超高效液相色谱-质谱法测定醋五味子中7种木脂素的含量北大核心CSCD

采用超高效液相色谱-质谱法测定醋五味子中五味子酯甲、五味子酚、五味子甲素、五味子乙素、五味子丙素、五味子醇甲和五味子醇乙等7种木脂素的含量。醋五味子样品0.200 0g用甲醇10mL超声提取30min。以ACQUITY UPLC BEH C_(18)色谱柱为分离柱,以不同体积比的乙腈和0.1%(体积分数)甲酸溶液的混合液为流动相进行梯度洗脱,质谱分析中采用电喷雾正离子源和选择离子监测模式。7种木脂素的质量浓度在一定范围内与其对应的峰面积呈线性关系,方法的检出限(3S/N)为0.001~0.050mg·L^(-1)。对6.0mg·L^(-1)的7种木脂素混合标准溶液连续测定6次,测定值的相对标准偏差为1.2%~3.5%。方法用于醋五味子样品的分析,加标回收率为85.4%~99.3%。     

超高效液相色谱-质谱法测定醋五味子中7种木脂素的含量

采用超高效液相色谱-质谱法测定醋五味子中五味子酯甲、五味子酚、五味子甲素、五味子乙素、五味子丙素、五味子醇甲和五味子醇乙等7种木脂素的含量。醋五味子样品0.200 0g用甲醇10mL超声提取30min。以ACQUITY UPLC BEH C_(18)色谱柱为分离柱,以不同体积比的乙腈和0.1%(体积分数)甲酸溶液的混合液为流动相进行梯度洗脱,质谱分析中采用电喷雾正离子源和选择离子监测模式。7种木脂素的质量浓度在一定范围内与其对应的峰面积呈线性关系,方法的检出限(3S/N)为0.001~0.050mg·L~(-1)。对6.0mg·L~(-1)的7种木脂素混合标准溶液连续测定6次,测定值的相对标准偏差为1.2%~3.5%。方法用于醋五味子样品的分析,加标回收率为85.4%~99.3%。     

高效液相色谱法测定北五味子中5种木脂素含量

应用高效液相色谱法测定北五味子中五味子醇甲、五味子酯甲、五味子甲素、五味子乙素和五味子丙素等5种木脂素的含量。北五味子样品(1.000g)在70℃温度下用甲醇(20mL)微波辅助提取5min。分取部分提取液,以Hypersil ODS C18色谱柱为固定相,用乙腈和水以不同比例混合的溶液为流动相进行梯度洗脱,在检测波长225nm处进行测定。5种木脂素在一定的质量浓度范围内与其峰面积呈线性关系,方法的检出限(3S/N)在0.029 2~0.050 7mg·L-1之间。以样品为基体,在3个浓度水平加入混合标准溶液进行回收试验,测得回收率在95.3%~101%之间,测定值的相对标准偏差(n=6)在1.1%~2.4%之间。     

超分子有序聚集凝固液相微萃取及其对五味子中木脂素类化合物的测定及质量评价

通过分析比较漂浮有机液滴凝固液相微萃取(SFODLPME)对木脂素类化合物萃取前后紫外光谱的变化, 提出了超分子有序聚集凝固液相微萃取(SSMOALPME)机理; 建立了简单、 快速、 灵敏的SSMOALPME高效液相色谱法(HPLC)同时测定中药五味子中5种低丰度木脂素类化合物含量的方法, 并对不同产地五味子的质量进行比较和评价. 在最佳的SSMOALPME条件下, 测得五味子醇甲, 五味子酯甲, 五味子甲素, 五味子乙素和五味子丙素的线性范围分别为2.48×10^-3~6.21, 2.27×10^-3~28.5, 2.31×10^-3~28.8, 2.27×10^-3~5.69和1.05×10^-3~5.25 μg/mL; 检出限分别为0.4, 0.4, 0.4, 0.08和0.08 ng/mL; 日内及日间精密度RSD<9.7%; 药材中分析物的回收率为91.9% ~104.7%; SSMOALPME对5种分析物的富集倍数分别在39 ~529倍之间. 本法测定结果与药典法测定结果相比无显著差异(P=95%). SSMOALPME方法的提出为液相微萃取的理论研究奠定了基础, 为反映中药多成分、 多靶点及协同作用的特性, 建立科学的质量控制方法提供了理论依据和实验基础.     

