛蕊花糖苷、异毛蕊花糖苷、绿原酸、新绿原酸、咖啡酸、芦丁的含量测定结果分别为2814.12 ～2951.41、2551.48 ～2675.66、288.12 ～312.36、439.88～494.60、452.00～ 500.74、329.76～358.68、5995.57～6283.13、70.16～73.81、22.95 ～24.21、5.56～6.39、997.32～1077.03、6.17～6.81、643.88 ～674.16、994.16 ～1063.20、1929.00～1984.85、2356.80～2518.96、247.68～ 256.64、38.02～43.18、228.84～241.4、227.17～234.87、129.61～150.39、28.97～31.90、622.85～643.23、526.05～542.73、70.09～78.64、152.41～ 166.3μg·g-1.结论:本方法准确灵敏,稳定性和重复性好,可用于养胃汤的质量控制.

目的 建立肉苁蓉药材超高效液相色谱(UPLC)指纹图谱及多成分含量测定方法,为其质量评价提供依据.方法 采用ACQUITY UPLC BEH C18色谱柱(2.1 mm×100 mm,1.7μm),以乙腈-0.1％磷酸溶液为流动相,梯度洗脱,流速0.3 mL/min,检测波长238 nm,柱温35℃,进样量1μL.结果 建立了2种基源肉苁蓉的UPLC指纹图谱,肉苁蓉确定了11个共有峰,管花肉苁蓉确定了9个共有峰,指认京尼平苷酸、松果菊苷、肉苁蓉苷A、毛蕊花糖苷、管花苷A、异毛蕊花糖苷和2'-乙酰基毛蕊花糖苷7种成分,并对其进行了含量测定,各成分色谱峰分离良好,且有较宽的线性范围和良好的线性关系,重复性、稳定性、回收率均符合要求.采用聚类分析和主成分分析方法可以对2种基源的肉苁蓉药材进行区分和鉴别.结论 UPLC指纹图谱结合多成分含量测定方法简便、准确,重复性良好,可快速鉴别不同基源肉苁蓉药材并评价其内在质量.

As a classic TCM prescription, LGZG has been widely used in clinical prevention and treatment of heart failure, nonalcoholic fatty liver, and hyperlipidemia. However, there are few studies on chemical components in recent years, and the basis of quality evaluation is not sufficient. This study was to find the active ingredients of the Lingguizhugan decoction using UPLC-MS/MS and network pharmacology. By comparing the retention time and MS dates of the reference and self-building database, the cleavage rules of chemical composition whose mass errors are less than 1 ppm(FL less than 3 ppm) are analyzed. On this basis, a network pharmacology method was used to find biomarkers for quantitative analysis. The results show that 149 compounds were preliminaries identified or inferred, including 63 flavonoids, 30 triterpenes, 22 phenylpropanoids, 13 organic acids, 6 lactones, 5 alkaloids, 4 anthraquinones, and 6 other compounds. According to the network pharmacology results, 20 chemical constituents were selected as the biomarkers, which were determined simultaneously for the first time, including poricoic acid A, poricoic acid B, glycyrrhizic acid, glycyrrhetinic acid, liquiritin, isoliquiritin, liquiritigenin, isoliquiritin apioside, cinnamic acid, caffeic acid, neochlorogenic acid, chlorogenic acid, cryptochlorogenic acid, isochlorogenic acid A, B, and C, atractylenolide I, II, and III, and coumarin. The methodological results show that the linearity, stability, precision, repeatability, and recovery of the method are satisfactory. Therefore, a comprehensive quality assessment system for LGZG was established on the basis of a systematic study of chemical substances and network pharmacology, which provided an important reference for the foundation of pharmacological action and its mechanics.

目的 比较薄荷和留兰香的非挥发性成分,为其质量评价提供依据.方法 采用Poroshell 120 EC-C18色谱柱,以甲醇-乙腈-5％乙酸溶液为流动相,梯度洗脱,流速0.6mL/min,柱温35℃,指纹图谱检测波长为305 nm,含量测定时隐绿原酸、咖啡酸、迷迭香酸、香叶木苷、蒙花苷、香叶木素检测波长为330 nm,橙皮苷、香蜂草苷为284 nm.采用聚类分析和主成分分析对薄荷和留兰香的非挥发性成分进行比较.结果 建立了薄荷和留兰香药材的HPLC指纹图谱,标定14个共有峰,指认其中7个成分.对薄荷和留兰香中隐绿原酸、咖啡酸、橙皮苷、迷迭香酸、香叶木苷、香蜂草苷、蒙花苷和香叶木素进行含量测定,各成分分离良好,方法重复性、稳定性、回收率均符合要求.聚类分析和主成分分析结果表明,薄荷和留兰香的非挥发性成分差异较小,不同采收期的药材质量差异较大.结论 HPLC指纹图谱结合多成分含量测定方法简便、准确,重复性良好,可为完善薄荷和留兰香的质量控制提供参考.

