基于UHPLC-Q-Exactive Orbitrap MS技术的正心降脂片化学成分研究

目的 建立一种快速鉴定中药复方制剂正心降脂片的高分辨质谱分析方法,系统阐明其化学成分组成。方法 采用超高效液相色谱-静电场轨道阱高分辨质谱(UHPLC-Q-Exactive Orbitrap MS)对正心降脂片成分进行分析,色谱柱为Thermo Accucore aQ RP18(2.1 mm×150 mm, 2.6 μm),流动相采用乙腈(A)-0.1%甲酸水(B)进行梯度洗脱,流速0.3 mL·min^-1。采用加热电喷雾离子源,正、负离子同时扫描模式采集数据。根据一级准分子离子精确质荷比、二级质谱碎片离子信息、文献报道和对照品比对鉴定正心降脂片的化学成分。结果 共鉴定了正心降脂片中105个化学成分,包括21个有机酸、59个黄酮类化合物(黄酮氧苷类37个,黄酮碳苷类10个,多甲氧基黄酮类化合物12个)、19个醌类化合物(11个蒽醌类和8个菲醌类)、3个二苯乙烯类化合物及3个其他类型化合物。其中29个化合物采用对照品比对进行了鉴定,并对各成分的药材来源进行了归属。结论 对正心降脂片的化学成分进行了系统、全面地分析,为其药效物质基础、质量控制及作用机制研究奠定了基础。     

基于UHPLC-Q-TOF-MS/MS和LTQ-MSn联用技术快速鉴定绞股蓝皂苷类化学成分

目的 建立超高液相色谱-飞行时间高分辨质谱(UHPLC-Q-TOF MS/MS)和超高液相线性离子阱质谱(LTQ-MSⁿ)联用技术对绞股蓝中皂苷类成分快速鉴定的方法。方法 采用Thermo Syncronis C₁₈(2.1 mm×100 mm,1.7 μm)色谱柱,以纯水-乙腈为流动相梯度洗脱,质谱采用电喷雾(ESI)离子源,在负离子模式下采集数据对绞股蓝皂苷类进行成分鉴定。结果 初步鉴定了81种绞股蓝皂苷,其中包括58种已知皂苷和23种可能的未知皂苷结构。结论 UHPLC-Q-TOF-MS/MS可以提供化合物的准确相对分子质量及二级碎片信息,LTQ-MSⁿ可以提供化合物多级质谱信息,该联用技术可以简单、快速鉴定绞股蓝皂苷类成分,并为其质量控制、药效物质基础研究及进一步临床应用提供理论依据和科学研究思路。     

基于UHPLC-LTQ-Orbitrap-MS/MS技术快速分析保心宁胶囊中的化学成分

目的 建立高效,稳定的超高效液相色谱-线性离子阱轨道阱串联质谱联用(UHPLC-LTQ-Orbitrap-MS/MS) 方法,系统、全面地定性分析中药制剂保心宁胶囊中的化学成分组成。为保心宁胶囊质量控制方法的开发,标准的完善以及临床应用提供依据。方法 采用UHPLC-LTQ-Orbitrap-MS/MS对保心宁胶囊中的化学成分进行快速分析。通过UHPLC-LTQ-Orbitrap-MS/MS扫描的到的化合物精确分子量,对照品和多级碎片离子信息,并结合相关文献以及裂解规律,实现对保心宁胶囊的准确定性分析。结果 共鉴定出103种化学成分,包括萜类、皂苷类、酚酸类、黄酮类、有机酸类、香豆素类、苯酞类及姜黄素类等,并对化合物的药材归属进行了分类。结论 本研究建立了对保心宁胶囊中化学成分的快速定性分析的方法,为保心宁胶囊的质量评价指标及药效物质基础研究提供参考。     

