Top

BMC Complementary Medicine and Therapies

Published in:

Open Access 01-12-2023 | Research

Authentication of milk thistle commercial products using UHPLC-QTOF-ESI + MS metabolomics and DNA metabarcoding

Authors: Ancuța Cristina Raclariu-Manolică, Quentin Mauvisseau, Renato Paranaiba, Hugo J. De Boer, Carmen Socaciu

Published in: BMC Complementary Medicine and Therapies | Issue 1/2023

Abstract

Background

Milk thistle is one of the most popular hepatoprotectants, and is often sold in combination with other ingredients. Botanical supplements are known to be vulnerable to contamination and adulteration, and emerging technologies show promise to improve their quality control.

Methods

Untargeted and semi-targeted metabolomics based on UHPLC-QTOF-ESI⁺MS techniques, UV spectrometry, and DNA metabarcoding using Illumina MiSeq were used to authenticate eighteen milk thistle botanical formulations (teas, capsules, tablets, emulsion).

Results

Untargeted metabolomics separated 217 molecules and by multivariate analysis the discrimination between the different preparations was established. The semi-targeted metabolomics focused on 63 phytochemicals, mainly silymarin flavonolignans and flavonoids, that may be considered as putative biomarkers of authenticity. All formulations contained molecules from silymarin complexes at different levels. The quantitative evaluation of silybins was done using in parallel UV spectrometry and UHPLC-QTOF-ESI⁺MS and their correlations were compared. DNA metabarcoding detected milk thistle in eleven out of sixteen retained preparations, whereas two others had incomplete evidence of milk thistle despite metabolomics validating specific metabolites, e.g., silymarin complex, identified and quantified in all samples. Meanwhile, the DNA metabarcoding provided insights into the total species composition allowing the interpretation of the results in a broad context.

Conclusion

Our study emphasizes that combining spectroscopic, chromatographic, and genetic techniques bring complementary information to guarantee the quality of the botanical formulations.

Available only for authorised users

Schuppan D, Jia J-D, Brinkhaus B, Hahn EG. Herbal products for liver diseases: a therapeutic challenge for the new millennium. Hepatology. 1999;30:1099–104. https://doi.org/10.1002/hep.510300437.CrossRefPubMed

Post-White J, Ladas EJ, Kelly KM. Advances in the use of milk thistle (Silybum marianum). Integr Cancer Ther. 2007;6:104–9. https://doi.org/10.1177/1534735407301632.CrossRefPubMed

Ross SM. Milk thistle (Silybum marianum): an ancient botanical medicine for modern times. Holist Nurs Pract. 2008;22:299–300. https://doi.org/10.1097/01.HNP.0000334924.77174.6d.CrossRefPubMed

Siegel AB, Stebbing J. Milk thistle: early seeds of potential. Lancet Oncol. 2013;14:929–30. https://doi.org/10.1016/S1470-2045(13)70414-5.CrossRefPubMedPubMedCentral

Krepkova LV, Babenko AN, Saybel’ OL, Lupanova IA, Kuzina OS, Job KM et al. Valuable hepatoprotective plants - how can we pptimize waste free uses of such highly versatile resources? Front Pharmacol 2021;12.

Raclariu-Manolică AC, Socaciu C. Detecting and profiling of milk thistle metabolites in food supplements: a safety-oriented approach by advanced analytics. Metabolites. 2023;13:440. https://doi.org/10.3390/metabo13030440.CrossRefPubMedPubMedCentral

Blumenthal M, Bussmann RW, Goldberg A, Gruenwald J, Hall T, Riggins CW, et al. The complete german commission E monographs: therapeutic guide to herbal medicines. Integrative medicine communications. Austin, TX/Boston, MA,: American Botanical Council; 1998.

Gillessen A, Schmidt HH-J. Silymarin as supportive treatment in liver diseases: a narrative review. Adv Ther. 2020;37:1279–301. https://doi.org/10.1007/s12325-020-01251-y.CrossRefPubMedPubMedCentral

Zecca E, Zuppa AA, D’Antuono A, Tiberi E, Giordano L, Pianini T, et al. Efficacy of a galactogogue containing silymarin-phosphatidylserine and galega in mothers of preterm infants: a randomized controlled trial. Eur J Clin Nutr. 2016;70:1151–4. https://doi.org/10.1038/ejcn.2016.86.CrossRefPubMed

10.

Bazzano AN, Cenac L, Brandt AJ, Barnett J, Thibeau S, Theall KP. Maternal experiences with and sources of information on galactagogues to support lactation: a cross-sectional study. Int J Womens Health. 2017;9:105–13. https://doi.org/10.2147/IJWH.S128517.CrossRefPubMedPubMedCentral

11.

Lawrence RM, Lawrence RA. 11 - medications, herbal preparations, and natural products in breast milk. In: Lawrence RA, Lawrence RM, editors. Breastfeeding (ninth edition). Philadelphia: Elsevier; 2022. pp. 326–92. https://doi.org/10.1016/B978-0-323-68013-4.00011-0.CrossRef

12.

Greenlee H, Abascal K, Yarnell E, Ladas E. Clinical applications of Silybum marianum in Oncology. Integr Cancer Ther. 2007;6:158–65. https://doi.org/10.1177/1534735407301727.CrossRefPubMed

13.

