綜述植物化學成分及其代謝物的定性和定量分析.doc

Recent developments in qualitative and quantitative analysis of phytochemical constituents and their metabolites using liquid chromatographymass spectrometry Haifeng Wua, , Jian Guob, , Shilin Chena, , Xin Liuc, , Yan Zhoud, , Xiaopo Zhanga, , Xudong Xua, , a Institute of Medicinal Plant Development, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100193, PR China b Department of DMPK, AstraZeneca Pharmaceuticals, 35 Gatehouse Drive, Waltham, MA 02451, USA c Beijing Entry-Exit Inspection and Quarantine Bureau, Beijing 100026, PR China d Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041, PR ChinaCorresponding author at: Institute of Medicinal Plant Development, Chinese Academy of Medical Sciences and Peking Union Medical College, No.151, Malianwa North Road, Haidian District, Beijing 100193, PR China. Tel.: +86 10 5783 3296; fax: +86 10 5783 3296.Received 14 May 2012Revised 30 August 2012Accepted 2 September 2012Available online 11 September 2012 http:/dx.doi.org/10.1016/j.jpba.2012.09.004, How to Cite or Link Using DOI Permissions & ReprintsView full text Purchase$31.501. Introduction2. Qualitative analysis3. Quantitative analysis4. Application of LCMS in fingerprinting analysis5. ConclusionsAcknowledgmentsReferencesAbstractOver the past few years, the applications of liquid chromatography coupled with mass spectrometry (LCMS) in natural product analysis have been dramatically growing because of the increasingly improved separation and detection capabilities of LCMS instruments. In particular, novel high-resolution hybrid instruments linked to ultra-high-performance LC and the hyphenations of LCMS with other separation or analytical techniques greatly aid unequivocal identification and highly sensitive quantification of natural products at trace concentrations in complex matrices. With the aim of providing an up-to-date overview of LCMS applications on the analysis of plant-derived compounds, papers published within the latest years (20072012) involving qualitative and quantitative analysis of phytochemical constituents and their metabolites are summarized in the present review. After briefly describing the general characteristics of natural products analysis, the most remarkable features of LCMS and sample preparation techniques, the present paper mainly focuses on screening and characterization of phenols (including flavonoids), alkaloids, terpenoids, steroids, coumarins, lignans, and miscellaneous compounds in respective herbs and biological samples, as well as traditional Chinese medicine (TCM) prescriptions using tandem mass spectrometer. Chemical fingerprinting analysis using LCMS is also described. Meanwhile, instrumental peculiarities and methodological details are accentuated.Keywords Liquid chromatography; Mass spectrometry; Medicinal plants; Traditional Chinese medicine; Fingerprinting抽象在過去的幾年中，液相色譜與質譜聯(lián)用（LC-MS）在天然產物分析的應用都得到了顯著增長，因為日益提高的分離和檢測能力的LC-MS儀器。特別是，新穎的高分辨率混合工具與其他分離或分析技術鏈接到超高性能LC的LC-MS和斷字大大有助于在復雜基質中的微量濃度的明確識別和天然產品的高度敏感的定量。提供最新的植物性化合物的分析概述LC-MS應用的目的，論文發(fā)表在最近幾年（2007-2012年），涉及的植物化學成分及其代謝物的定性和定量分析總結在本次審查中。在簡要說明天然產物的分析，最顯著的特點LC-MS和樣品制備技術的一般特點，本論文主要集中在酚類物質（包括類黃酮），生物堿，萜類化合物，類固醇，香豆素，木脂素類化合物的篩選和鑒定，和雜項在各自的草藥化合物和生物樣品，以及中國傳統(tǒng)醫(yī)學（中醫(yī)）處方使用串聯(lián)質譜儀?；瘜W指紋分析用LC-MS也被描述。同時，儀器的特點和方法的細節(jié)突出。Figures and tables from this article:Fig. 1.Chemical structures of caged xanthones (115) identified from G. hanburyi.Reproduced with permission from 89. 氧雜蒽酮的化學結構（1-15）確定Figure options View in workspaceFig. 2.UHPLCMS chromatograms of the standard xanthones and the crude extracts of G. hanburyi. (A) UHPLC chromatograms of 12 standard xanthones, (B) TIC of the 12 standard xanthones, (C) UHPLC chromatograms of the crude extracts of G. hanburyi, (D) TIC of the crude extracts of G. hanburyi. 