Recent development in mass spectrometry and its hyphenated techniques for the analysis of medicinal plants.

INTRODUCTION Medicinal plants are gaining increasing attention worldwide due to their empirical therapeutic efficacy and being a huge natural compound pool for new drug discovery and development. The efficacy, safety and quality of medicinal plants are the main concerns, which are highly dependent on the comprehensive analysis of chemical components in the medicinal plants. With the advances in mass spectrometry (MS) techniques, comprehensive analysis and fast identification of complex phytochemical components have become feasible, and may meet the needs, for the analysis of medicinal plants. OBJECTIVE Our aim is to provide an overview on the latest developments in MS and its hyphenated technique and their applications for the comprehensive analysis of medicinal plants. METHODOLOGY Application of various MS and its hyphenated techniques for the analysis of medicinal plants, including but not limited to one-dimensional chromatography, multiple-dimensional chromatography coupled to MS, ambient ionisation MS, and mass spectral database, have been reviewed and compared in this work. RESULTS Recent advancs in MS and its hyphenated techniques have made MS one of the most powerful tools for the analysis of complex extracts from medicinal plants due to its excellent separation and identification ability, high sensitivity and resolution, and wide detection dynamic range. CONCLUSION To achieve high-throughput or multi-dimensional analysis of medicinal plants, the state-of-the-art MS and its hyphenated techniques have played, and will continue to play a great role in being the major platform for their further research in order to obtain insight into both their empirical therapeutic efficacy and quality control.

[1]  Rawi Ramautar,et al.  CE–MS for metabolomics: Developments and applications in the period 2014–2016 , 2016, Electrophoresis.

[2]  Claude Roux,et al.  Forensic applications of desorption electrospray ionisation mass spectrometry (DESI-MS). , 2013, Forensic science international.

[3]  F. Fernández,et al.  Ambient mass spectrometry in metabolomics. , 2017, The Analyst.

[4]  R. Cooks,et al.  Direct analysis of camptothecin from Nothapodytes nimmoniana by desorption electrospray ionization mass spectrometry (DESI-MS). , 2011, The Analyst.

[5]  J. Wiseman,et al.  Direct analysis of Salvia divinorum leaves for salvinorin A by thin layer chromatography and desorption electrospray ionization multi-stage tandem mass spectrometry. , 2010, Rapid communications in mass spectrometry : RCM.

[6]  Sebastian Böcker,et al.  Computational mass spectrometry for small molecules , 2013, Journal of Cheminformatics.

[7]  Yi-Tong Wang,et al.  Acid/Salt/pH Gradient Improved Resolution and Sensitivity in Proteomics Study Using 2D SCX-RP LC-MS. , 2017, Journal of proteome research.

[8]  Liang Liu,et al.  Metabolites Software-Assisted Flavonoid Hunting in Plants Using Ultra-High Performance Liquid Chromatography-Quadrupole-Time of Flight Mass Spectrometry , 2015, Molecules.

[9]  Kristof Engelen,et al.  Insights into the Role of the Berry-Specific Ethylene Responsive Factor VviERF045 , 2016, Frontiers in plant science.

[10]  Ye Li,et al.  Direct Analysis in Real-time Mass Spectrometry for Rapid Identification of Traditional Chinese Medicines with Coumarins as Primary Characteristics. , 2017, Phytochemical analysis : PCA.

[11]  P. Marriott,et al.  Multidimensional gas chromatography in food analysis , 2017 .

[12]  Mingquan Guo,et al.  Current Advances in the Metabolomics Study on Lotus Seeds , 2016, Front. Plant Sci..

[13]  Jianjun Li,et al.  Advances in coupling microfluidic chips to mass spectrometry. , 2015, Mass spectrometry reviews.

[14]  Jentaie Shiea,et al.  Ambient ionization mass spectrometry: a tutorial. , 2011, Analytica chimica acta.

[15]  P. Marriott,et al.  Two-dimensional retention indices improve component identification in comprehensive two-dimensional gas chromatography of saffron. , 2015, Analytical chemistry.