Tajmohammadi A, Razavi BM, Hosseinzadeh H. Silybum marianum (milk thistle) and its main constituent, silymarin, as a potential therapeutic plant in metabolic syndrome: a review. Phytother Res. 2018;32:1933–49. https://doi.org/10.1002/ptr.6153.CrossRefPubMed

14.

Mengs U, Pohl R-T, Mitchell T, Legalon® SIL. The antidote of choice in patients with acute hepatotoxicity from amatoxin poisoning. Curr Pharm Biotechnol. 2012;13:1964–70.CrossRefPubMedPubMedCentral

15.

Lee DY-W, Liu Y. Molecular structure and stereochemistry of silybin A, silybin B, isosilybin A, and isosilybin B, isolated from Silybum marianum (milk thistle). J Nat Prod. 2003;66:1171–4. https://doi.org/10.1021/np030163b.CrossRefPubMed

16.

Smith WA, Lauren DR, Burgess EJ, Perry NB, Martin RJ. A silychristin isomer and variation of flavonolignan levels in milk thistle (Silybum marianum) fruits. Planta Med. 2005;71:877–80. https://doi.org/10.1055/s-2005-864187.CrossRefPubMed

17.

Csupor D, Csorba A, Hohmann J. Recent advances in the analysis of flavonolignans of Silybum marianum. J Pharm Biomed Anal. 2016;130:301–17. https://doi.org/10.1016/j.jpba.2016.05.034.CrossRefPubMed

18.

Bijak M. Silybin, a major bioactive component of milk thistle (Silybum marianum L. Gaernt.)—chemistry, bioavailability, and metabolism. Molecules 2017;22:1942. https://doi.org/10.3390/molecules22111942.

19.

Aziz M, Saeed F, Ahmad N, Ahmad A, Afzaal M, Hussain S, et al. Biochemical profile of milk thistle (Silybum Marianum L.) with special reference to silymarin content. Food Sci Nutr. 2021;9:244–50. https://doi.org/10.1002/fsn3.1990.CrossRefPubMed

20.

AbouZid SF, Chen S-N, Pauli GF. Silymarin content in Silybum marianum populations growing in Egypt. Ind Crops Prod. 2016;83:729–37. https://doi.org/10.1016/j.indcrop.2015.12.012.CrossRefPubMedPubMedCentral

21.

Javeed A, Ahmed M, Sajid AR, Sikandar A, Aslam M, Hassan T, ul, et al. Comparative assessment of phytoconstituents, antioxidant activity and chemical analysis of different parts of milk thistle Silybum marianum L. Molecules. 2022;27:2641. https://doi.org/10.3390/molecules27092641.CrossRefPubMedPubMedCentral

22.

Abenavoli L, Izzo AA, Milić N, Cicala C, Santini A, Capasso R. Milk thistle (Silybum marianum): a concise overview on its chemistry, pharmacological, and nutraceutical uses in liver diseases. Phytother Res. 2018;32:2202–13. https://doi.org/10.1002/ptr.6171.CrossRefPubMed

23.

Rainone F. Milk thistle. Am Fam Physician. 2005;72:1285–8.PubMed

24.

Calani L, Brighenti F, Bruni R, Del Rio D. Absorption and metabolism of milk thistle flavanolignans in humans. Phytomedicine. 2012;20:40–6. https://doi.org/10.1016/j.phymed.2012.09.004.CrossRefPubMed

25.

Zhu H-J, Brinda BJ, Chavin KD, Bernstein HJ, Patrick KS, Markowitz JS. An assessment of pharmacokinetics and antioxidant activity of free silymarin flavonolignans in healthy volunteers: a dose escalation study. Drug Metab Dispos. 2013;41:1679–85. https://doi.org/10.1124/dmd.113.052423.CrossRefPubMedPubMedCentral

26.

Khazaei R, Seidavi A, Bouyeh M. A review on the mechanisms of the effect of silymarin in milk thistle (Silybum marianum) on some laboratory animals. Veterinary Med Sci. 2022;8:289–301. https://doi.org/10.1002/vms3.641.CrossRef

27.

Garcia-Alvarez A, Egan B, de Klein S, Dima L, Maggi FM, Isoniemi M, et al. Usage of plant food supplements across six european countries: findings from the PlantLIBRA consumer survey. PLoS ONE. 2014;9:e92265. https://doi.org/10.1371/journal.pone.0092265.CrossRefPubMedPubMedCentral

28.

Smith T, Majid F, Eckl V, Reynolds CM. Herbal Supplement sales in US increase by record-breaking 17.3% in 2020 2017:14.

29.

Ekor M. The growing use of herbal medicines: issues relating to adverse reactions and challenges in monitoring safety. Front Pharmacol. 2014;4:177. https://doi.org/10.3389/fphar.2013.00177.CrossRefPubMedPubMedCentral

30.

Binns CW, Lee MK, Lee AH. Problems and prospects: public health regulation of dietary supplements. Annu Rev Public Health. 2018;39:403–20. https://doi.org/10.1146/annurev-publhealth-040617-013638.CrossRefPubMed

31.

