Characterization and classification of seven citrus herbs by liquid chromatography-quadrupole time-of-flight mass spectrometry and genetic algorithm optimized support vector machines.

Citrus herbs have been widely used in traditional medicine and cuisine in China and other countries since the ancient time. However, the authentication and quality control of Citrus herbs has always been a challenging task due to their similar morphological characteristics and the diversity of the multi-components existed in the complicated matrix. In the present investigation, we developed a novel strategy to characterize and classify seven Citrus herbs based on chromatographic analysis and chemometric methods. Firstly, the chemical constituents in seven Citrus herbs were globally characterized by liquid chromatography combined with quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). Based on their retention time, UV spectra and MS fragmentation behavior, a total of 75 compounds were identified or tentatively characterized in these herbal medicines. Secondly, a segmental monitoring method based on LC-variable wavelength detection was developed for simultaneous quantification of ten marker compounds in these Citrus herbs. Thirdly, based on the contents of the ten analytes, genetic algorithm optimized support vector machines (GA-SVM) was employed to differentiate and classify the 64 samples covering these seven herbs. The obtained classifier showed good prediction performance and the overall prediction accuracy reached 96.88%. The proposed strategy is expected to provide new insight for authentication and quality control of traditional herbs.

[1]  J. Xu,et al.  Quality evaluation of Polygonum multiflorum in China based on HPLC analysis of hydrophilic bioactive compounds and chemometrics. , 2013, Journal of pharmaceutical and biomedical analysis.

[2]  Jing Zhao,et al.  Advanced development in analysis of phytochemicals from medicine and food dual purposes plants used in China. , 2011, Journal of chromatography. A.

[3]  Shao-Ping Li,et al.  Advanced phytochemical analysis of herbal tea in China. , 2013, Journal of chromatography. A.

[4]  S. Liang,et al.  A support vector machine based pharmacodynamic prediction model for searching active fraction and ingredients of herbal medicine: Naodesheng prescription as an example. , 2011, Journal of pharmaceutical and biomedical analysis.

[5]  Ian H. Witten,et al.  Data mining: practical machine learning tools and techniques, 3rd Edition , 1999 .

[6]  M. Claeys,et al.  Structure characterization of flavonoid O-diglycosides by positive and negative nano-electrospray ionization ion trap mass spectrometry. , 2001, Journal of mass spectrometry : JMS.

[7]  Xiao‐he Xiao,et al.  Direct determination of fourteen underivatized amino acids from Whitmania pigra by using liquid chromatography-evaporative light scattering detection. , 2007, Journal of chromatography. A.

[8]  Xinmiao Liang,et al.  UPLC/Q-TOFMS/MS as a powerful technique for rapid identification of polymethoxylated flavones in Fructus aurantii. , 2009, Journal of pharmaceutical and biomedical analysis.

[9]  Yung-Sheng Huang,et al.  Polymethoxy flavones are responsible for the anti-inflammatory activity of citrus fruit peel , 2010 .

[10]  B. Bian,et al.  Chemical profiling and quantification of Chinese medicinal formula Huang-Lian-Jie-Du decoction, a systematic quality control strategy using ultra high performance liquid chromatography combined with hybrid quadrupole-orbitrap and triple quadrupole mass spectrometers. , 2013, Journal of chromatography. A.

[11]  Lian‐Wen Qi,et al.  A segmental monitoring strategy based on variable wavelength detection for quality control of three Polygonaceae herbs. , 2012, Journal of pharmaceutical and biomedical analysis.

[12]  Wenyuan Liu,et al.  Characterization and simultaneous quantification of multiple constituents in Aurantii Fructus Immaturus extracts by HPLC-DAD-ESI-MS/MS , 2012 .

[13]  M. Yano,et al.  Antiproliferative activity of flavonoids on several cancer cell lines. , 1999, Bioscience, biotechnology, and biochemistry.

[14]  B. Patil,et al.  Electron ionization mass spectrometry of citrus limonoids. , 2003, Rapid communications in mass spectrometry : RCM.