建立液质联用(UPLC-MS/MS)方法同时测定橘红中7个成分(绿原酸、芦丁、芸香柚皮苷、橙皮苷、甜橙黄酮、川陈皮素、橘皮素)的含量.采用Shim-pack GIST C 18色谱柱(100 mm×2.1 mm,2.0 μtm),以乙腈(A)-0.1％甲酸水(B)为流动相,进行梯度洗脱,柱温为30℃,流速为0.4 mL.min-1,进样量为1 μL,分析时间为12 min.采用电喷雾电离源(ESI源),以多重反应监测模式正负离子检测.所测7种化学成分在测定浓度范围内线性关系良好,相关系数均大于0.9973,精密度、重复性和稳定性良好,平均加样回收率为99.32％～107.75％,RSD≤3.94％.本实验所建立的方法准确灵敏,稳定性和重复性好,可用于橘红药材的质量控制.

目的 制备首乌藤饮片标准汤剂,并进行质量标准研究.方法 按照标准汤剂的制备要求,制备15批不同产地首乌藤饮片的标准汤剂,以2,3,5,4'-四羟基二苯乙烯-2-O-β-D-葡萄糖苷和大黄素-8-O-β-D-葡萄糖苷作为定量检测指标,计算其转移率及出膏率,并建立超高液相色谱特征图谱分析方法.结果 通过对15批首乌藤饮片标准汤剂进行测定,2,3,5,4'-四羟基二苯乙烯-2-O-β-D-葡萄糖苷的转移率为3.94％～53.53％,大黄素-8-O-β-D-葡萄糖苷的转移率为2.53％～37.06％,出膏率为1.46％～15.91％.采用《中药色谱指纹图谱相似度评价系统》软件进行特征图谱分析,标定了14个共有峰,指认了其中4个色谱峰.15批首乌藤饮片标准汤剂相似度评价结果显示,其相似度均大于0.90.结论 首乌藤饮片标准汤剂制备规范,测定方法精密度、稳定性和重复性良好,可为首乌藤配方颗粒的质量控制提供参考.

Hydrophilic interaction liquid chromatography (HILIC), as a powerful LC method for polar compounds, has gained increasing attention in developing new HILIC stationary phases and analytical methods. Instead of using standardized substance representing different molecular force types to evaluate chromatographic performance, the analyte targets, structural analogues of matrine and oxymatrine, are applied to modulate the preparation of carboxyl group modified column in a HILIC mode. The feasibility of target-modulating preparation of HILIC column was demonstrated that target-involved optimization could effectively reflect the performance of analytes directly onto the modulation of column preparation, and hence optimize out suitable preparation conditions different from otherwise methods. And the resulting monolith was tested in the analysis of the standard medicinal materials of Sophorae flavescentis radix. The target-modulating strategy was proved to be an efficient alternative to guide the preparation of HILIC monolith column.

目的 制备忍冬藤饮片标准煎液,并建立其质量控制方法.方法 按照标准煎液制备要求制备15批忍冬藤饮片标准煎液,以绿原酸、咖啡酸、马钱苷作为定量检测指标,计算出膏率、含量和转移率,并建立超高液相色谱特征图谱分析方法.结果 15批忍冬藤饮片标准煎液的出膏率范围为6.44％～11.95％,绿原酸、咖啡酸、马钱苷含量范围分别为12.17～22.61 mg/g、2.75～5.12 mg/g、21.71～40.32 mg/g,转移率范围分别为28.13％～52.25％、53.93％～100.15％、40.04％～74.36％.采用《中药色谱指纹图谱相似度评价系统(2012版)》软件进行分析和相似度评价,标定了10个共有特征峰,并指认绿原酸、咖啡酸、马钱苷3个色谱峰.通过与对照图谱比对,相似度均高于0.96.结论 本研究建立的忍冬藤饮片标准煎液的质量评价方法准确、稳定、重复性良好,可为忍冬藤配方颗粒的质量控制提供参考.