同时测定制剂中添加3种卡波地那非类似物的研究

目的 建立制剂中添加3种卡波地那非类似物的分析方法。方法 以乙腈为提取溶剂,样品经Agilent Eclipse Plus C₁₈(4.6 mm×250 mm,5 μm) 色谱柱分离,高效液相色谱仪-二级管阵列(DAD)检测器定性、定量检测3种制剂中的3种卡波地那非类似物(去甲基卡波地那非、二硫去甲基卡波地那非、二甲基哌嗪二硫去甲基卡波地那非)。用Dikma Spursil C₁₈(2.1 mm×150 mm,3 μm)色谱柱分离,高效液相色谱-质谱联用仪以一级及二级质谱定性确证3种卡波地那非类似物。结果 3种卡波地那非类似物检测的线性相关系数r≥0.995 8;方法精密度相对标准偏差(RSD) 为2.2%～4.3%;3个添加水平的方法回收率为95.3%～102.8%;定量限为22～58 ng。结论 本方法准确,操作简单、快捷,可作为3种制剂中卡波地那非类似物化学成分的定性、定量检测方法。     

基于UHPLC-Q-Exactive Orbitrap MS/MS的川乌生物碱成分分析

目的 建立超高效液相色谱-四极杆-静电场轨道阱串联质谱(UHPLC-Q-Exactive Orbitrap MS/MS)技术对川乌中生物碱类化学成分进行快速鉴定的方法。方法 采用ACQUITY UHPLC BEH C₁₈柱(2.1 mm×100 mm, 1.7 μm)色谱柱,以0.1%氨水(A)-乙腈(B)为流动相;洗脱程序为0~3 min,0~15% B;3~10 min,15%~40% B;10~16 min,40%~70% B;16~20 min,70%~90%进行梯度洗脱,柱温35 ℃,流速为0.3 mL·min^-1,进样量2 μL,正离子模式扫描。结果 最终从川乌中鉴定了141种生物碱类成分。其中单酯型生物碱37种,双酯型生物碱21种,三酯型生物碱2种,醇胺型生物碱80种及其他类生物碱1种。结论 该研究所建立的定性分析方法可系统快速地识别川乌中生物碱类化学成分,并为川乌的作用机制研究和产业开发提供一定的参考依据。     

延边产朝药材肾炎草的高效液相色谱指纹图谱研究

目的 建立朝药材肾炎草的HPLC-UV指纹图谱。方法 采用SunFire^TM C₁₈ (4.6 mm×250 mm, 5 μm)色谱柱;以乙腈(B)-0.4%冰醋酸溶液(A)梯度洗脱,检测波长253 nm,柱温40 ℃,进样量10 μL,流速1.0 mL · min^-1,采用对照品指认进行成分分析。结果 建立了朝药材肾炎草的HPLC-UV特征指纹图谱共有模式,标定了21个共有峰,指认了其中3个黄酮碳苷成分。10批次药材的相似度结果均大于0.95,相似程度高。结论 该方法简便,精密度、重复性和稳定性很好,特征性和专属性强,可为肾炎草药材整体质量控制提供有效手段。     

注射用磺苄西林钠的杂质谱研究

目的 建立高效液相色谱串联高分辨质谱检测器的方法,研究注射用磺苄西林钠的杂质谱并进行来源归属。方法 采用Agilent 1290 HPLC-6538 Q-TOF高效液相色谱质谱联用仪,流动相为10 mmol·L^-1甲酸铵溶液-8 mmol·L^-1甲酸铵溶液(体积分数80%乙腈溶液作溶剂)=87∶13;色谱柱为Ultimate XB C₁₈(4.6 mm×250 mm,5 μm);流速1.0 mL·min^-1;质谱检测器采用电喷雾离子源(ESI),负离子扫描模式;数据采集范围m/z 50~1 000,离子源前进样分流比2∶1,毛细管电压3.5 kV,锥孔电压65 V,喷雾气压310 kPa,干燥气(氮气)流量12 L·min^-1,干燥气温度325 ℃,碎裂电压150 V。通过分析主成分与未知杂质多级质谱行为的相关性以及主成分的合成工艺推定其结构。结果 将5个厂家样品中的主要杂质归纳为14个未知杂质,解析其质谱碎片进行结构推测和来源归属。结论 研究结果对注射用磺苄西林钠的质量控制和工艺评价具有指导意义。     

