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Rapid on-site TLC–SERS detection of four antidiabetes drugs used as adulterants in botanical dietary supplements

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Abstract

A novel facile method has been established for rapid on-site detection of antidiabetes chemicals used to adulterate botanical dietary supplements (BDS) for diabetes. Analytes and components of pharmaceutical matrices were separated by thin-layer chromatography (TLC) then surface-enhanced Raman spectroscopy (SERS) was used for qualitative identification of trace substances on the HPTLC plate. Optimization and standardization of the experimental conditions, for example the method used for preparation of silver colloids, the mobile phase, and the concentration of colloidal silver, resulted in a very robust and highly sensitive method which enabled successful detection when the amount of adulteration was as low as 0.001 % (w/w). The method was also highly selective, enabling successful identification of some chemicals in extremely complex herbal matrices. The established TLC–SERS method was used for analysis of real BDS used to treat diabetes, and the results obtained were verified by liquid chromatography–triple quadrupole mass spectrometry (LC–MS–MS). The study showed that TLC–SERS could be used for effective separation and detection of four chemicals used to adulterate BDS, and would have good prospects for on-site qualitative screening of BDS for adulterants.

Experimental procedure of TLC-SERS method

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References

  1. Schmidt BM, Ribnicky DM, Lipsky PE, Raskin I (2007) Revisiting the ancient concept of botanical therapeutics. Nat Chem Biol 3:360–366

    Article  CAS  Google Scholar 

  2. Jordan SA, Cunningham DG, Marles RJ (2010) Assessment, of herbal medicinal products: challenges, and opportunities to increase the knowledge base for safety assessment. Toxicol Appl Pharmacol 243:198–216

    Article  CAS  Google Scholar 

  3. Gardiner P, Phillips R, Shaughnessy AF (2008) Herbal and dietary supplement-drug interactions in patients with chronic illnesses. Am Fam Physician 77:73–8

    Google Scholar 

  4. Applequist WL, Miller JS (2013) Selection and authentication of botanical materials for the development of analytical methods. Anal Bioanal Chem 405:4419–28

    Article  CAS  Google Scholar 

  5. Venhuis B, Kaste D (2012) Towards a decade of detecting new analogues of sildenafil, tadalafil and vardenafil in food supplements: a history, analytical aspects and health risks. J Pharm Biomed Anal 69:196–205

    Article  CAS  Google Scholar 

  6. Chen Y, Zhao L, Lu F, Yu Y, Chai Y, Wu Y (2009) Determination of synthetic drugs used to adulterate botanical dietary supplements using QTRAP LC–MS–MS. Food Add Contam 26:595–603

    Article  CAS  Google Scholar 

  7. Pang W, Yang H, Wu Z, Huang M, Hu J (2009) LC–MS–MS in MRM mode for detection and structural identification of synthetic hypoglycemic drugs added illegally to ‘natural’ anti-diabetic herbal products. Chromatographia 70:1353–1359

    Article  CAS  Google Scholar 

  8. Cui M, Li N, Qin F, Li F, Xiong Z (2010) Simultaneous determination of 14 illegal adulterants in Chinese proprietary medicines using reversed-phase ion-pair LC. Chromatographia 72:1189–1194

    Article  CAS  Google Scholar 

  9. Zhou Z, Zhang J, Zhang W, Bai Y, Liu H (2011) Rapid screening for synthetic antidiabetic drug adulteration in herbal dietary supplements using direct analysis in real time mass spectrometry. Analyst 136:2613–2618

    Article  CAS  Google Scholar 

  10. Han X, Zhao B, Ozaki Y (2009) Surface-enhanced Raman scattering for protein detection. Anal Bioanal Chem 394:1719–1727

    Article  CAS  Google Scholar 

  11. Botti S, Cantarini L, Palucci A (2010) Surface-enhanced Raman spectroscopy for trace-level detection of explosives. J Raman Spectrosc 41:866–869

    Article  CAS  Google Scholar 

  12. Brosseau C, Rayner K, Casadio F, Grzywacz C, Van Duyne RP (2009) Surface-enhanced Raman spectroscopy: a direct method to identify colorants in various artist media. Anal Chem 81:7443–7447