高效液相色谱法测定五味子和含五味子的制剂中五味子乙素及多种活性成分时流动相体系的选择

建立了用高效液相色谱法测定五味子和含五味子的制剂中五味子乙素的流动相体系。用Shim-pack VP-ODS (250 mm×4.6 mm,5 μm)色谱柱,在柱温30 ℃、检测波长285 nm、流速1.0 mL/min的条件下,用不同的流动相组成及其不同比例研究了五味子提取液中3种木脂素(五味子乙素、安五脂素和五味子甲素)的保留时间及其分离情况,从中选择测定五味子乙素的最佳流动相体系。结果表明,在甲醇-水、甲醇-冰醋酸-水的流动相体系中,安五脂素和五味子乙素很难完全分离;而在乙腈-甲醇-水和乙腈-冰醋酸-水流动相体系中,3种木脂素可很好地分离。以乙腈-甲醇-水(体积比为17:58:25)为流动相测定五味子和护肝片中3种木脂素的含量,相对标准偏差(n4)为0.95%～5.8%,平均加标回收率为94.50%～105.6%。将该流动相体系用于供试品中3种木脂素含量的测定,分离效果好,结果令人满意。     

五味子优良品种优选的模式识别方法

通过超高效液相色谱法,对不同生长特征的五味子样品中5种主要的木脂素成分:五味子醇甲、五味子醇乙、五味子酯甲、五味子甲素和五味子乙素进行测定,同时考察其抗氧化活性。 对所得到的5种木脂素成分的含量及抗氧化数据进行聚类分析和主成分分析,并且通过逐步判别分析建立判别函数,从而筛选五味子优良品种。 主成分分析和聚类结果基本一致,均将样品分为3大类,逐步判别分析的正确率高达90%。     

基于响应面法的基质固相分散萃取土壤中有机磷阻燃剂

有机磷阻燃剂(OPFRs)被广泛添加于商业品和日用品中，由于具有环境持久性、生物富集性和潜在毒性，已成为一种新兴的持久性有机污染物。因此需要建立能准确定量环境中OPFRs的检测方法。该文基于基质固相分散萃取(MSPD),结合气相色谱-串联质谱(GC-MS/MS)法测定土壤中10种有机磷阻燃剂，筛选对OPFRs具有高选择性的吸附剂，最终确定MSPD最佳萃取条件。该文基于单因素分析法考察了常见吸附剂(C18、PSA、Florisil、石墨化炭黑(GCB)和多壁碳纳米管(MWCNT))及其用量、洗脱溶剂及其体积、研磨时间对OPFRs萃取效率的影响。在此结果基础上，进一步利用响应面法(RSM)考察了3个关键因素(吸附剂用量、洗脱剂用量和研磨时间)以及交互作用对OPFRs萃取效率的影响。最终确定最优条件：吸附剂GCB,用量0.3 g;洗脱溶剂乙酸乙酯，用量10 mL;研磨时间5 min,此时10种OPFR的萃取效率为87.5%。在GC-MS/MS的多反应监测模式(MRM)下，以¹³C-PCB208为内标物进行定量。10种OPFRs在6个浓度梯度下，获得较好的线性，相关系数大...     

固相萃取-反相高效液相色谱法测定水中的邻苯二甲酸酯

建立了固相萃取-反相高效液相色谱法检测水中3种邻苯二甲酸酯类物质邻苯二甲酸二甲酯、邻苯二甲酸二(2-乙基己基)酯、邻苯二甲酸二正辛酯的方法. 考察了固相萃取柱、洗脱溶剂、洗脱体积、上样速度以及洗脱速度对萃取效率的影响. 通过综合分析, 选定SupelcleanLC-18 SPE Tube固相萃取柱, 甲醇为洗脱剂, 洗脱体积2 mL, 上样速度为4 mL/min, 洗脱速度为1 mL/min. 在此萃取条件下, 萃取回收率在83.4%～121.2%之间. 邻苯二甲酸二甲酯、邻苯二甲酸二(2-乙基己基)酯、邻苯二甲酸二正辛酯质量浓度在2～100 mg/L之间均为线性. 经萃取后, 方法的最低检出限分别为邻苯二甲酸二甲酯0.06 μg/L, 邻苯二甲酸二(2-乙基己基)酯0.16 μg/L, 邻苯二甲酸二正辛酯0.08 μg/L. 方法的精密度在10%～15%之间. 应用该方法测定自来水中酞酸酯类化合物的含量, 加标回收率为83.6%～110.2%.     