目的 制备川芎饮片标准汤剂,测定川芎标准汤剂中阿魏酸的含量,并建立特征图谱以进行质量标准研究.方法 依照标准汤剂的制备要求,制备15批不同产地的川芎饮片标准汤剂.以阿魏酸作为定量检测指标,计算转移率与出膏率,并建立超高液相色谱特征图谱,用《中药色谱指纹图谱相似度评价系统(2012版)》软件进行特征图谱分析.结果 15批川芎标准汤剂的出膏率范围为5.4％～10.1％;阿魏酸含量范围为2.39～4.44 mg/g,转移率范围为9.28％～17.24％.川芎标准汤剂特征图谱共标定了10个共有峰,指认其中4个共有峰.15批川芎饮片标准汤剂相似度均大于0.90.结论 川芎饮片标准汤剂制备规范,测定方法精密度、稳定性和重复性良好,可为川芎配方颗粒的质量控制提供参考.

Molecularly imprinted polymers (MIPs) have been attracting increasing attention and used in various applications.

This present study aims to establish a UPLC method for simultaneously determining eleven components such as new chlorogenic acid,chlorogenic acid,caffeic acid,cryptochlorogenic acid,artichoke,isochlorogenic acid A,isochlorogenic acid B,isochlorogenic acid C,rutin,hibisin and loganin in Lonicerae Japonicae Flos,Lonicerae Japonicae Caulis and leaves of Lonicera japonica and comparing the differences in the contents of phenolic acids,flavonoids and iridoid glycosides of Lonicerae Japonicae Flos,Lonicerae Japonicae Caulis and leaves of Lonicera japonica.The method was carried out on an ACQUITY UPLC BEH C18column(2.1 mm×100 mm,1.7 μm) by a gradient elution using acetonitrile and 0.1% phosphoric acid.The flow rate was 0.3 mL·min-1.The column temperature was maintained at 30 ℃.The sample room temperature was 8 ℃.The wavelength was set at 326 nm for new chlorogenic acid,chlorogenic acid,caffeic acid,cryptochlorogenic acid,artichoke,isochlorogenic acid A,isochlorogenic acid B and isochlorogenic acid C,352 nm for rutin and lignin,and 238 nm for loganin.The injection volume was 1 μL.The eleven components has good resolution and was separated to baseline.Each component had a wide linear range and a good linear relationship(r≥0.999 6),the average recovery rate(n=9) was 98.96%,100.7%,97.24%,97.06%,99.53%,96.78%,98.12%,95.20%,95.12%,100.2%,98.61%and with RSD was 2.5%,1.4%,1.9%,2.1%,1.7%,1.9%,1.6%,2.0%,1.4%,2.2%,2.0%,respectively.Based on the results of the content determination,the chemometric methods such as cluster analysis and principal component analysis were used to compare the Lonicerae Japonicae Flos,Lonicerae Japonicae Caulis and leaves of Lonicera japonica.The results showed that Lonicerae Japonicae Flos and leaves of Lonicera japonica were similar in the chemical constituents,but both showed chemical constituents difference compored to Lonicerae Japonicae Caulis.The established multi-component quantitative analysis method can provide a reference for the quality control of Lonicerae Japonicae Flos,Lonicerae Japonicae Caulis and leaves of Lonicera japonica.

目的 建立并比较川芎药材、破壁饮片、标准煎液、配方颗粒的 UPLC指纹图谱,分析其相似度并对川芎不同饮片形式进行聚类分析(cluster analysis,CA)及主成分分析(principal component analysis,PCA),为川芎不同的饮片形式提供质量控制依据.方法 采用 Waters ACQUITY UPLC BEH CI8色谱拉(2.1mm×100 mm,1.7 μm);以乙腈-0.1％磷酸为流动相,梯度洗脱;流速 0.3 mL·min-1;检测波长 276 nm;柱温 35 ℃;进样量 2 μL.对 12批川芎药材及其标准煎液、7批破壁饮片、以及 6 家厂家的川芎配方颗粒进行检测,采用国家药典委员会中药色谱指纹图谱相似度评价系统软件(2012年版)中位数法计算其相似度,并运用 SPSS 22.0统计软件进行化学模式识别分析.结果 川芎各饮片形式相似度均＞0.9,川芎药材、破壁饮片、标准煎液、配方颗粒与对照图谱的相似度分别为 0.534,0.449,0.979,0.968.CA及 PCA分析揭示了川芎不同饮片形式之间的相似性及差异性.结论 以指纹图谱数据为基础,将 CA与 PCA相结合,可以看出川芎每种饮片形式质量较稳定,并且川芎破壁饮片与药材相似度较高,川芎标准煎液与川芎配方颗粒相似度较高.