[16]  Hong Wang,et al.  Rapid screening of transferrin-binders in the flowers of Bauhinia blakeana Dunn by on-line high-performance liquid chromatography-diode-array detector-electrospray ionization-ion-trap-time-of-flight-mass spectrometry-transferrin-fluorescence detection system. , 2016, Journal of chromatography. A.

[17]  J. Tam,et al.  A novel strategy for the discrimination of gelatinous Chinese medicines based on enzymatic digestion followed by nano-flow liquid chromatography in tandem with orbitrap mass spectrum detection , 2015, International journal of nanomedicine.

[18]  Kazuki Saito,et al.  Modern plant metabolomics: advanced natural product gene discoveries, improved technologies, and future prospects. , 2015, Natural product reports.

[19]  Yu Bai,et al.  Direct Analysis in Real Time Mass Spectrometry: a Powerful Tool for Fast Analysis , 2015 .

[20]  Bin Hu,et al.  Fast Screening of Authentic Ginseng Products by Surface Desorption Atmospheric Pressure Chemical Ionization Mass Spectrometry , 2012, Planta Medica.

[21]  T. V. van Beek,et al.  Hyphenation of optimized microfluidic sample preparation with nano liquid chromatography for faster and greener alkaloid analysis. , 2013, Analytica chimica acta.

[22]  Ying-Ning Ho,et al.  Imaging mass spectrometry for metabolites: technical progress, multimodal imaging, and biological interactions , 2017, Wiley interdisciplinary reviews. Systems biology and medicine.

[23]  R. Cooks,et al.  Direct analysis of Stevia leaves for diterpene glycosides by desorption electrospray ionization mass spectrometry. , 2009, The Analyst.

[24]  Jiewei Deng,et al.  Analysis of pharmaceutical products and herbal medicines using ambient mass spectrometry , 2016 .

[25]  H. Rogers,et al.  Use of TD-GC–TOF-MS to assess volatile composition during post-harvest storage in seven accessions of rocket salad (Eruca sativa) , 2016, Food chemistry.

[26]  Mingquan Guo,et al.  Phenolic Profiling of Duchesnea indica Combining Macroporous Resin Chromatography (MRC) with HPLC-ESI-MS/MS and ESI-IT-MS , 2015, Molecules.

[27]  R. Cooks,et al.  Mass Spectrometry Sampling Under Ambient Conditions with Desorption Electrospray Ionization , 2004, Science.

[28]  Shuying Liu,et al.  Rapid identification of traditional Chinese herbal medicine by direct analysis in real time (DART) mass spectrometry. , 2014, Analytica chimica acta.

[29]  Charles C. Liu,et al.  Rapid determination of 1-deoxynojirimycin in Morus alba L. leaves by direct analysis in real time (DART) mass spectrometry. , 2015, Journal of pharmaceutical and biomedical analysis.

[30]  I. Elmi,et al.  Conventional and enantioselective gas chromatography with microfabricated planar columns for analysis of real-world samples of plant volatile fraction. , 2016, Journal of chromatography. A.

[31]  F Haghighi,et al.  Through the years with on-a-chip gas chromatography: a review. , 2015, Lab on a chip.

[32]  Emmanuel Mikros,et al.  Recent advances and new strategies in the NMR-based identification of natural products. , 2014, Current opinion in biotechnology.

[33]  A. Aharoni,et al.  More than Pictures: When MS Imaging Meets Histology. , 2016, Trends in plant science.

[34]  Sebastian Böcker,et al.  Computational mass spectrometry for small-molecule fragmentation , 2014 .

[35]  B. Vaz,et al.  The Spatial Distribution of Alkaloids in Psychotria prunifolia (Kunth) Steyerm and Palicourea coriacea (Cham.) K. Schum Leaves Analysed by Desorption Electrospray Ionisation Mass Spectrometry Imaging. , 2018, Phytochemical analysis : PCA.

[36]  H. Stuppner,et al.  Mass spectrometry and NMR spectroscopy: modern high-end detectors for high resolution separation techniques--state of the art in natural product HPLC-MS, HPLC-NMR, and CE-MS hyphenations. , 2013, Natural product reports.

[37]  Steven Ray Wilson,et al.  Nano-LC in proteomics: recent advances and approaches. , 2015, Bioanalysis.

