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Title: Chemical profiling and quantification of monacolins and citrinin in red yeast rice commercial raw materials and dietary supplements using liquid chromatography-accurate QToF mass spectrometry: chemometrics application

Author
item AVULA, BHARATHI - University Of Mississippi
item COHEN, PIETER - University Of Mississippi
item WANG, YAN-HONG - University Of Mississippi
item SAGI, SATYANARAYANARA - University Of Mississippi
item FENG, WEI - University Of Mississippi
item WANG, MEI - University Of Mississippi
item ZWEIGENBAUM, JERRY - University Of Mississippi
item SHUANGCHENG, MA - 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: 7/31/2014
Publication Date: 8/9/2014
Publication URL: https://handle.nal.usda.gov/10113/62281
Citation: Avula, B., Cohen, P.A., Wang, Y., Sagi, S.J., Feng, W., Wang, M., Zweigenbaum, J., Shuangcheng, M., Khan, I.A. 2014. Chemical profiling and quantification of monacolins and citrinin in red yeast rice commercial raw materials and dietary supplements using liquid chromatography-accurate QToF mass spectrometry: chemometrics application. Journal of Pharmaceutical and Biomedical Analysis. 100:243-253.

Interpretive Summary: The method was found to be simple, precise, accurate, specific and sensitive and can be used for routine quality control of raw materials/dietary supplements and for the quantification of compounds. Chromatographic fingerprinting demonstrated the similarities and differences between RYR samples analyzed. Consumers of red yeast rice (RYR) dietary supplements are unable to obtain important information regarding dosage, adverse effects and herb-drug interactions from the dietary supplement labels. Monacolin K (lovastatin) content in 600 mg of authentic RYR samples ranged from 1.2 mg to 1.4 mg. Amounts of monacolin K in dietary supplements labeled as containing 600 mg of RYR ranged from 0.03 mg to 2.18 mg. PCA was applied to the authentic and commercial samples of RYR and dietary supplements as a quality control assessment in order to differentiate their chemical profiles.

Technical Abstract: Red yeast rice (RYR) is prepared by fermenting rice with various strains of the yeast Monascus spp of the Aspergillaceae family. Depending on the Monascus strains and the fermentation conditions, the products may contain monacolins, pigments and citrinin as secondary metabolites. Authentic and commercial RYR samples were analyzed using UHPLC-PDA-QToFMS for monacolins, pigments and citrinin. A separation by LC was achieved using a reversedphase column and a gradient of water/acetonitrile each containing formic acid as the mobile phase. Accurate mass ToF spectrometry was used to distinguish isobaric monacolins. Principle component analysis (PCA), a chemometric technique was used to discriminate between authentic RYR, commercial RYR raw materials and dietary supplements. Three authentic RYR samples, 31 commercial RYR raw materials and 14 RYR dietary supplements were analyzed. Monacolin K content in 600 mg of authentic RYR samples ranged from 1.2 mg to 1.38 mg. Amounts of monacolin K in dietary supplements labeled as containing 600 mg of RYR varied more than 40-fold from 0.03 mg to 2.18 mg. Monacolin K content of dietary supplements labeled as containing 1200 mg RYR varied more than 20-fold from 0.22 mg to 5.23 mg. In addition to large variations in quantity of monacolin K found in dietary supplements, RYR dietary supplements contained ratios of monacolins that differed significantly from authentic samples. The results indicated that RYR commercial products are of variable quality and the analytical method is suitable for quality control testing of a variety of RYR products.