Planta Med 2016; 82(03): 250-262
DOI: 10.1055/s-0035-1558113
Natural Product Chemistry & Analytical Studies
Original Papers
Georg Thieme Verlag KG Stuttgart · New York

Comparison of Flow Injection MS, NMR, and DNA Sequencing: Methods for Identification and Authentication of Black Cohosh (Actaea racemosa)

James Harnly
1   Food Composition and Methods Development Laboratory, Beltsville Human Nutrition Research Center, Agricultural Research Service, U. S. Department of Agriculture, Beltsville, MD, USA
,
Pei Chen
1   Food Composition and Methods Development Laboratory, Beltsville Human Nutrition Research Center, Agricultural Research Service, U. S. Department of Agriculture, Beltsville, MD, USA
,
Jianghao Sun
1   Food Composition and Methods Development Laboratory, Beltsville Human Nutrition Research Center, Agricultural Research Service, U. S. Department of Agriculture, Beltsville, MD, USA
,
Huilian Huang
1   Food Composition and Methods Development Laboratory, Beltsville Human Nutrition Research Center, Agricultural Research Service, U. S. Department of Agriculture, Beltsville, MD, USA
,
Kimberly L. Colson
2   Bruker BioSpin, Billerica, MA, USA
,
Jimmy Yuk
2   Bruker BioSpin, Billerica, MA, USA
,
Joe-Ann H. McCoy
3   The North Carolina Arboretum Germplasm Repository, Asheville, NC, USA
,
Danica T. Harbaugh Reynaud
4   AuthenTechnologies LLC, Richmond, CA, USA
,
Peter B. Harrington
5   Center for Intelligent Chemical Instrumentation, Department of Chemistry and Biochemistry, Clippinger Laboratories, Ohio University, Athens, OH, USA
,
Edward J. Fletcher
6   Strategic Sourcing, Inc., Banner Elk, NC, USA
› Author Affiliations
Further Information

Publication History

received 29 January 2015
revised 02 September 2015

accepted 03 September 2015

Publication Date:
21 December 2015 (online)

Abstract

Flow injection mass spectrometry and proton nuclear magnetic resonance spectrometry, two metabolic fingerprinting methods, and DNA sequencing were used to identify and authenticate Actaea species. Initially, samples of Actaea racemosa from a single source were distinguished from other Actaea species based on principal component analysis and soft independent modeling of class analogies of flow injection mass spectrometry and proton nuclear magnetic resonance spectrometry metabolic fingerprints. The chemometric results for flow injection mass spectrometry and proton nuclear magnetic resonance spectrometry agreed well and showed similar agreement throughout the study. DNA sequencing using DNA sequence data from two independent gene regions confirmed the metabolic fingerprinting results. Differences were observed between A. racemosa samples from four different sources, although the variance within species was still significantly less than the variance between species. A model based on the combined A. racemosa samples from the four sources consistently permitted distinction between species. Additionally, the combined A. racemosa samples were distinguishable from commercial root samples and from commercial supplements in tablet, capsule, or liquid form. DNA sequencing verified the lack of authenticity of the commercial roots but was unsuccessful in characterizing many of the supplements due to the lack of available DNA.