[38]  Mingquan Guo,et al.  Flavonoids of Lotus (Nelumbo nucifera) Seed Embryos and Their Antioxidant Potential. , 2017, Journal of food science.

[39]  M. Maldini,et al.  Variability of chemical composition and antioxidant activity of essential oils between Myrtus communis var. Leucocarpa DC and var. Melanocarpa DC. , 2016, Food chemistry.

[40]  Aurélien Thomas,et al.  Current approaches and challenges for the metabolite profiling of complex natural extracts. , 2015, Journal of chromatography. A.

[41]  Jesús Martín,et al.  Combined LC/UV/MS and NMR Strategies for the Dereplication of Marine Natural Products , 2016, Planta Medica.

[42]  L. Mondello,et al.  Performance evaluation of a versatile multidimensional chromatographic preparative system based on three-dimensional gas chromatography and liquid chromatography-two-dimensional gas chromatography for the collection of volatile constituents. , 2015, Journal of chromatography. A.

[43]  Emma L. Schymanski,et al.  Mass spectral databases for LC/MS- and GC/MS-based metabolomics: state of the field and future prospects , 2016 .

[44]  Xu Zhou,et al.  Current mass spectrometry approaches and challenges for the bioanalysis of traditional Chinese medicines. , 2016, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[45]  Z. Yao,et al.  Direct analysis of traditional Chinese medicines by mass spectrometry. , 2016, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[46]  Yu Jin,et al.  Combination of off-line two-dimensional hydrophilic interaction liquid chromatography for polar fraction and two-dimensional hydrophilic interaction liquid chromatography×reversed-phase liquid chromatography for medium-polar fraction in a traditional Chinese medicine. , 2012, Journal of chromatography. A.

[47]  Shengli Han,et al.  Overview of online two-dimensional liquid chromatography based on cell membrane chromatography for screening target components from traditional Chinese medicines. , 2017, Journal of separation science.

[48]  R. Cooks,et al.  Rapid in situ detection of alkaloids in plant tissue under ambient conditions using desorption electrospray ionization. , 2005, The Analyst.

[49]  T. Hankemeier,et al.  Lab-on-a-Chip hyphenation with mass spectrometry: strategies for bioanalytical applications. , 2015, Current opinion in biotechnology.

[50]  Xuan Ding,et al.  Development of APTES-Decorated HepG2 Cancer Stem Cell Membrane Chromatography for Screening Active Components from Salvia miltiorrhiza. , 2016, Analytical chemistry.

[51]  Jian-Bo Wan,et al.  Application of two-dimensional chromatography in the analysis of Chinese herbal medicines. , 2014, Journal of chromatography. A.

[52]  Shilin Chen,et al.  Recent developments in qualitative and quantitative analysis of phytochemical constituents and their metabolites using liquid chromatography-mass spectrometry. , 2012, Journal of pharmaceutical and biomedical analysis.

[53]  Wen Gao,et al.  Affinity selection-based two-dimensional chromatography coupled with high-performance liquid chromatography-mass spectrometry for discovering xanthine oxidase inhibitors from Radix Salviae Miltiorrhizae , 2014, Analytical and Bioanalytical Chemistry.

[54]  R. Musah,et al.  Plant seed species identification from chemical fingerprints: a high-throughput application of direct analysis in real time mass spectrometry. , 2015, Analytical chemistry.

[55]  Liang Liu,et al.  Rapid identification of new minor chemical constituents from Smilacis Glabrae Rhizoma by combined use of UHPLC-Q-TOF-MS, preparative HPLC and UHPLC-SPE-NMR-MS techniques. , 2015, Phytochemical analysis : PCA.

[56]  Lars Ridder,et al.  Automatic chemical structure annotation of an LC-MS(n) based metabolic profile from green tea. , 2013, Analytical chemistry.

[57]  E. Čellárová,et al.  Interspecific variation in localization of hypericins and phloroglucinols in the genus Hypericum as revealed by desorption electrospray ionization mass spectrometry imaging. , 2016, Physiologia plantarum.

[58]  R. Cody,et al.  Versatile new ion source for the analysis of materials in open air under ambient conditions. , 2005, Analytical chemistry.

