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Title: Quantitative determination of phenolic compounds by UHPLC-UV-MS and use of principal component analysis to differentiate chemo-types of chamomile/chrysanthemum flowerheads

Author
item AVULA, BHARATHI - University Of Mississippi
item WANG, YAN-HONG - University Of Mississippi
item WANG, MEI - University Of Mississippi
item AVONTO, CRISTINA - University Of Mississippi
item ZHAO, JIANPING - University Of Mississippi
item SMILLIE, TROY - University Of Mississippi
item KHAN, IKHLAS - University Of Mississippi

Submitted to: Journal of Pharmaceutical and Biomedical Analysis
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: 8/20/2013
Publication Date: 1/1/2014
Citation: Avula, B., Wang, Y., Wang, M., Avonto, C., Zhao, J., Smillie, T.J., Khan, I. 2014. Quantitative determination of phenolic compounds by UHPLC-UV-MS and use of principal component analysis to differentiate chemo-types of chamomile/chrysanthemum flowerheads. Journal of Pharmaceutical and Biomedical Analysis. 88:278-288.

Interpretive Summary: This study was done to differentiate the Roman from German Chamomiles and Chrysanthemum morifolium (Chinese Chamomile). Fast UHPLC-UV-QTOF method developed for determination of phenolic compounds from flower heads of Chamomiles and Chrysanthemum species. Principal component analysis was used to discriminate chamomiles and Chrysanthemum samples according to their different chemical entities which showed the chemo-diversity present in various types of chamomiles. LC-mass spectrometry used for confirmation of phenolic compounds in samples of chamomiles. 28 samples of German chamomile (M. recutita), 5 samples of Roman chamomile (A. nobilis), 17 samples of Chrysanthemum morifolium, 7 dietary products (capsules and liquid extracts containing German chamomile), 11 tea bags, 7 body and hair care products claiming to contain German Chamomile were used for analysis. Chamaemeloside (0.1-1.7 %) is a marker compound for Roman chamomile and was not detected in any other chamomiles or chrysanthemum samples. It is a useful analytical tool for routine analysis and to ensure the quality control of chamomile preparations used as herbal supplements and cosmetic products.

Technical Abstract: A new rapid UHPLC-UV-QTOF/MS method has been developed for the simultaneous analysis of nine phenolic compounds [cis-GMCA, chlorogenic acid, trans-GMCA, quercetagetin-7-O-ß-D-glucopyranoside, luteolin-7-O-ß-D-glucoside, apigenin-7-O- ß-Dglucoside, chamaemeloside, apigenin 7-O-(6"-O-acetyl-ß-D-glucopyranoside), apigenin] and one polyacetylene (tonghaosu) from the flower heads of Chamomile/Chrysanthemum samples. The chromatographic separation was achieved using a reversed phase C18 column with a mobile phase of water and acetonitrile, both containing 0.05 % formic acid. The ten compounds were completely separated within 15 minutes at a flow rate of 0.25mL/min with a 2 µL injection volume. The different chemo-types of Chamomiles /Chrysanthemum displayed variations in the presence of chemical constituents. German Chamomile samples confirmed the presence of cis-GMCA, trans-GMCA, apigenin-7-O-ß-D-glucoside and tonghaosu as major constituents whereas Roman chamomile samples confirmed the presence of chamamaeloside and apigenin as major compounds. The Chrysanthemum morifolium samples showed the presence of luteolin-7-O-ß-Dglucose as the major compound. The method was applied for the analysis of various commercial products including capsules, tea bags, body and hair care products. LC-mass spectrometry with electrospray ionization (ESI) interface method is described for the evaluation of ten compounds in plant samples and commercial products. This method involved the detection of [M+Na]+ and [M+H]+ ions in the positive mode. An innovative chemometrics analytical tool for visualizing commercial samples quality was also developed and may be of value for discriminating between Chamomile types and Chrysanthemum with regards to the relative content of individual constituents. The results indicated that the method is suitable as a quality control test for various Chamomile/Chrysanthemum samples and market products.