 
  • References

  • 1 Blumenthal M. Herb sales down 7.4 percent in mainstream market; garlic is top-selling herb; herb combinations see increase. HerbalGram 2005; 66: 63
  • 2 Hildreth J, Hrabeta-Robinson E, Applequist W, Betz L. Standard operating procedure for the collection and preparation of voucher plant specimens for use in the nutraceutical industry. Anal Bioanal Chem 2007; 389: 13-17
  • 3 Hall RD. Plant metabolomics from holistic hope, to hype, to hot topic. New Phytol 2006; 169: 453-468
  • 4 AOAC International, Guideline Working Group. AOAC INTERNATIONAL guidelines for validation of botanical identification methods. J AOAC Int 2012; 95: 268-272
  • 5 LaBudde R, Harnly JM. Probability of identification (POI): a statistical model for the validation of qualitative botanical identification methods. J AOAC Int 2012; 95: 273-285
  • 6 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: 1461-1476
  • 7 Qiu F, McAlpine JB, Lankin DC, Burton I, Karakach T, Chen SN, Pauli GF. 2D NMR barcoding and differential analysis of complex mixtures for chemical identification: the Actaea terpenes. Anal Chem 2014; 86: 3964-3972
  • 8 Masada-Atsumi S, Kumeta Y, Takahashi Y, Hakamatsuka T, Goda Y. Evaluation of the botanical origin of black cohosh products by generic and chemical analyses. Biol Pharm Bull 2014; 37: 454-460
  • 9 He K, Pauli GF, Zheng B, Wang H, Bai N, Peng T, Roller M, Zheng Q. Cimicifuga species identification by high performance liquid chromatography-photodiode array/mass spectrometric/evaporative light scattering detection for quality control of black cohosh products. J Chromatogr A 2006; 1112: 241-254
  • 10 Harnly JM, Harrington PB. Adulteration of American with Asian ginseng: spectral addition and experimental verification of probability of identification. J AOAC Int 2013; 96: 1258-1265
  • 11 Harnly JM, Luthria DL, Chen P. Detection of adulterated Ginkgo biloba supplements using chromatographic and spectral fingerprints. J AOAC Int 2012; 95: 1579-1587
  • 12 Harnly JM, Mukhopadhyay S, Lin LZ, Luthria DL. A comparison of analytical and data preprocessing methods for spectral fingerprinting. Appl Spectrosc 2011; 65: 250-259
  • 13 Luthria DL, Lin LZ, Robbins RJ, Finley JW, Banuelos GS, Harnly JM. Discriminating between cultivars and treatments of broccoli using mass spectral fingerprinting and analysis of variance principal component analysis. J Agric Food Chem 2008; 56: 9819-9827
  • 14 Chen P, Luthria D, Harrington PB, Harnly JM. Discrimination among Panax species using spectral fingerprinting. J AOAC Int 2011; 94: 1411-1421
  • 15 Huang H, Sun J, McCoy JA, Zhong H, Fletcher EJ, Harnly JM, Chen P. Use of flow injection mass spectrometric fingerprinting (FIMS) and chemometrics for differentiation of three black cohosh species. Spectrochim Acta 2014; , in press
  • 16 Chen P, Sun J, Ford P. Differentiation of the four major species of cinnamons (C. burmannii, C. verum, C. cassia, and C. loureiroi) using a flow injection mass spectrometric (FIMS) fingerprinting method. J Agric Food Chem 2014; 62: 2516-2521
  • 17 Safer S, Cicek A, Pieri V, Schwaiger P, Schneider P, Wissemann V, Stuppner H. Metabolic fingerprinting of Leontopodium species (Asteraceaea) by means of 1 H-NMR and HPLC-ESI-MS. Phytochemistry 2011; 72: 1379-1389
  • 18 Yilmaz A, Nyberg N, Mølgaard P, Asili J, Jaroszewski J. 1H NMR metabolic fingerprinting of saffron extracts. Metabolomics 2010; 6: 511-517
  • 19 Ali K, Maltese F, Zyprian E, Rex M, Choi YH, Verpoorte R. NMR metabolic fingerprinting based identification of grapevine metabolites associated with downy mildew resistance. J Agric Food Chem 2009; 57: 9599-9606
  • 20 Kim HY, Choi YH, Erkelens C, Lefeber AW, Verpoorte R. Metabolic fingerprinting of Ephedra species using 1 H-NMR spectroscopy and principal component analysis. Chem Pharm Bull (Tokyo) 2005; 53: 105-109
  • 21 Kim HK, Saifullah. Khan S, Wilson EG, Kricun SD, Meissner A, Goraler S, Deelder AM, Choi YH, Verpoorte R. Metabolic classification of South American Ilex species by NMR-base metabolomics. Phytochemistry 2010; 71: 773-784
  • 22 Wold S. Pattern-recognition by means of disjoint principal components models. Pattern Recogn 1976; 8: 127-139
  • 23 Wabuyele BW, Harrington PD. Fuzzy optimal associative memory for background prediction of near-infrared spectra. Appl Spectrosc 1996; 50: 35-42
  • 24 Harrington PB, Kister J, Artaud J, Dupuy N. Automated principal component-based orthogonal signal correction applied to fused near infrared-mid-infrared spectra of French olive oils. Anal Chem 2008; 81: 7160-7169
  • 25 Harrington PB. Fuzzy multivariate rule-building expert systems – minimal neural networks. J Chemometr 1991; 5: 467-486
  • 26 CBOL Plant Working Group. A DNA barcode for land plants. Proc Natl Acad Sci U S A 2009; 106: 12794-12797
  • 27 Gafner S, Blumenthal M, Reynaud DH, Foster S, Techen N. ABC review and critique of the research article “DNA barcoding detects contamination and substitution in North American herbal products” by Newmaster et al. HerbalEGram 2013; 10: 11
  • 28 Reynaud D, Handy S. Primers for short DNA sequences. AuthenTechnologies, LLC and US Food and Drug Administration. Personal communication 2015
  • 29 Reynaud D. DNA sequencing of SRM 3295, Actaea racemosa . AuthenTechnologies, LLC. Personal communication 2014
  • 30 Strobel G, Daisy B. Bioprospecting for microbial endophytes and their natural products. Microbiol Mol Biol Rev 2003; 67: 491-502
  • 31 Genazzani AD, Rodbard D. Use of the receiver operating characteristic curve to evaluate sensitivity, specificity, and accuracy of methods for detection of peaks in hormone time-series. Acta Endocrinol (Copenh) 1991; 124: 295-306
  • 32 Hanley JA, Mcneil BJ. The meaning and use of the area under a receiver operating characteristic (Roc) curve. Radiology 1982; 143: 29-36
  • 33 Harrington PDB. Statistical validation of classification and calibration models using bootstrapped Latin partitions. Trends Anal Chem 2006; 25: 1112-1124
  • 34 Sun XB, Zimmermann CM, Jackson GP, Bunker CE, Harrington PB. Classification of jet fuels by fuzzy rule-building expert systems applied to three-way data by fast gas chromatography-fast scanning quadrupole ion trap mass spectrometry. Talanta 2011; 83: 1260-1268