五味子超临界CO2提取物的气相色谱-质谱分析

将五味子样品于25 MPa、45 ℃下用超临界CO2提取2 h,提取物经气相色谱-质谱分析,共测得16个成分,经与对照品、NIST谱库对照和结构解析,鉴定出其中的7种木脂素成分,占色谱峰总面积的80.5%,其中五味子甲素9.39%、五味子乙素30.58%、五味子醇甲16.00%、五味子丙素5.95%和五味子醇乙15.17%。     

南北五味子荧光光谱差异的原因

建立了用荧光法快速鉴别五味子和部分含五味子制剂中五味子是属于北五味子还是南五味子的方法,探明了南北五味子荧光光谱差异的主要原因。研究了五味子的五种活性成分五味子醇甲、五味子酯甲、五味子甲素、五味子乙素和安五脂素的荧光性质和五味子以及护肝片乙醇提取液的荧光光谱,并用高效液相色谱测定了供试品五种活性成分的含量。研究表明：发光效率按安五脂素、五味子乙素、五味子甲素和五味子醇甲依次减弱,五味子酯甲不具有荧光性;北五味子的主要荧光物质为五味子乙素,而南五味子的主要荧光物质是安五脂素,它们是导致南北五味子荧光光谱差异的主要原因。用荧光法鉴别南北五味子具有简单、快速和灵敏的特点     

Analysis of Schisandra chinensis and Schisandra sphenanthera

Wuweizi (Fructus Schisandrae) is classified in traditional Chinese medicine as a superior drug, and has been used for thousands of years. Modern pharmacological research has demonstrated that most of the biological actions and pharmacological effects of Wuweizi can be attributed to its lignan constituents, particularly the dibenzocyclooctadiene-type lignans, which can lower the serum glutamate-pyruvate transaminase (SGPT) level, inhibit platelet aggregation, and show antioxidative, calcium antagonism, antitumor-promoting, and anti-HIV (human immunodeficiency virus) effects. The dried ripe fruits of both Schisandra chinensis and Schisandra sphenanthera have long been used as Wuweizi, although their chemical constituents and contents of the bioactive components are quite different. Since 2000, they have been accepted as two different crude drugs, Bei-Wuweizi and Nan-Wuweizi, respectively, by the Chinese Pharmacopoeia. In order to provide a useful reference for good quality control of Wuweizi, many studies on the chemical constituents, pharmacological effects, identification and quality control methods of the two drugs have been reported in the literature and are summarized herein. Particular attention was given to the different methodologies developed for the qualitative and quantitative analysis of the major bioactive lignans. In our opinion, thin-layer chromatography (TLC) is the most simple and convenient method for identification of these two crude drugs, and high-performance liquid chromatography with UV detection (HPLC-UV) is the preferred method for quantitative analysis based on the bioactive lignans. Some newly developed methods, particularly hyphenated chromatographic-analytical techniques, are effective in determination of the lignans that occur in low content and those difficult to be fully separated with HPLC.     

超声细胞粉碎萃取结合超高效液相色谱用于六味地黄丸的整体分析（英文）

针对中药复方制剂六味地黄丸的质量控制提出了一种多指标全药材整体分析新策略。从组成六味地黄丸的每一味药材中选取1~2个药效成分,即选取熟地黄中的毛蕊花糖苷、山茱萸中的莫诺苷和马钱苷、牡丹皮中的丹皮酚和芍药苷、山药中的尿囊素、茯苓中的茯苓酸、泽泻中的23-乙酰泽泻醇B作为六味地黄丸的质量控制指标成分,采用快速、简便、高效的超声细胞粉碎提取(UCGE)法对这8个指标成分进行同步提取。用响应曲面分析中的Box-Behnken模式对UCGE提取过程中对提取效率影响较大的料液比、提取时间和提取温度等参数进行了优化。得到最优的提取条件:料液比1∶45(g/mL)、提取时间40 min、提取温度20℃。进一步利用超高效液相色谱-二极管阵列检测(UPLC-PAD)技术实现多指标成分在同一根色谱柱上的同步分离和检测,从而建立六味地黄丸的多指标全药材整体色谱。采用HSS T3色谱柱(50 mm×2.1 mm,1.8μm),以乙腈-水为流动相进行梯度洗脱,基于指标成分的紫外光谱特征选择5个检测波长同时检测,并进行了线性关系、检出限、定量限、精密度、稳定性、重复性、准确性等方法学验证。该研究为六味地黄丸质量标准的建立提供了依据,同时也为中药复方制剂提供了一种质量控制新模式和新理念。     