Fitzgerald M, Heinrich M, Booker A. Medicinal plant analysis: a historical and regional discussion of emergent complex techniques. Front Pharmacol. 2020;10. https://doi.org/10.3389/fphar.2019.01480.

32.

World Health Organization (WHO). (2007). World Health Organization guidelines for assessing quality of herbal medicines with reference to contaminants and residues. http://apps.who.int/iris/bitstream/10665/43510/1/9789241594448_eng.pdf.

33.

World Health Organization (WHO). World Health Organization traditional medicine strategy: 2014–2023. WHO; 2013. http://www.who.int/medicines/publications/traditional/trm_strategy14_23/en/.

34.

Rietjens IMCM, Slob W, Galli C, Silano V. Risk assessment of botanicals and botanical preparations intended for use in food and food supplements: emerging issues. Toxicol Lett. 2008;180:131–6. https://doi.org/10.1016/j.toxlet.2008.05.024.CrossRefPubMed

35.

Heinrich M. Quality and safety of herbal medical products: regulation and the need for quality assurance along the value chains. Br J Clin Pharmacol. 2015;80:62–6. https://doi.org/10.1111/bcp.12586.CrossRefPubMedPubMedCentral

36.

Thakkar S, Anklam E, Xu A, Ulberth F, Li J, Li B, et al. Regulatory landscape of dietary supplements and herbal medicines from a global perspective. Regul Toxicol Pharmacol. 2020;114:104647. https://doi.org/10.1016/j.yrtph.2020.104647.CrossRefPubMed

37.

Simmler C, Graham JG, Chen S-N, Pauli GF. Integrated analytical assets aid botanical authenticity and adulteration management. Fitoterapia. 2018;129:401–14. https://doi.org/10.1016/j.fitote.2017.11.017.CrossRefPubMed

38.

De Boer HJ, Ichim MC, Newmaster SG. DNA barcoding and pharmacovigilance of herbal medicines. Drug Saf. 2015;38:611–20. https://doi.org/10.1007/s40264-015-0306-8.CrossRefPubMed

39.

Dwyer JT, Coates PM, Smith MJ. Dietary supplements: regulatory challenges and research resources. Nutrients. 2018;10:41. https://doi.org/10.3390/nu10010041.CrossRefPubMedPubMedCentral

40.

Heinrich M, Appendino G, Efferth T, Fürst R, Izzo AA, Kayser O, et al. Best practice in research – overcoming common challenges in phytopharmacological research. J Ethnopharmacol. 2020;246:112230. https://doi.org/10.1016/j.jep.2019.112230.CrossRefPubMed

41.

Kunle. Standardization of herbal medicines - a review. Int J Biodvers Conserv. 2012;4. https://doi.org/10.5897/IJBC11.163.

42.

Zhang J, Wider B, Shang H, Li X, Ernst E. Quality of herbal medicines: challenges and solutions. Complement Ther Med. 2012;20:100–6. https://doi.org/10.1016/j.ctim.2011.09.004.CrossRefPubMed

43.

Bilia AR. Science meets regulation. J Ethnopharmacol. 2014;158(Pt B):487–94. https://doi.org/10.1016/j.jep.2014.06.036.CrossRef

44.

Ichim MC. The DNA-Based authentication of commercial herbal products reveals their globally widespread adulteration. Front Pharmacol 2019;10.

45.

Saller R, Meier R, Brignoli R. The use of silymarin in the treatment of liver diseases. Drugs. 2001;61:2035–63. https://doi.org/10.2165/00003495-200161140-00003.CrossRefPubMed

46.

Xue Y, Sheng Y, Wang J, Huang Q, Zhang F, Wen Y et al. Fast screening and identification of illegal adulterated glucocorticoids in dietary supplements and herbal products using UHPLC-QTOF-MS with All-Ion Fragmentation Acquisition combined with characteristic fragment Ion List classification. Frontiers in Chemistry 2021;9.

47.

Šimánek V, Kren V, Ulrichová J, Vicar J, Cvak L. Silymarin: What is in the name ...? An appeal for a change of editorial policy. Hepatology 2000;32:442–4. https://doi.org/10.1053/jhep.2000.9770.

48.

Kroll DJ, Shaw HS, Oberlies NH. Milk thistle nomenclature: why it matters in cancer research and pharmacokinetic studies. Integr Cancer Ther. 2007;6:110–9. https://doi.org/10.1177/1534735407301825.CrossRefPubMed

49.

Martin RJ, Lauren DR, Smith WA, Jensen DJ, Deo B, Douglas JA. Factors influencing silymarin content and composition in variegated thistle (Silybum marianum). Null. 2006;34:239–45. https://doi.org/10.1080/01140671.2006.9514413.CrossRef

50.

Habán M, Habánová M, Otepka P, Kobida Ľ. Milk thistle (Silybum marianum [L.] Gaertn. Cultivated in polifunctional crop rotation and its evaluation 2010:7.

51.

Anthony K, Saleh MA. Chemical profiling and antioxidant activity of commercial milk thistle food supplements. J Chem Pharm Res 2012;4.

52.