采用二维高效色谱-串联四级杆飞行时间质谱法对注射用头孢美唑钠的未知杂质进行结构解析

目的 建立一种二维高效液相色谱-串联质谱方法,对注射用头孢美唑钠在含不挥发性流动相的一维色谱中检出的未知杂质进行结构解析。方法 一维色谱的流动相为磷酸二氢铵溶液(取磷酸二氢铵5.75 g,加水730 mL使溶解,加10 %四丁基氢氧化铵19.2 mL)-四氢呋喃-甲醇混合液(730∶12.5∶300)(用磷酸调pH值至4.5),色谱柱采用Shim-pack GIS C₁₈(4.6 mm×250 mm,5 μm)柱,流速1.0 mL·min^-1。二维色谱流动相为1%甲酸水溶液(A相)/乙腈(B相),梯度洗脱,采用Shim-pack GIS C₁₈(4.6 mm×150 mm, 5 μm)色谱柱,流速1.0 mL·min^-1,柱温为25 ℃。采用50 μL定量环收集一维色谱分离到的未知杂质成分。质谱采用电喷雾离子源(ESI)源进行离子化,氩气做碰撞气,全扫描-数据相关分析模式(DDA)进行检测。基于未知杂质的母离子和子离子的精确分子量、头孢美唑的质谱裂解规律和同位素分布等信息,推断出可能的分子结构。结果 对注射用头孢美唑钠中的3种未知杂质进行了结构鉴定,杂质1和杂质3为头孢美唑钠的同分异构体,为热降解杂质,杂质2为7-甲巯基头孢美唑,是头孢美唑钠的工艺杂质。结论 本方法采用二维色谱对注射用头孢美唑钠中3种超过鉴别限的未知杂质进行了结构分析,为采用不挥发性流动相分离得到的β-内酰胺类抗生素中未知杂质的定性研究提供了解决方案。     

基于UPLC-Q-Orbitrap HRMS的川佛手化学成分分析

目的:应用超高效液相色谱-四极杆-静电场轨道阱高分辨质谱(UPLC-Q-Orbitrap HRMS)技术,分析鉴定中药川佛手中的化学成分。方法:采用Thermo Scientific Accucore~(TM)C_(18)色谱柱(3 mm×100 mm,2.6μm),流动相0.1%甲酸水溶液-0.1%甲酸乙腈溶液梯度洗脱,流速0.3 m L·min~(-1),柱温30℃。高分辨质谱采用电喷雾离子源(ESI),正离子模式扫描,扫描方式为全扫描/数据依赖二级扫描(Full MS/dd-MS~2)。数据运用Compound Discoverer 3.0软件分析,根据化合物的精确相对分子质量、色谱保留时间、特征离子碎片信息,结合mz Cloud网络数据库、中药成分高分辨质谱数据库(OTCML)、文献信息和相关对照品进行鉴定。结果:从川佛手中共鉴定了54个化学成分,包括黄酮类16个,香豆素类17个,柠檬苦素类3个,核苷及其碱基类6个,有机酸类2个,芳香醛类3个,氨基酸类1个,其他类成分6个。结论:该法可全面、准确地分析鉴定川佛手中的主要化学成分,研究结果为阐明川佛手的药效物质基础、优选质量控制指标提供了方法学参考和理论依据,对进一步开发利用川佛手资源具有指导意义。     

檵木水溶性化学成分研究

目的 研究檵木水溶性化学成分。方法 采用大孔树脂、硅胶、凝胶、制备高效液相等色谱技术进行分离,根据波谱数据对化合物进行结构鉴定。结果 从檵木叶中分离得到10个化合物,分别鉴定为(6S,9R)-roseoside(1),rhododendrin(2),epirhododendrin(3),(1S,2R,4S,5S)(-)-Angelicoidenol 2-O-β-D-glucopyranoside(4),dihydroalangionoside A(5),(Z)-3-hexenyl β-primeveroside(6),benzyl β-primeveroside(7),(Z)-3-hexenyl O-α-L-rhamnopyranosyl-(1→6)-β-D-glucopyranoside(8),rhododendrol 4'-O-β-D-glucopyranoside(9),3-(4-hydroxyphenol)propyl β-D-glucopyranoside(10)。结论 化合物1~7,9,10均首次从该属植物中分离得到。     

彝族药姜味草指纹图谱的建立和化学模式识别分析及含量测定

目的 建立彝族药姜味草的高效液相色谱法(HPLC)指纹图谱分析方法,结合化学模式识别,对其质量进行分析,并测定其中4种成分的含量.方法 采用Agilent-C18色谱柱(4.6 mm×250 mm,4 μm),以乙腈-0.2％磷酸水为流动相,梯度洗脱,以迷迭香酸为参照,建立15批不同来源样品的HPLC特征图谱,结合相似...     

