Expeditious discrimination of four species of the Panax genus using direct infusion-MS/MS combined with multivariate statistical analysis.

A practical approach based on direct infusion-MS/MS (DI-MS/MS) was demonstrated for metabolomic classification of four species in the Panax genus. The species Panax ginseng, Panax notoginseng, Panax quinquefolius and Panax vietnamensis were analyzed to develop an efficient tool for authenticating ginseng. Four target ions (m/z 783.5, 945.5, 1107.5 and 1149.2) were selected from LC-MS screening results for DI-MS/MS analysis. The target ions served as classifiers of the four species. As a targeted analysis, DI-MS/MS provided the structural identities of the target ions, clear spectral data and high sensitivity in a shorter time than routine LC-MS analysis. Principal component analysis and partial least squares-discriminant analysis of the DI-MS/MS fingerprinting revealed distinct grouping of the data. The results were validated by cross-validation and a permutation test to examine the utility of the statistical models. The spectral intensities of each species were compared with one another using box plots, which allowed straightforward authentication of the Panax species. The proposed method showed improved efficiency over other current methods for discrimination of large quantities of plant material. Additionally, to the best of our knowledge, this is the first study in which DI-MS/MS has been used to classify plant samples.

[1]  X. Wang,et al.  Determination of ginsenosides in plant extracts from Panax ginseng and Panax quinquefolius L. by LC/MS/MS. , 1999, Analytical chemistry.

[2]  Michael Edberg Hansen,et al.  A comparison of direct infusion MS and GC-MS for metabolic footprinting of yeast mutants. , 2007, Biotechnology and bioengineering.

[3]  Lothar Willmitzer,et al.  High-resolution direct infusion-based mass spectrometry in combination with whole 13C metabolome isotope labeling allows unambiguous assignment of chemical sum formulas. , 2008, Analytical chemistry.

[4]  Lian‐Wen Qi,et al.  Diagnostic ion filtering to characterize ginseng saponins by rapid liquid chromatography with time-of-flight mass spectrometry. , 2012, Journal of chromatography. A.

[5]  E. Simó-Alfonso,et al.  Classification of vegetable oils according to their botanical origin using amino acid profiles established by direct infusion mass spectrometry. , 2007, Rapid communications in mass spectrometry : RCM.

[6]  N. Fuzzati.  Analysis methods of ginsenosides. , 2004, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[7]  S. Kwon,et al.  Comparison of primary and secondary metabolites for suitability to discriminate the origins of Schisandra chinensis by GC/MS and LC/MS. , 2013, Food chemistry.

[8]  W. Maccrehan,et al.  Simplified ultrasonically- and microwave-assisted solvent extractions for the determination of ginsenosides in powdered Panax ginseng rhizomes using liquid chromatography with UV absorbance or electrospray mass spectrometric detection , 2013, Analytical and Bioanalytical Chemistry.

[9]  C. Becker,et al.  Quantification of proteins and metabolites by mass spectrometry without isotopic labeling. , 2007, Methods in molecular biology.

[10]  A. Calafat,et al.  Quantification of 22 phthalate metabolites in human urine. , 2007, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[11]  P. Mielke,et al.  Permutation Methods: A Distance Function Approach , 2007 .

[12]  J. V. Sancho,et al.  Metabolomic approaches for orange origin discrimination by ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry. , 2014, Food chemistry.

[13]  Jizhong Yan,et al.  Profiling the ginsenosides of three ginseng products by LC-Q-TOF/MS. , 2013, Journal of food science.

[14]  Lian-Wen Qi,et al.  Isolation and analysis of ginseng: advances and challenges. , 2011, Natural product reports.

[15]  Matej Oresic,et al.  MZmine 2: Modular framework for processing, visualizing, and analyzing mass spectrometry-based molecular profile data , 2010, BMC Bioinformatics.

[16]  M. Gershwin,et al.  Quantitative determination of ginsenosides by high-performance liquid chromatography-tandem mass spectrometry. , 2001, Phytochemical analysis : PCA.