Chambers CS, Holečková V, Petrásková L, Biedermann D, Valentová K, Buchta M, et al. The silymarin composition? and why does it matter??? Food Research International 2017;100:339–53. https://doi.org/10.1016/j.foodres.2017.07.017.

53.

Pendry BA, Kemp V, Hughes MJ, Freeman J, Nuhu HK, Sanchez-Medina A, et al. Silymarin content in Silybum marianum extracts as a biomarker for the quality of commercial tinctures. J Herb Med. 2017;10:31–6. https://doi.org/10.1016/j.hermed.2017.07.001.CrossRef

54.

Marceddu R, Dinolfo L, Carrubba A, Sarno M, Di Miceli G. Milk thistle (Silybum marianum L.) as a novel multipurpose crop for agriculture in marginal environments: a review. Agronomy. 2022;12:729. https://doi.org/10.3390/agronomy12030729.CrossRef

55.

Fenclova M, Novakova A, Viktorova J, Jonatova P, Dzuman Z, Ruml T, et al. Poor chemical and microbiological quality of the commercial milk thistle-based dietary supplements may account for their reported unsatisfactory and non-reproducible clinical outcomes. Sci Rep. 2019;9:11118. https://doi.org/10.1038/s41598-019-47250-0.CrossRefPubMedPubMedCentral

56.

Viktorova J, Stranska-Zachariasova M, Fenclova M, Vitek L, Hajslova J, Kren V, et al. Complex evaluation of antioxidant capacity of milk thistle dietary supplements. Antioxidants. 2019;8:317. https://doi.org/10.3390/antiox8080317.CrossRefPubMedPubMedCentral

57.

Stickel F, Egerer G, Seitz HK. Hepatotoxicity of botanicals. Public Health Nutr. 2000;3:113–24. https://doi.org/10.1017/s1368980000000161.CrossRefPubMed

58.

Tournas VH, Rivera Calo J, Sapp C. Fungal profiles in various milk thistle botanicals from US retail. Int J Food Microbiol. 2013;164:87–91. https://doi.org/10.1016/j.ijfoodmicro.2013.03.026.CrossRefPubMed

59.

Frommenwiler DA, Sharaf MHM, Reich E. The truth behind herbal products: how HPTLC can help herbal industry detect adulteration? Planta Med. 2019;85:ISL–EA.

60.

McCutcheon A. Adulteration of milk thistle (Silybum marianum). Botanical Adulterants Prevention Bulletin (Austin, TX: ABC-AHPNCNPR Botanical Adulterants Prevention Program) 2020.

61.

Eklund L, Simon JP, Ballenger J. High performance liquid chromatography of flavonolignans in commercial milk thistle supplements. Bios. 2009;80:164–9. https://doi.org/10.1893/011.080.0404.CrossRef

62.

Booker A, Heinrich M. Value chains of botanical and herbal medicinal products: a european perspective. HerbalGram. 2016;112:40–5.

63.

De Boer HJ, Ichim MC, Newmaster SG. DNA barcoding and pharmacovigilance of herbal medicines. Drug Saf. 2015;38:611–20. https://doi.org/10.1007/s40264-015-0306-8.CrossRefPubMed

64.

Lüde S, Vecchio S, Sinno-Tellier S, Dopter A, Mustonen H, Vucinic S, et al. Adverse effects of plant food supplements and plants consumed as food: results from the poisons centres-based PlantLIBRA Study. Phytother Res. 2016;30:988–96. https://doi.org/10.1002/ptr.5604.CrossRefPubMed

65.

Raclariu AC, Heinrich M, Ichim MC, de Boer H. Benefits and limitations of DNA barcoding and metabarcoding in herbal product authentication. Phytochem Anal. 2018;29:123–8. https://doi.org/10.1002/pca.2732.CrossRefPubMed

66.

Pang Z, Zhou G, Ewald J, Chang L, Hacariz O, Basu N, et al. Using MetaboAnalyst 5.0 for LC-HRMS spectra processing, multi-omics integration and covariate adjustment of global metabolomics data. Nat Protoc. 2022;17:1735–61. https://doi.org/10.1038/s41596-022-00710-w.CrossRefPubMed

67.

Wishart DS, Guo A, Oler E, Wang F, Anjum A, Peters H, et al. HMDB 5.0: the human metabolome database for 2022. Nucleic Acids Res. 2022;50:D622–31. https://doi.org/10.1093/nar/gkab1062.CrossRefPubMed

68.

Fahy E, Subramaniam S, Murphy RC, Nishijima M, Raetz CRH, Shimizu T, et al. Update of the LIPID MAPS comprehensive classification system for lipids. J Lipid Res. 2009;50:9–14. https://doi.org/10.1194/jlr.R800095-JLR200.CrossRef

69.

Rothwell JA, Perez-Jimenez J, Neveu V, Medina-Remón A, M’Hiri N, García-Lobato P, et al. Phenol-explorer 3.0: a major update of the phenol-explorer database to incorporate data on the effects of food processing on polyphenol content. Database. 2013;2013:bat070. https://doi.org/10.1093/database/bat070.CrossRefPubMedPubMedCentral

70.