[15]  B. Patil,et al.  Antioxidant activity of citrus limonoids, flavonoids, and coumarins. , 2005, Journal of agricultural and food chemistry.

[16]  D. Barreca,et al.  Flavonoid composition of Citrus juices. , 2007, Molecules.

[17]  Tansel Özyer,et al.  A Consistency-Based Feature Selection Method Allied with Linear SVMs for HIV-1 Protease Cleavage Site Prediction , 2013, PloS one.

[18]  Wan-ying Wu,et al.  Comparison of two officinal Chinese pharmacopoeia species of Ganoderma based on chemical research with multiple technologies and chemometrics analysis. , 2012, Journal of chromatography. A.

[19]  Sanghyun Lee,et al.  Simultaneous determination of polymethoxyflavones in Citrus species, Kiyomi tangor and Satsuma mandarin, by high performance liquid chromatography. , 2012, Food chemistry.

[20]  Min Yang,et al.  Phytochemical analysis of traditional Chinese medicine using liquid chromatography coupled with mass spectrometry. , 2009, Journal of chromatography. A.

[21]  Per Broberg,et al.  Analysis and Understanding of High‐Dimensionality Data by Means of Multivariate Data Analysis , 2005, Chemistry & biodiversity.

[22]  Eslam Pourbasheer,et al.  Application of genetic algorithm-support vector machine (GA-SVM) for prediction of BK-channels activity. , 2009, European journal of medicinal chemistry.

[23]  A. Crozier,et al.  Flavonoids in tropical citrus species. , 2011, Journal of agricultural and food chemistry.

[24]  Corinna Cortes,et al.  Support-Vector Networks , 1995, Machine Learning.

[25]  Run-tao Tian,et al.  Evaluation of traditional Chinese herbal medicine: Chaihu (Bupleuri Radix) by both high-performance liquid chromatographic and high-performance thin-layer chromatographic fingerprint and chemometric analysis. , 2009, Journal of chromatography. A.

[26]  J. Koropatnick,et al.  Tangeretin and nobiletin induce G1 cell cycle arrest but not apoptosis in human breast and colon cancer cells. , 2007, Cancer letters.

[27]  Ping Li,et al.  Rapid resolution liquid chromatography-electrospray ionisation tandem mass spectrometry method for identification of chemical constituents in Citri Reticulatae Pericarpium. , 2013, Food chemistry.

[28]  M. Jalali-Heravi,et al.  Chromatographic fingerprint analysis of secondary metabolites in citrus fruits peels using gas chromatography-mass spectrometry combined with advanced chemometric methods. , 2012, Journal of chromatography. A.

[29]  B. Gallo,et al.  New features on the fragmentation and differentiation of C-glycosidic flavone isomers by positive electrospray ionization and triple quadrupole mass spectrometry. , 2008, Rapid communications in mass spectrometry : RCM.

[30]  B. Patil,et al.  Supercritical fluid extraction of limonoid glucosides from grapefruit molasses. , 2006, Journal of agricultural and food chemistry.

[31]  C. Duan,et al.  The flavonoid composition of flavedo and juice from the pummelo cultivar (Citrus grandis (L.) Osbeck) and the grapefruit cultivar (Citrus paradisi) from China , 2011 .

[32]  Lian‐Wen Qi,et al.  Analysis of Chinese herbal medicines with holistic approaches and integrated evaluation models , 2008 .

[33]  Wen Gao,et al.  Unbiased metabolite profiling by liquid chromatography-quadrupole time-of-flight mass spectrometry and multivariate data analysis for herbal authentication: classification of seven Lonicera species flower buds. , 2012, Journal of chromatography. A.

[34]  A. Murakami,et al.  Identification of coumarins from lemon fruit (Citrus limon) as inhibitors of in vitro tumor promotion and superoxide and nitric oxide generation. , 1999, Journal of agricultural and food chemistry.

[35]  Ping Li,et al.  Simultaneous determination of six bioactive flavonoids in Citri Reticulatae Pericarpium by rapid resolution liquid chromatography coupled with triple quadrupole electrospray tandem mass spectrometry. , 2013, Food chemistry.