。2。UHPLC-MS色譜圖的標準呫噸酮和G. hanburyi粗提物中。 （A）（B）UHPLC色譜圖的12個標準氧雜蒽酮，TIC的12個標準氧雜蒽酮（C）UHPLC色譜G. hanburyi粗提物中，（D）議會的粗提物的G. hanburyi。Reproduced with permission from 89.Figure options View in workspaceFig. 3.(A) MS/MS spectra of isogambogenin (13) of selected M+H+ at m/z 615, (B) MS/MS/MS spectra of selected ion at m/z 491 from m/z 615, (C) MS/MS spectra of isomorellinol (14) of selected M+H+ at m/z 547, (D) MS/MS/MS spectra of selected ion at m/z 461 from m/z 547, (E) MS/MS spectra of compound 15 of selected M+H+ at m/z 545, (F) MS/MS/MS spectra of selected ion at m/z 461 from m/z 545 (collision energy at 30eV).圖。3。（A）MS /，MS譜isogambogenin（13）選定的M+ H + m / z為615，（B）選擇離子從m / z615，m / z為491 MS / MS / MS譜（C）MS / MS，光譜isomorellinol（14）選擇M+ H + m / z為547（D）MS / MS / MS譜的選擇離子為m / z461 M / Z547，（E）MS/ MS譜的化合物15，所選的M + H+為m/ z545（F）MS / MS/ MS譜圖，從m / z545（碰撞能量30 eV的選擇離子為m / z461）。Reproduced with permission from 89.Figure options View in workspaceFig. 4.Proposed fragment pathways of M+H+ for: (A) isogambogenin (13), (B) isomorellinol (14), (C) 15.Reproduced with permission from 89.Figure options View in workspaceFig. 5.HSCCC chromatogram of gamboge extract (190mg). Fraction I (17.26mg), fr. II (5.48mg), fr. III (3.81mg), fr. IV (3.56mg), fr. V (7.66mg), fr. VI (3.21mg), fr. VII (8.21mg), fr. VIII (35.25mg), fr. IX (76.78mg), fr. X (6.04mg), fr. XI (4.34mg).Reproduced with permission from 92.圖。4。已提議片段途徑的M + H+為：（A）isogambogenin（13），（B）isomorellinol（14），（C）15。轉載許可89。Figure options View in workspaceFig. 6.Scheme of the HPLC on-line coupled to ESI-MS and DPPH assay. The arrows indicate flow directions.圖。6。計劃的HPLC上線耦合到：ESI-MS法和DPPH。箭頭表示流動方向。Reproduced with permission from 95.Figure options View in workspaceFig. 7.The overview of the NMR/LCMS parallel dynamic spectroscopy (NMR/LCMS PDS) combined with an uncompleted separation strategy for simultaneous structure identification of natural products in crude extract.圖。 7。未完成的同時進行結構鑒定天然產物粗提物中分離策略，結合NMR/ LC-MS，并行動態(tài)光譜儀（NMR / LC-MS PDS）的概述。Reproduced with permission from 96.Figure options View in workspaceFig. 8.Proposed metabolic pathways for human liver phase 1 metabolism of isoliquiritigenin.圖。8。建議第1階段人類肝臟代謝，異甘草素的代謝途徑。Reproduced with permission from 100.Figure options View in workspaceFig. 9.The schematic diagram of VEGFR-CMC-on-line-LCMS system. UV: ultraviolet detector; DAD/MS: diode array detector/mass spectrometer detector; 1D CMC column: the VEGFR-CMC column playing as the first dimensional column. 2D analytical column: the VP-ODS column playing as the second dimensional column.圖。 9。VEGFR-CMC-線LC-MS系統(tǒng)的示意圖。 UV：紫外檢測器，DAD / MS：二極管陣列檢測/質譜法等檢測;一維CMC柱中：VEGFR-軍委縱隊打的第一維列。二維分析柱：VP-ODS柱打的第二維列。Reproduced with permission from 109.Figure options View in workspaceFig. 10.Framework for high-throughput screening of cardio-protective compounds from medicinal plant extracts.。10。從藥用植物提取物的保護心血管的化合物的高通量篩選的框架。Reproduced with permission from 155.Figure options View in workspaceFig. 11.UHPLCQTOF base peak intensity (BPI) chromatograms of six Meconopsis species for identification: (af) BPI of ESI (+) TOF-MS from M. torquata; M. racemosa; M. integrifolia; M. quintuplinervia; M. betonicifolia; M. horridula.圖。 11。UHPLC-QTOF基峰強度（BPI）色譜綠絨蒿物種識別：（A-F）BPI的ESI（+）TOF-MS從M. torquata; M.鵑，M. integrifolia，M. quintuplinervia，; M.betonicifolia; M. horridula。Reproduced with permission from 175.Figure options View in workspaceFig. 12.Structures assigned in the extracts of Meconopsis species.圖。 12。綠絨蒿屬物種的提取物中分配的結構。Reproduced with permission from 175.Figure options View in workspace