Kim S, Chen J, Cheng T, Gindulyte A, He J, He S, et al. PubChem in 2021: new data content and improved web interfaces. Nucleic Acids Res. 2021;49:D1388–95. https://doi.org/10.1093/nar/gkaa971.CrossRefPubMed

71.

Doyle JJ, Doyle JL. Isolation of plant DNA from fresh tissue. Focus. 1987;12:13–5.

72.

Raclariu AC, Paltinean R, Vlase L, Labarre A, Manzanilla V, Ichim MC, et al. Comparative authentication of Hypericum perforatum herbal products using DNA metabarcoding, TLC and HPLC-MS. Sci Rep. 2017;7:1291. https://doi.org/10.1038/s41598-017-01389-w.CrossRefPubMedPubMedCentral

73.

Kolter A, Gemeinholzer B. Internal transcribed spacer primer evaluation for vascular plant metabarcoding. Metabarcoding and Metagenomics. 2021;5:e68155. https://doi.org/10.3897/mbmg.5.68155.CrossRef

74.

Fadrosh DW, Ma B, Gajer P, Sengamalay N, Ott S, Brotman RM, et al. An improved dual-indexing approach for multiplexed 16S rRNA gene sequencing on the Illumina MiSeq platform. Microbiome. 2014;2:6. https://doi.org/10.1186/2049-2618-2-6.CrossRefPubMedPubMedCentral

75.

Ribas TFA, Sales JB, de Boer L, Anmarkrud H, Oliveira JA, Laux RRM. Unexpected diversity in the diet of Doryteuthis sanpaulensis (Brakoniecki, 1984) (Mollusca: Cephalopoda) from the southern brazilian sardine fishery identified by metabarcoding. Fish Res. 2021;239:105936. https://doi.org/10.1016/j.fishres.2021.105936.CrossRef

76.

Zhang J, Kobert K, Flouri T, Stamatakis A. PEAR: a fast and accurate Illumina paired-end reAd mergeR. Bioinformatics. 2014;30:614–20. https://doi.org/10.1093/bioinformatics/btt593.CrossRefPubMed

77.

Boyer F, Mercier C, Bonin A, Le Bras Y, Taberlet P, Coissac E. Obitools: a unix-inspired software package for DNA metabarcoding. Mol Ecol Resour. 2016;16:176–82. https://doi.org/10.1111/1755-0998.12428.CrossRefPubMed

78.

Edgar RC. Search and clustering orders of magnitude faster than BLAST. Bioinformatics. 2010;26:2460–1. https://doi.org/10.1093/bioinformatics/btq461.CrossRefPubMed

79.

Edgar RC. UNOISE2: improved error-correction for Illumina 16S and ITS amplicon sequencing 2016:081257. https://doi.org/10.1101/081257.

80.

Camacho C, Madden T, Tao T, Agarwala R, Morgulis A. BLAST® Command Line Applications user Manual. National Center for Biotechnology Information (US); 2008.

81.

Booker A, Johnston D, Heinrich M. Value chains of herbal medicines—Research needs and key challenges in the context of ethnopharmacology. J Ethnopharmacol. 2012;140:624–33. https://doi.org/10.1016/j.jep.2012.01.039.CrossRefPubMed

82.

Wallace S, Carrier DJ, Beitle RR, Clausen EC, Griffis CL, HPLC-UV, LC-MS-MS. Characterization of silymarin in milk thistle seeds and corresponding products. J Nutraceuticals Funct Med Foods. 2003;4:37–48. https://doi.org/10.1300/J133v04n02_05.CrossRef

83.

Petrásková L, Káňová K, Biedermann D, Křen V, Valentová K. Simple and Rapid HPLC separation and quantification of flavonoid, flavonolignans, and 2,3-dehydroflavonolignans in silymarin. Foods. 2020;9:116. https://doi.org/10.3390/foods9020116.CrossRefPubMedPubMedCentral

84.

Fiehn O. Metabolomics–the link between genotypes and phenotypes. Plant Mol Biol. 2002;48:155–71.CrossRefPubMed

85.

Goodacre R, Vaidyanathan S, Dunn WB, Harrigan GG, Kell DB. Metabolomics by numbers: acquiring and understanding global metabolite data. Trends Biotechnol. 2004;22:245–52. https://doi.org/10.1016/j.tibtech.2004.03.007.CrossRefPubMed

86.

Villas-Bôas SG, Rasmussen S, Lane GA. Metabolomics or metabolite profiles? Trends Biotechnol. 2005;23:385–6. https://doi.org/10.1016/j.tibtech.2005.05.009.CrossRefPubMed

87.

Alonso A, Marsal S, Julià A. Analytical methods in untargeted metabolomics: state of the art in 2015. Front Bioeng Biotechnol 2015;3.

88.

Yang Q, Zhang A, Miao J, Sun H, Han Y, Yan G, et al. Metabolomics biotechnology, applications, and future trends: a systematic review. RSC Adv. 2019;9:37245–57. https://doi.org/10.1039/C9RA06697G.CrossRefPubMedPubMedCentral

89.

Song Q, Zhang A, Yan G, Liu L, Wang X. Technological advances in current metabolomics and its application in tradition chinese medicine. RSC Adv. 2017;7:53516–24. https://doi.org/10.1039/C7RA02056B.CrossRef

90.