基于UPLC-ESI-Q-TOF-MS/MS技术快速鉴定彝族药双参的化学成分

目的 应用超高效液相色谱-电喷雾/四极杆飞行时间串联质谱(UPLC-ESI-Q-TOF-MS/MS)技术快速鉴定双参药材的化学成分。方法 采用Acquity UPLC BEH C₁₈色谱柱(2.1 mm×100 mm, 1.7μm)分离,以体积分数0.1%甲酸水溶液(A相)-乙腈(B相)为流动相进行梯度洗脱,流速0.4 mL·min^-1,采用电喷雾离子源(ESI),在正、负离子模式下采集数据,扫描范围m/z 100～2 000,通过与对照品的保留时间及质谱数据信息对比,并结合精确相对分子质量、质谱裂解规律、质谱数据库(ChemicalBook, ChemSpider, Pubmed等)及相关文献,对双参的化学成分进行快速鉴定。结果 从彝族药双参中共鉴定出59个化合物,其中包括11个环烯醚萜类、23个有机酸类、14个三萜类、4个糖苷、其他类(1个香豆素类、1个生物碱类、2个酯类、1个多酚类、2个核苷类),其中通过与对照品对比鉴定了8个化合物,分别为绿原酸、隐绿原酸、异绿原酸A、异绿原酸B、异绿原酸C、马钱苷、马钱苷酸和樟芽菜苷。结论 该研究首次...     

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??OBJECTIVE To identify the chemical components of bile acids from bear bile powder, the intermediate of bear bile powder and Tanreqing capsules by HPLC-MS/MS. METHODS All samples were extracted with 70% methanol(V/V), and an Ultimate XB C₁₈ column (4.6 mm??250 mm, 5 ??m) was employed for separation with acetonitrile-0.1% formic acid as mobile phase in gradient elution. The MS spectrum was acquired in both positive and negative ion mode using ESI ion source. The chemical components were identified by the second mass spectrometric pyrolysis fragments, chromatographic peak retention time and fragmentation regularity summarized from the reference standards and the available literature. RESULTS A total of 33 compounds were successfully identified or tentatively predicted, and six chemical compounds including tauroursodeoxycholic acid, taurochenodeoxycholic acid, ursodeoxycholic acid, chenodeoxycholic acid, 7??-hydroxy-3-oxo-5??-cholanic acid and one unknown constituent were finally transferred to Tanreqing capsules through the intermediate of bear bile powder. Moreover, 21 new chemical compounds (major ingredients of free bile acids) were generated during the production process of the intermediate, and 19 components were also detected in Tanreqing capsules. CONCLUSION The investigation of the change of constituents in bear bile powder during Tanreqing capsules production provides a basis for the quality control and evaluation of Tanreqing capsules during production process.     

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??OBJECTIVE To qualitatively analyze the chemical constituents of Folium hibisci Mutabilis by high performance liquid chromatography-electrospray ionization-quadrupole-time of flight-mass spectrometry (UHPLC-Q-TOF-MS/MS).METHODS The separation was performed on a UHPLC Welch C₁₈ column (2.1 mm??100 mm,1.7 ??m), with acetonitrile-0.1% formic acid as the mobile phase for gradient elution;ESI ion source was used; the data was collected in a negative ion mode.The chemical components of Folium hibisci Mutabilis were identified by analyzing the retention time, exact relative molecular mass, and cleavage fragments of MS/MS.RESULTS A total of 73 compounds were identified in Folium hibisci Mutabilis,including 42 flavonoids,15 triterpenoids,11 organic acids,3 coumarins,and 2 other kinds of compounds by UPLC-Q-TOF-MS.CONCLUSION LC-MS/MS can identify the chemical components of Folium hibisci Mutabilis in a simple,which would provide a foundation for further exploration of the effective substances of Folium hibisci Mutabilis.     