High-Throughput Structural Elucidation of Lignans in Flaxseed by High-Performance Liquid Chromatography Coupled with Electrospray Ionization Mass Spectrometry

Methods based on high-performance liquid chromatography coupled with mass spectrometry and quadrupole time-of-flight mass spectrometry were developed for the rapid identification of lignans in flaxseed. The lignans were extracted from dried flaxseed extract power by ultrasonic extraction. The fragment ions were further investigated for structural elucidation and the MS/MS spectra provided an abundance of structural information for the identification. A total of eleven lignans were investigated and three were new compounds. This research demonstrates the rapid characterization of bioactive constituents in plant extracts while avoiding tedious and difficult separation and purification steps.     

Rapid characterization of the chemical constituents of Cortex Fraxini by homogenate extraction followed by UHPLC coupled with Fourier transform ion cyclotron resonance mass spectrometry and GC–MS

Cortex Fraxini is an important traditional Chinese medicine. In this work, a rapid and reliable homogenate extraction method was applied for the fast extraction for Cortex Fraxini, and the method was optimized by response surface methodology. Ultra high performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry and gas chromatography with mass spectrometry were established for the separation and characterization of the constituents of Cortex Fraxini. Liquid chromatography separation was conducted on a C₁₈ column (150 mm × 2.1 mm, 1.8 μm), and gas chromatography separation was performed on a capillary with a 5% phenyl‐methylpolysiloxane stationary phase (30 m × 0.25 mm × 0.25 mm) by injection of silylated samples. According to the results, 33 chemical compounds were characterized by liquid chromatography with mass spectrometry, and 11 chemical compounds were characterized by gas chromatography with mass spectrometry, and coumarins were the major components characterized by both gas chromatography with mass spectrometry and liquid chromatography with mass spectrometry. The proposed homogenate extraction was an efficient and rapid method, and coumarins, phenylethanoid glycosides, iridoid glycosides, phenylpropanoids, and lignans were the main constituents of Cortex Fraxini. This work laid the foundation for further study of Cortex Fraxini and will be helpful for the rapid extraction and characterization of ingredients in other traditional Chinese medicines.     

Chemical Constituents and Antibacterial and Antifungal Activities of Two Aglaia Species

In the course of searching bioactive natural products from the plant genus Aglaia, we selected two species, A. cordata and A. testicularis, for further chemical study. Totally twenty natural compounds were obtained and structurally elucidated with which eleven of them were discovered for the first time. Among these compounds, lignans, rocaglamides,aglains and bisamides were the main constituents of the two plant species. The results from a bioactive screening indicated that some of the lignans possess potent antibacterial and antifungal activity.     

New Eremophilane Sesquiterpenes from Cacalia ainsliaeflora

Cacalia ainsliaeflora, a compositae distributed in the west of China, has long been used as Chinese traditional medicine for invigorating the circulation of blood, curing pellagra, rheumatismal edema and as an insecticide. [1] We recently reported the isolation and identification of five eremophilane sesquiterpenes from this plant. [2] In our continuing research on the bioactive constituents from Cacalia species, we reinvestigated the chemical constituents of the roots of C. ainsliaeflora. As a result, seven new eremophilane sesquiterpenes (2 ～ 8), and a known erempphilanolide (1) were isolated. Their structures were elucidated by spectroscopic methods.     