Atanasov A, Zotchev S, Dirsch V, Orhan I, Banach M, Rollinger J, et al. Natural products in drug discovery: advances and opportunities. Nat Rev Drug Discovery. 2021;20:1–17. https://doi.org/10.1038/s41573-020-00114-z.CrossRef

91.

Ahmad S, Katiyar CK, Ulrich-Merzenich GS, Mukherjee PK. Editorial: Metabolomics and ethnopharmacology in the development of herbal and traditional medicine. Front Pharmacol 2022;13.

92.

Zhao J, Wang M, Saroja SG, Khan IA. NMR technique and methodology in botanical health product analysis and quality control. J Pharm Biomed Anal. 2022;207:114376. https://doi.org/10.1016/j.jpba.2021.114376.CrossRefPubMed

93.

Abraham EJ, Kellogg JJ. Chemometric-guided approaches for profiling and authenticating botanical materials. Front Nutr. 2021;0. https://doi.org/10.3389/fnut.2021.780228.

94.

Socaciu C. From phytochemistry to metabolomics: eight decades of research in plant and food science. Studia UBB Chemia. 2019;64:205–24. https://doi.org/10.24193/subbchem.2019.4.15.CrossRef

95.

Harrieder E-M, Kretschmer F, Böcker S, Witting M. Current state-of-the-art of separation methods used in LC-MS based metabolomics and lipidomics. J Chromatogr B. 2022;1188:123069. https://doi.org/10.1016/j.jchromb.2021.123069.CrossRef

96.

Dunn WB, Ellis DavidI. Metabolomics: current analytical platforms and methodologies. TRAC Trends Anal Chem. 2005;24:285–94. https://doi.org/10.1016/j.trac.2004.11.021.CrossRef

97.

Lee K-M, Jeon J-Y, Lee B-J, Lee H, Choi H-K. Application of metabolomics to quality control of natural product derived medicines. Biomol Ther (Seoul). 2017;25:559–68. https://doi.org/10.4062/biomolther.2016.249.CrossRefPubMed

98.

Alseekh S, Fernie AR. Metabolomics 20 years on: what have we learned and what hurdles remain? Plant J. 2018;94:933–42. https://doi.org/10.1111/tpj.13950.CrossRefPubMed

99.

Emwas A-H, Roy R, McKay RT, Tenori L, Saccenti E, Gowda GAN et al. NMR spectroscopy for metabolomics research. Metabolites 2019;9. https://doi.org/10.3390/metabo9070123.

100.

Roberts LD, Souza AL, Gerszten RE, Clish CB. Targeted metabolomics. Curr Protoc Mol Biol. 2012;CHAPTER. https://doi.org/10.1002/0471142727.mb3002s98. :Unit30.2.

101.

Billet K, Malinowska MA, Munsch T, Unlubayir M, Adler S, Delanoue G, et al. Semi-targeted metabolomics to validate biomarkers of grape downy mildew infection under field conditions. Plants. (Basel). 2020;9:1008. https://doi.org/10.3390/plants9081008.CrossRef

102.

Choi YH, Choi H-K, Hazekamp A, Bermejo P, Schilder Y, Erkelens C, et al. Quantitative analysis of bilobalide and ginkgolides from Ginkgo biloba Leaves and Ginkgo products using. Chem Pharm Bull. 2003;51:158–61. https://doi.org/10.1248/cpb.51.158.CrossRef

103.

Yang SY, Kim HK, Lefeber AW, Erkelens C, Angelova N, Choi YH, et al. Application of two-dimensional nuclear magnetic resonance spectroscopy to quality control of ginseng commercial products. Planta Med. 2006;72:364–9.CrossRefPubMed

104.

Booker A, Zhai L, Gkouva C, Li S, Heinrich M. From traditional resource to global commodities: a comparison of Rhodiola species using NMR spectroscopy-metabolomics and HPTLC. Front Pharmacol 2016;7. https://doi.org/10.3389/fphar.2016.00254.

105.

Booker A, Jalil B, Frommenwiler D, Reich E, Zhai L, Kulic Z, et al. The authenticity and quality of Rhodiola rosea products. Phytomedicine. 2016;23:754–62. https://doi.org/10.1016/j.phymed.2015.10.006.CrossRefPubMed

106.

Seethapathy GS, Tadesse M, Urumarudappa SKJ, Gunaga V, Vasudeva S, Malterud R. Authentication of Garcinia fruits and food supplements using DNA barcoding and NMR spectroscopy. Sci Rep. 2018;8:10561. https://doi.org/10.1038/s41598-018-28635-z.CrossRefPubMedPubMedCentral

107.

Windarsih A, Rohman A, Swasono RT. Application of 1H-NMR based metabolite fingerprinting and chemometrics for authentication of Curcuma longa adulterated with C. heyneana. J Appl Res Med Aromatic Plants. 2019;13:100203. https://doi.org/10.1016/j.jarmap.2019.100203.CrossRef

108.

Marchev AS, Koycheva IK, Aneva IY, Georgiev MI. Authenticity and quality evaluation of different Rhodiola species and commercial products based on NMR-spectroscopy and HPLC. Phytochem Anal. 2020;31:756–69. https://doi.org/10.1002/pca.2940.CrossRefPubMed

109.