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??OBJECTIVE To qualitatively analyze the major chemical constituents of Magnoliae Officinalis Cortex by UFLC-Triple TOF-MS/MS. METHODS The analysis was carried out on an Agilent ZORBAX SB-C₁₈ column(4.6 mm ??250 mm,5 ??m)with gradient elution of 0.1% formic acid-acetonitrile under both positive and negative ionization modes of ESI, respectively. The chemical components of Magnoliae Officinalis Cortex were identified by analyzing the accurate mass of molecular and product ions provided by UFLC-Triple TOF-MS/MS, comparison with reference standards and the literature data. RESULTS A total of 24 compounds were identified or tentative presumed in Magnolia Officinalis Cortex, including 12 lignans, 9 alkaloids, and 3 phenylpropanoid glycosides. CONCLUSION This study provides the foundation and support for study on material foundation of efficacy and the overall assessment of quality of Magnoliae Officinalis Cortex.     

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??OBJECTIVE To analyze the differences in chemical composition of Magnolia officinalis var. biloba Rehd. et Wils from different commercial specifications. METHODS The difference in chemical constituents of Magnolia officinalis var. biloba Rehd. et Wils from different commercial specifications was analyzed by LC-Triple TOF MS/MS combined with multivariate statistical analysis. Through analysis of the multistage tandem mass spectrometry, the characteristic peaks were extracted with mass spectrometry data peak matching, peak alignment, and noise filtering. Principal component analysis(PCA)and partial least-squares discriminant analysis(PLS-DA)were used for data processing. The components were identified according to MS accurate mass and MS/MS spectrometry fragmentation information, combined with the database search and literature. RESULTS The chemical constituents in Magnolia officinalis var. biloba Rehd. et Wils from different commercial specifications were clearly distinguished. Twenty-two chemical constituents had significant differences. Among them, 10 kinds of common different chemical constituents, such as leonoside A, syringaresinol-4'-O-??-D-glucopyranoside, magnolignan D, magnolignan A or C, randaiol, honokiol, obovatol, magnolignan G,(??)9-HODE and piperitylmagnolol, presented different changing laws. CONCLUSION This study can provide references for establishment of a mathematical model for prediction of the specifications of chemical information of Magnoliae Officinalis Cortex based on metabolomics and comprehensive evaluation of the quality of medicinal herbs.     

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??OBJECTIVE To study the chemical constituents from the rhizome of Drynaria fortunei and the protective effects of them on PC12 cells induced by A??_25-35. METHODS The compounds were isolated and purified by silica gel, Sephadex LH-20, ODS column chromatography, and their structures were identified on basis of spectroscopic methods, such as MS and NMR. PC12 cells were treated with A??_25-35 to establish the Alzheimer' s disease models. The compounds of different concentrations were added into culture medium to detect the protection. MTT assay was used to detect cell vitality and to observe the protective effects of compounds on PC12 cells induced by A??_25-35. RESULTS Nine compounds were isolated and identified as naringin(1), neoeriocitrin(2), 5,7-dihydroxychromone-7-neohesperidoside(3), (E)-4-O-??-D-glucopyranosyl caffeic acid(4), kaempferol(5), luteolin(6), protocatechoic acid(7), psoralen(8), and ??-sitosterol(9) . The cell experiments were performed on the compounds 1-8 and the results showed they can promote the proliferation of PC12 cells. The cell vitality increase with concentration rising, and the difference is statistically significant (P<0.05). CONCLUSION Compounds 1-8 play an important role in protecting A??_25-35-induced injury in PC12 cells and they are the main active components of Drynaria fortunei in the protection of central nervous function.     

绵马贯众中新间苯三酚类化合物

目的 研究药材绵马贯众中间苯三酚类化学成分.方法 采用大孔吸附树脂富集(体积分数为10％乙醇、30％乙醇、50％乙醇、70％乙醇和95％乙醇等依次洗脱),以及制备C18柱色谱(色谱柱:49 mm×460 mm,分别用体积分数10％甲醇、20％甲醇水、30％甲醇、50％甲醇、70％甲醇和100％甲醇依次洗脱)、凝胶柱色谱...