目的 制备山萸肉饮片标准汤剂并进行质量研究,为相关研究与药物开发提供参考.方法 根据中药饮片标准汤剂制备原则,制备15批不同产地的山萸肉饮片标准汤剂,以莫诺苷、马钱苷和山茱萸新苷作为定量检测指标,计算转移率与出膏率,并建立超高液相色谱(UPLC)特征图谱分析方法.结果 15批山萸肉饮片标准汤剂的出膏率为43.9％～48.2％,莫诺苷转移率为55.8％～90.8％,马钱苷转移率为52.8％～68.3％,山茱萸新苷转移率为47.2％～61.6％.采用《中药色谱指纹图谱相似度评价系统(2012版)》软件进行特征图谱分析,标定了13个共有峰,对15批山萸肉饮片及标准汤剂进行相似度评价,其相似度均大于0.9.结论 本研究山萸肉饮片标准汤剂制备规范,测定方法准确可靠,能够反映山萸肉水煎制剂的内在质量,可为山萸肉配方颗粒的质量控制提供参考.

目的 采用UPLC法建立金银花、忍冬叶和忍冬藤指纹图谱,对忍冬不同部位采用指纹图谱相似度评价及聚类分析和主成分分析等化学模式识别技术进行研究,以期为忍冬药材的综合利用提供科学依据.方法 采用ACQUITY UPLC BEH C18(100 mm×2.1 mm,1.7μm)色谱柱,以乙腈-0.1％磷酸溶液为流动相梯度洗脱,体积流量0.3 mL/min,柱温30℃,样品室温度8℃,检测波长326、238、350 nm,进样量1μL.结果 28批样品有14个共有峰,与对照品色谱峰比对,指认了10个色谱峰,分别为新绿原酸、绿原酸、隐绿原酸、咖啡酸、马钱苷、芦丁、木犀草苷、异绿原酸B、异绿原酸A和异绿原酸C,金银花(10批)、忍冬叶(9批)和忍冬藤(9批)化学成分组成及量均存在一定差异.采用聚类分析及主成分分析从化学成分上揭示了忍冬不同部位28批样品的相似性及差异性.结论 金银花与忍冬叶化学成分较为相似,而与忍冬藤间存在差异,所建立的指纹图谱方法可为金银花、忍冬叶、忍冬藤的质量控制提供参考.

目的 制备女贞子饮片标准煎液,并进行质量标准研究.方法 制备16批不同产地女贞子饮片标准煎液,以特女贞苷为定量检测指标,计算转移率与出膏率,并建立其UPLC特征图谱,采用《中药色谱指纹图谱相似度评价系统(2012版)》软件进行分析.结果 16批女贞子标准煎液特女贞苷转移率为33.57％～56.91％,出膏率为23.20％～26.87％.UPLC特征图谱标定了10个共有峰,指认了其中1个峰.16批女贞子饮片标准煎液相似度评价结果显示其相似度均大于0.90.聚类分析将16批女贞子标准煎液分为2类;主成分分析提取出了3个主成分,其累积贡献率达92.73％.结论 本研究可为女贞子标准煎液及其配方颗粒的质量控制提供参考.

Objective:To prepare Flos Albiziae standard decoction and determine the content of quercetin in standard decoction and establish chromatographic fingerprint for studying the quality standard decoction.Methods:Fifteen batches of Flos Albiziae standard decoctions were prepared according to the standardization method.With quercetin as the detection index, the transfer rate and extraction rate were calculated and a UPLC characteristic chromatograms analysis method was established.Results:According to the measurement of 15 batches of standard decoctions, the transfer rate ranged from 72.33％to41.51％and extract rate was at the range of 26.6％ to 23.4％.Besides, the Similarity Evaluation System for Chromatographic Fingerprint of traditional Chinese medicine TCM was used to analyze and compare the characteristic chromatograms, five peaks were calibrated.Moreover, the similarity of fifteen batches was over 0.90.Conclusion:Samples were prepared by a standard method.The method displayed a good precision stability and repeatability.Therefore, this study can provide a reference for the quality control of Flos Albiziae formula granules.

目的 建立快速鉴别地榆及其炮制品地榆炭配方颗粒的红外方法.方法 采用红外光谱结合二阶导数光谱及二维相关光谱法分析地榆及其炮制品配方颗粒的光谱特征.结果 地榆与炮制品配方颗粒的红外光谱基本相似,仅在2 932、1041、918、760 cm-1处位置变化;二阶导数光谱在1 200～1 800 cm-1差异较大,二维相关光谱图差异明显.结论 通过比较地榆及其炮制品红外光谱图、二阶导数光谱图及二维相关光谱图,可以准确、快速鉴别地榆及其炮制品地榆炭配方颗粒.