Hebert PDN, Cywinska A, Ball SL, deWaard JR. Biological identifications through DNA barcodes. Proceedings of the Royal Society of London B: Biological Sciences 2003;270:313–21. https://doi.org/10.1098/rspb.2002.2218.

110.

Taberlet P, Coissac E, Pompanon F, Brochmann C, Willerslev E. Towards next-generation biodiversity assessment using DNA metabarcoding. Mol Ecol. 2012;21:2045–50. https://doi.org/10.1111/j.1365-294X.2012.05470.x.CrossRefPubMed

111.

Epp LS, Boessenkool S, Bellemain EP, Haile J, Esposito A, Riaz T, et al. New environmental metabarcodes for analysing soil DNA: potential for studying past and present ecosystems. Mol Ecol. 2012;21:1821–33. https://doi.org/10.1111/j.1365-294X.2012.05537.x.CrossRefPubMed

112.

Coghlan ML, White NE, Murray DC, Houston J, Rutherford W, Bellgard MI, et al. Metabarcoding avian diets at airports: implications for birdstrike hazard management planning. Invest Genet. 2013;4:27. https://doi.org/10.1186/2041-2223-4-27.CrossRef

113.

Nielsen UN, Wall DH. The future of soil invertebrate communities in polar regions: different climate change responses in the Arctic and Antarctic? Ecol Lett. 2013;16:409–19. https://doi.org/10.1111/ele.12058.CrossRefPubMed

114.

Soininen EM, Zinger L, Gielly L, Bellemain E, Bråthen KA, Brochmann C, et al. Shedding new light on the diet of norwegian lemmings: DNA metabarcoding of stomach content. Polar Biol. 2013;36:1069–76. https://doi.org/10.1007/s00300-013-1328-2.CrossRef

115.

Dormontt EE, van Dijk K, Bell KL, Biffin E, Breed MF, Byrne M et al. Advancing DNA barcoding and metabarcoding applications for plants requires systematic analysis of herbarium collections—an australian perspective. Front Ecol Evol 2018;6. https://doi.org/10.3389/fevo.2018.00134.

116.

Raclariu-Manolică AC, de Boer HJ. Chapter 8 - DNA barcoding and metabarcoding for quality control of botanicals and derived herbal products. In: Mukherjee PK, editor. Evidence-Based Validation of Herbal Medicine (Second Edition), Elsevier; 2022, p. 223–38. https://doi.org/10.1016/B978-0-323-85542-6.00004-4.

117.

Coghlan ML, Haile J, Houston J, Murray DC, White NE, Moolhuijzen P, et al. Deep sequencing of plant and animal DNA contained within traditional chinese medicines reveals legality issues and health safety oncerns. PLOS Genet. 2012;8:e1002657. https://doi.org/10.1371/journal.pgen.1002657.CrossRefPubMedPubMedCentral

118.

Coghlan ML, Maker G, Crighton E, Haile J, Murray DC, White NE, et al. Combined DNA, toxicological and heavy metal analyses provides an auditing toolkit to improve pharmacovigilance of traditional chinese medicine (TCM). Sci Rep. 2015;5:17457. https://doi.org/10.1038/srep17475.CrossRef

119.

Cheng X, Su X, Chen X, Zhao H, Bo C, Xu J, et al. Biological ingredient analysis of traditional chinese medicine preparation based on high-throughput sequencing: the story for Liuwei Dihuang Wan. Sci Rep. 2014;4:5147. https://doi.org/10.1038/srep05147.CrossRefPubMedPubMedCentral

120.

Ivanova NV, Kuzmina ML, Braukmann TWA, Borisenko AV, Zakharov EV. Authentication of herbal supplements using next-generation sequencing. PLoS ONE. 2016;11:e0156426. https://doi.org/10.1371/journal.pone.0156426.CrossRefPubMedPubMedCentral

121.

Raclariu AC, Mocan A, Popa MO, Vlase L, Ichim MC, Crisan G, et al. Veronica officinalis product authentication using DNA metabarcoding and HPLC-MS reveals widespread adulteration with Veronica chamaedrys. Front Pharmacol. 2017;8. https://doi.org/10.3389/fphar.2017.00378.

122.

Seethapathy GS, Raclariu-Manolica A-C, Anmarkrud JA, Wangensteen H, de Boer HJ. DNA metabarcoding authentication of ayurvedic herbal products on the european market raises concerns of quality and fidelity. Front Plant Sci. 2019;10. https://doi.org/10.3389/fpls.2019.00068.

123.

Robasky K, Lewis NE, Church GM. The role of replicates for error mitigation in next-generation sequencing. Nat Rev Genet. 2014;15:56–62. https://doi.org/10.1038/nrg3655.CrossRefPubMed

124.

Ficetola GF, Pansu J, Bonin A, Coissac E, Giguet-Covex C, De Barba M, et al. Replication levels, false presences and the estimation of the presence/absence from eDNA metabarcoding data. Mol Ecol Resour. 2015;15:543–56. https://doi.org/10.1111/1755-0998.12338.CrossRefPubMed

125.