[17]  W. Dunn,et al.  Evaluation of automated electrospray-TOF mass spectrometryfor metabolic fingerprinting of the plant metabolome , 2005, Metabolomics.

[18]  Hwee-Ling Koh,et al.  Ultra-performance liquid chromatography/time-of-flight mass spectrometry based metabolomics of raw and steamed Panax notoginseng. , 2007, Rapid communications in mass spectrometry : RCM.

[19]  J A Kirwan,et al.  Characterising and correcting batch variation in an automated direct infusion mass spectrometry (DIMS) metabolomics workflow , 2013, Analytical and Bioanalytical Chemistry.

[20]  K. H. Laursen,et al.  Discrimination of conventional and organic white cabbage from a long-term field trial study using untargeted LC-MS-based metabolomics , 2014, Analytical and Bioanalytical Chemistry.

[21]  Y. Choi,et al.  Quality control of herbal material and phytopharmaceuticals with MS and NMR based metabolic fingerprinting. , 2009, Planta medica.

[22]  David S. Wishart,et al.  MetaboAnalyst: a web server for metabolomic data analysis and interpretation , 2009, Nucleic Acids Res..

[23]  Royston Goodacre,et al.  Application of high-throughput Fourier-transform infrared spectroscopy in toxicology studies: contribution to a study on the development of an animal model for idiosyncratic toxicity. , 2004, Toxicology letters.

[24]  Xiaomei Yan,et al.  Direct infusion mass spectrometry or liquid chromatography mass spectrometry for human metabonomics? A serum metabonomic study of kidney cancer. , 2010, The Analyst.

[25]  T. Annesley.  Ion suppression in mass spectrometry. , 2003, Clinical chemistry.

[26]  David I. Ellis,et al.  Metabolic fingerprinting in disease diagnosis: biomedical applications of infrared and Raman spectroscopy. , 2006, The Analyst.

[27]  John C. Lindon,et al.  NMR-based metabonomic studies on the biochemical effects of commonly used drug carrier vehicles in the rat. , 2002 .

[28]  D. Guo,et al.  Mass Spectrometry-Based Approach in Ginseng Research: A Promising Way to Metabolomics , 2012 .

[29]  P. But,et al.  Differentiation and authentication of Panax ginseng, Panax quinquefolius, and ginseng products by using HPLC/MS. , 2000, Analytical chemistry.

[30]  Multivariate chromatographic fingerprint preparation and authentication of plant material from the genus Bauhinia. , 2008, Phytochemical analysis : PCA.

[31]  Z Jandrić,et al.  Assessment of fruit juice authenticity using UPLC-QToF MS: a metabolomics approach. , 2014, Food chemistry.

[32]  F. Song,et al.  Differentiation and identification of ginsenoside isomers by electrospray ionization tandem mass spectrometry , 2005 .

[33]  Fulvio Mattivi,et al.  Metabolite profiling on apple volatile content based on solid phase microextraction and gas-chromatography time of flight mass spectrometry. , 2011, Journal of chromatography. A.

[34]  Age K. Smilde,et al.  Double-check: validation of diagnostic statistics for PLS-DA models in metabolomics studies , 2011, Metabolomics.

[35]  Peteris Prusis,et al.  Proteochemometric modeling of HIV protease susceptibility , 2008, BMC Bioinformatics.

[36]  Byeong Yeob Choi,et al.  Metabolomic approach for age discrimination of Panax ginseng using UPLC-Q-Tof MS. , 2011, Journal of agricultural and food chemistry.

[37]  Shengshan Dou,et al.  Identification of Multiple Constituents in the TCM-Formula Shexiang Baoxin Pill by LC Coupled with DAD-ESI-MS-MS , 2009 .

[38]  Drupad K. Trivedi,et al.  The Application of SIMCA P+ in Shotgun Metabolomics Analysis of ZICHILIC-MS Spectra of Human Urine - Experience with the Shimadzu IT-TOF and Profiling Solutions Data Extraction Software , 2012 .