Inhibitory Activities on α-Glucosidase and Composition Analysis of Different Fractions of Ethanol Extracts from Actinidia chinensis Radix

Tlie inhibitory actions of ethyl acetate,n-butanol and water fractions from Actinidia chinensis Radix (A. chinensis Radix) ethanol extracts on glucosidase were investigated. We found that the inhibitory activity of different ethanol extract fractions on α-glucosidase is concentration-dependent. At the same concentration, the ethyl acetate and n-butaiiol fractions showed higher inliibitory activities on gglucosidase in comparison witli acarbose. We then determined the chemical constituents of tlie ethyl acetate and n-butanol fractions through ultra performance liquid cliromatography-triple-time of flight/mass spectrometry(UPLC-Triple-TOF/MS). Based on the mass spectrometry analysis and the databases Scitinder and Reaxys, 21 compoiinds(A1-A21) were identified from the ethyl acetate fraction. In addition, 11 of those compounds(A2, A3, A5, A6, A8, A10, A11, A13, A15, A19, A20) were identified for the first time from A. chinensis Radix. We also identified 14 compounds(A22-A32 and A4-A6) from tlie w-butanol fraction and compound A29 is a new natural product. From the n-butanol fraction, 7 additional compounds (A22, A25, A27, A28, A30-A32) were identified from A. chinensis Radix for the first time.     

Chemical Constituent Analysis of Ranunculus sceleratus L. Using Ultra-High-Performance Liquid Chromatography Coupled with Quadrupole-Orbitrap High-Resolution Mass Spectrometry

Ranunculus sceleratus L.(RS) has shown various pharmacological effects in traditional Chinese medicine. In our previous study, the positive therapeutic effect on α-naphthylisothiocyanate induced intrahepatic cholestasis in rats was obtained using TianJiu treatment with fresh RS. However, the chemical profile of RS has not been clearly clarified, which impedes the research progress on the therapeutic effect of RS. Herein, an ultra-high performance liquid chromatography coupled with quadrupole Orbitrap high-resolution mass spectrometry (UHPLC-Q-Orbitrap HRMS) method was developed to rapidly separate and identify multiple constituents in the 80% methanol extract of RS. A total of sixty-nine compounds (19 flavonoids, 22 organic acids, 6 coumarins, 4 lignans, 14 nitrogenous compounds, and 4 anthraquinones) were successfully characterized. A total of 12 of these compounds were unambiguously identified by standard samples. Their mass spectrometric fragmentation pathways were investigated. It is worth noting that flavonoids and lignans were identified for the first time in RS. In this study, we successfully provide the first comprehensive report on identifying major chemical constituents in RS by UHPLC-Q-Orbitrap HRMS. The obtained results enrich the RS chemical profile, paving the way for further phytochemical study, quality control, and pharmacological investigation of RS.     

水果蔬菜中多种杀菌剂的基质固相分散液相色谱测定方法研究

采用基质固相分散(MSPD)代替液液分配和固相萃取,从蔬菜水果中提取、净化10种常用杀菌剂农药残留,用C18硅胶交联剂作为固相吸附剂,乙酸乙酯作为洗脱液,用HPLC/PDA和LC-MS进行分析检测。10种杀菌剂在0.5~5 mg/kg含量的添加回收率在65%~110%之间,相对标准偏差小于10%,使用HPLC、PDA和LC-MS的检出限分别在0.02~0.2 mg/kg和0.002~0.01 mg/kg之间。该方法节省溶剂,提取和净化一步完成,适用于新鲜水果和蔬菜中10种杀菌剂的残留分析。     

Quality evaluation of Eucommiae Cortex processed by different methods and “sweating” conditions based on simultaneous determination of multiple bioactive constituents combined with gray relational analysis

Eucommiae Cortex is a classical traditional Chinese medicine, which needs to be processed by “sweating” methods. To select the suitable processing method and “sweating” processing condition for Eucommiae Cortex, in this study, the quality of Eucommiae Cortex was evaluated based on simultaneous determination of multiple bioactive constituents combined with gray relational analysis. The contents of lignans, iridoids, penylpropanoids, flavonoids, and phenols in samples were simultaneously determined using ultra‐fast performance liquid chromatography coupled with triple quadrupole‐linear ion trap tandem mass spectrometry. The chromatographic separation was performed on a Synergiۛ Hydro‐RP 100 Å column (100 mm × 2.0 mm, 2.5 μm) at 30°C with a gradient elution of acetonitrile with 0.1% formic acid/0.1% aqueous formic acid as the mobile phase. Furthermore, gray relational analysis was performed to evaluate and sort the samples according to the contents of 14 constituents by calculating the relative correlation degree of each sample. The results demonstrated that the quality of Eucommiae Cortex “sweating” at source area was better and the better “sweating” condition was to scrape off the cork layer before “sweating” with straw covering and sun drying. The developed method could provide the foundation and support for “sweating” processing method of Eucommiae Cortex in normalization and standardization.