Pawluczyk M, Weiss J, Links MG, Egaña Aranguren M, Wilkinson MD, Egea-Cortines M. Quantitative evaluation of bias in PCR amplification and next-generation sequencing derived from metabarcoding samples. Anal Bioanal Chem. 2015;407:1841–8. https://doi.org/10.1007/s00216-014-8435-y.CrossRefPubMed

126.

Novak J, Grausgruber-Gröger S, Lukas B. DNA-based authentication of plant extracts. Food Res Int. 2007;40:388–92. https://doi.org/10.1016/j.foodres.2006.10.015.CrossRef

127.

Särkinen T, Staats M, Richardson JE, Cowan RS, Bakker FT. How to open the treasure chest? Optimising DNA extraction from herbarium specimens. PLoS ONE. 2012;7:e43808.CrossRefPubMedPubMedCentral

128.

Costa J, Amaral JS, Fernandes TJR, Batista A, Oliveira MBPP, Mafra I. DNA extraction from plant food supplements: influence of different pharmaceutical excipients. Mol Cell Probes. 2015;29:473–8. https://doi.org/10.1016/j.mcp.2015.06.002.CrossRefPubMed

129.

Piñol J, Mir G, Gomez-Polo P, Agustí N. Universal and blocking primer mismatches limit the use of high-throughput DNA sequencing for the quantitative metabarcoding of arthropods. Mol Ecol Resour. 2015;15:819–30. https://doi.org/10.1111/1755-0998.12355.CrossRefPubMed

130.

Giguet-Covex C, Pansu J, Arnaud F, Rey P, Griggo C, Gielly L, et al. Long livestock farming history and human landscape shaping revealed by lake sediment DNA. Nat Communications; Lond. 2014;5:3211. https://doi.org/10.1038/ncomms4211.CrossRef

131.

Dobrovolny S, Uhlig S, Frost K, Schlierf A, Nichani K, Simon K, et al. Interlaboratory validation of a DNA metabarcoding assay for mammalian and poultry species to detect food adulteration. Foods. 2022;11:1108. https://doi.org/10.3390/foods11081108.CrossRefPubMedPubMedCentral

132.

Sgamma T, Lockie-Williams C, Kreuzer M, Williams S, Scheyhing U, Koch E, et al. DNA barcoding for industrial quality assurance. Planta Med. 2017;83:1117–29. https://doi.org/10.1055/s-0043-113448.CrossRefPubMed

133.

Raclariu-Manolica AC, Mauvisseau Q, De Boer H. Horizon scan of DNA-based methods for quality control and monitoring of herbal preparations. Front Pharmacol 2023;14. https://doi.org/10.3389/fphar.2023.1179099.

134.

Durazzo A, Sorkin BC, Lucarini M, Gusev PA, Kuszak AJ, Crawford C et al. Analytical challenges and metrological approaches to ensuring dietary supplement quality: International Perspectives. Frontiers in Pharmacology 2022;12.

135.

Raclariu AC, Ţebrencu CE, Ichim MC, Ciupercǎ OT, Brysting AK, de Boer H. What’s in the box? Authentication of Echinacea herbal products using DNA metabarcoding and HPTLC. Phytomedicine. 2018;44:32–8. https://doi.org/10.1016/j.phymed.2018.03.058.CrossRefPubMed

Title: Authentication of milk thistle commercial products using UHPLC-QTOF-ESI + MS metabolomics and DNA metabarcoding
Authors: Ancuța Cristina Raclariu-Manolică
Quentin Mauvisseau
Renato Paranaiba
Hugo J. De Boer
Carmen Socaciu
Publication date: 01-12-2023
Publisher: BioMed Central
Published in: BMC Complementary Medicine and Therapies / Issue 1/2023
Electronic ISSN: 2662-7671
DOI: https://doi.org/10.1186/s12906-023-04091-9

Keynote webinar | Spotlight on medication adherence

Springer Medicine

Authentication of milk thistle commercial products using UHPLC-QTOF-ESI + MS metabolomics and DNA metabarcoding

Abstract

Background

Methods

Results

Conclusion

Keynote webinar | Spotlight on medication adherence

Springer Medicine

Abstract

Background

Methods

Results

Conclusion

Please log in to get access to this content

Other articles of this Issue 1/2023

Biological activities of extracts and compounds from Thai Kae-Lae (Maclura cochinchinensis (Lour.) Corner)

The beneficial effects of simultaneous supplementation of Lactobacillus reuteri and calcium fluoride nanoparticles on ovariectomy-induced osteoporosis

Catechin, epicatechin, curcumin, garlic, pomegranate peel and neem extracts of Indian origin showed enhanced anti-inflammatory potential in human primary acute and chronic wound derived fibroblasts by decreasing TGF-β and TNF-α expression

Origanum majorana L. protects against neuroinflammation-mediated cognitive impairment: a phyto-pharmacological study

Traditional medicine users in a treated chronic disease population: a cross-sectional study in Indonesia

Combination of bioaffinity ultrafiltration-UFLC-ESI-Q/TOF-MS/MS, in silico docking and multiple complex networks to explore antitumor mechanism of topoisomerase I inhibitors from Artemisiae Scopariae Herba