[59]  A. Venter,et al.  Mechanisms of real-time, proximal sample processing during ambient ionization mass spectrometry. , 2014, Analytical chemistry.

[60]  L. Mondello,et al.  Rapid collection and identification of a novel component from Clausena lansium Skeels leaves by means of three-dimensional preparative gas chromatography and nuclear magnetic resonance/infrared/mass spectrometric analysis. , 2013, Analytica chimica acta.

[61]  Mingquan Guo,et al.  Analysis of Flavonoids in Lotus (Nelumbo nucifera) Leaves and Their Antioxidant Activity Using Macroporous Resin Chromatography Coupled with LC-MS/MS and Antioxidant Biochemical Assays , 2015, Molecules.

[62]  L. Mondello,et al.  Improving the productivity of a multidimensional chromatographic preparative system by collecting pure chemicals after each of three chromatographic dimensions. , 2016, Journal of Chromatography A.

[63]  Zhimou Guo,et al.  Recent development in liquid chromatography stationary phases for separation of Traditional Chinese Medicine components. , 2016, Journal of pharmaceutical and biomedical analysis.

[64]  P. Mohana Kumara,et al.  Ambient ionization mass spectrometry imaging of rohitukine, a chromone anti-cancer alkaloid, during seed development in Dysoxylum binectariferum Hook.f (Meliaceae). , 2015, Phytochemistry.

[65]  Luigi Mondello,et al.  Comprehensive two-dimensional gas chromatography-mass spectrometry: Recent evolution and current trends. , 2016, Mass spectrometry reviews.

[66]  S. Ohla,et al.  Chip-based separation devices coupled to mass spectrometry. , 2012, Current opinion in chemical biology.

[67]  Brijesh Kumar,et al.  Rapid fingerprinting of Rauwolfia species using direct analysis in real time mass spectrometry combined with principal component analysis for their discrimination , 2015 .

[68]  Jentaie Shiea,et al.  Ambient ionization mass spectrometry. , 2010, Annual review of analytical chemistry.

[69]  R. Cooks,et al.  Direct analysis of steviol glycosides from Stevia leaves by ambient ionization mass spectrometry performed on whole leaves. , 2012, The Analyst.

[70]  Xi-jun Wang,et al.  UHPLC-MS for the analytical characterization of traditional Chinese medicines , 2014 .

[71]  A. Venter,et al.  Ambient ionization mass spectrometry: real-time, proximal sample processing and ionization , 2017 .

[72]  Dinesh Kumar Nuclear Magnetic Resonance (NMR) Spectroscopy For Metabolic Profiling of Medicinal Plants and Their Products , 2016, Critical reviews in analytical chemistry.

[73]  R. Cooks,et al.  Chemical aspects of the extractive methods of ambient ionization mass spectrometry. , 2013, Annual review of physical chemistry.

[74]  Prabha Dwivedi,et al.  Mass spectrometry: recent advances in direct open air surface sampling/ionization. , 2013, Chemical reviews.

[75]  A. Jarmusch,et al.  Emerging capabilities of mass spectrometry for natural products. , 2014, Natural product reports.

[76]  Xin Lu,et al.  Metabolic Profiling with Gas Chromatography-Mass Spectrometry and Capillary Electrophoresis-Mass Spectrometry Reveals the Carbon-Nitrogen Status of Tobacco Leaves Across Different Planting Areas. , 2016, Journal of proteome research.

[77]  M. Sjerps,et al.  Forensic potential of comprehensive two-dimensional gas chromatography , 2016 .

[78]  S. Heinisch,et al.  Two‐dimensional liquid chromatography in pharmaceutical analysis. Instrumental aspects, trends and applications , 2017, Journal of pharmaceutical and biomedical analysis.

[79]  Na Li,et al.  Metabolomic profiling delineate taste qualities of tea leaf pubescence. , 2017, Food research international.

[80]  S. Ceccarelli,et al.  LC-SPE-NMR-MS: a total analysis system for bioanalysis. , 2009, Bioanalysis.

[81]  Jacques Vervoort,et al.  LC-UV-solid-phase extraction-NMR-MS combined with a cryogenic flow probe and its application to the identification of compounds present in Greek oregano. , 2003, Analytical chemistry.