Authentication of black cohosh (Actaea racemosa) dietary supplements based on chemometric evaluation of hydroxycinnamic acid esters and hydroxycinnamic acid amides
Ester and amide derivatives of hydroxycinnamic acids are found in black cohosh (Actaea racemosa) and other Actaea plants. These two compound groups were evaluated for authentication of black cohosh dietary supplements. The hydroxycinnamic acid esters (HCAE) were profiled by ultra-performance liquid chromatography-photodiode array detection (UPLC-PDA). The hydroxycinnamic acid amides (HCAA) were acquired simultaneously by mass spectrometry-multiple reaction monitoring (UPLC-MRM) mode. In contrast with the traditional HCAE method using 8 compounds, profiles of HCAA using only 4 feruloyl dopamine-O-hexosides was more convenient for peak by peak comparison. Partial least square discriminant analysis (PLS-DA) was applied to both HCAE and HCAA datasets. Authenticated plant samples of five Actaea species were randomly divided into training and test sets to build and validate the two PLS-DA models. Both models provided reasonable estimates for the classification of A. racemosa and other Actaea plant samples. However, HCAA model performs better in sensitivity, specificity, and accuracy. Assessment of supplement samples provided quite different results for the solid and liquid dietary supplement samples, indicating the dosage form could affect the composition of marker compounds.
KeywordsHydroxycinnamic acid amide glycoside Hydroxycinnamic acid ester UPLC-MRM Nitrogen-containing PLS-DA
This research is supported by the Agricultural Research Service of the US Department of Agriculture and an Interagency Agreement with the Office of Dietary Supplements of the National Institutes of Health (Grant Y01 OD001298-01).
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
- 1.Predny ML, De Angelis P, Chamberlain JL, United S, Forest S, Southern Research S. Black cohosh (Actaea racemosa) : an annotated bibliography. Asheville: Southern Research Station; 2006.Google Scholar
- 2.Dietary Supplement Label Database. 2018. National Institutes of Health. http://www.dsld.nlm.nih.gov/dsld/index.jsp.
- 4.Foster S. Exploring the peripatetic maze of black cohosh adulteration: a review of the nomenclature, distribution, chemistry, market status, analytical methods and safety. HerbalGram. 2013;98:32–51.Google Scholar
- 6.Gafner S. Black cohosh adulteration laboratory guidance document. 2015Google Scholar
- 10.Gafner S, Sudberg S, Sudberg EM, Villinski JR, Gauthier R, Bergeron C. Chromatographic fingerprinting as a means of quality control: distinction between Actaea racemosa and four different Actaea species. Acta Hortic. 2006;720(Proceedings of the IVth International Conference on Quality and Safety Issues Related to Botanicals, 2005):83–94. https://doi.org/10.17660/ActaHortic.2006.720.8.CrossRefGoogle Scholar
- 13.Ma C, Kavalier AR, Jiang B, Kennelly EJ. Metabolic profiling of Actaea species extracts using high performance liquid chromatography coupled with electrospray ionization time-of-flight mass spectrometry. J Chromatogr A. 2011;1218(11):1461–76. https://doi.org/10.1016/j.chroma.2011.01.033.CrossRefGoogle Scholar
- 19.Jiang B, Kronenberg F, Nuntanakorn P, Qiu M-H, Kennelly EJ. Evaluation of the botanical authenticity and phytochemical profile of black cohosh products by high-performance liquid chromatography with selected ion monitoring liquid chromatography-mass spectrometry. J Agric Food Chem. 2006;54(9):3242–53. https://doi.org/10.1021/jf0606149.CrossRefGoogle Scholar
- 20.Geng P, Harnly JM, Sun J, Zhang M, Chen P. Feruloyl dopamine-O-hexosides are efficient marker compounds as orthogonal validation for authentication of black cohosh (Actaea racemosa)—an UHPLC-HRAM-MS chemometrics study. Anal Bioanal Chem. 2017;409(10):2591–600. https://doi.org/10.1007/s00216-017-0205-1.CrossRefGoogle Scholar
- 21.Li C, Chen D, Xiao P, Hong S, Ma L. Chemical constituents of traditional Chinese drug “Sheng-ma” (Cimicifuga Dahurica). II. Chemical structure of Cimicifugamide. Acta Chim Sin. 1994;52(3):296–300.Google Scholar
- 22.Li C, Chen D, Xiao P. Studies on phenolic glycosides isolated from Cimicifuga dahurica. Acta Pharm Sin. 1994;29:199.Google Scholar
- 24.Zhang F, Han L-F, Pan G-X, Peng S, Andre N. A new phenolic amide glycoside from Cimicifuga dahurica. Acta Pharm Sin. 2013;48(8):1281–5.Google Scholar
- 25.Reynaud D. DNA sequencing of SRM 3295, Actaea racemosa: AuthenTechnologies, LLC; 2014.Google Scholar