    Article  CAS  Google Scholar 

  13. Zhang X, Zou M, Qi X, Liu F, Zhu X, Zhao B (2010) Detection of melamine in liquid milk using surface-enhanced Raman scattering spectroscopy. J Raman Spectrosc 41:1655–1660

    Article  Google Scholar 

  14. Lindahl I, Masson P (1990) Improved sample and reagent pipetting with the MINILAB. J Clin Chem Clin Biochem 28:949–950

    CAS  Google Scholar 

  15. Risha P, Msuya Z, Clark M, Johnson K (2008) The use of Minilabs to improve the testing capacity of regulatory authorities in resource limited settings: Tanzanian experience. Health policy 87:217–222

    Article  Google Scholar 

  16. Huang R, Han S, Li X (2013) Detection of tobacco-related biomarkers in urine samples by surface-enhanced Raman spectroscopy coupled with thin-layer chromatography. Anal Bioanal Chem 405:6815–6822

    Article  CAS  Google Scholar 

  17. Li D, Qu L, Zhai W, Xue J, Fossey J, Long Y (2011) Facile on-site detection of substituted aromatic pollutants in water using thin layer chromatography combined with surface-enhanced Raman spectroscopy. Environ Sci Technol 45:4046–4052

    Article  CAS  Google Scholar 

  18. Pozzi F, Shibayama N, Leona M, Lombardi J (2013) TLC–SERS study of Syrian rue (Peganum harmala) and its main alkaloid constituents. J Raman Spectrosc 44:102–107

    Article  CAS  Google Scholar 

  19. Lucotti A, Tommasini M, Casella M, Morganti A, Gramatica F, Zerbi G (2012) TLC-surface enhanced Raman scattering of apomorphine in human plasma. Vib Spectrosc 62:286–291

    Article  CAS  Google Scholar 

  20. Lee P, Meisel D (1982) Adsorption and surface-enhanced Raman of dyes on silver and gold sols. J Phys Chem 86:3391–3395

    Article  CAS  Google Scholar 

  21. Yin L, Zhang Y (2010) Character of the nano silver particles and the surface enhanced Raman of nano silver particles after adding different aggregating agent. Chin J Pharm Ana 30:2352–2355

    CAS  Google Scholar 

  22. Shirtclife N, Nickel U, Schneider S (1999) Reproducible preparation of silver sols with small particle size using borohydride reduction: for use as nuclei for preparation of larger particles. J Colloid Interface Sci 211:122–129

    Article  Google Scholar 

  23. Leopold N, Lendl B (2003) A new method for fast preparation of highly surface-enhanced Raman scattering (SERS) active silver colloids at room temperature by reduction of silver nitrate with hydroxylamine hydrochloride. J Phys Chem B 107:5723–5727

    Article  CAS  Google Scholar 

  24. István K, Keresztury G, Szép A (2003) Normal Raman and surface enhanced Raman spectroscopic experiments with thin layer chromatography spots of essential amino acids using different laser excitation sources. Spectrochim Acta A Mol Biomol Spectrosc 59:1709–1723

    Article  Google Scholar 

  25. Horváth E, Kátay G, Tyihák E, Kristóf J, Redey A (2000) Critical evaluation of experimental conditions influencing the surface-enhanced Raman spectroscopic (SERS) detection of substances separated by layer liquid chromatographic techniques. Chromatographia 51:297–301

    Article  Google Scholar 

  26. Trefry J, Monahan J, Weaver K, Meyerhoefer A, Markopolous M, Arnold Z, Wooley D, Pavel I (2010) Size selection and concentration of silver nanoparticles by tangential flow ultrafiltration for sers-based biosensors. J Am Chem Soc 132:10970–10972

    Article  CAS  Google Scholar 

  27. Wang J, Chen B, Yao S (2008) Analysis of six synthetic adulterants in herbal weight-reducing dietary supplements by LC electrospray ionization-MS. Food Add Contam 25:882–830

    Google Scholar 

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Acknowledgments

This project was supported by the Ministry of Science and Technology of the People’s Republic of China (grant no. 2012YQ180132) and Shanghai Municipal Science and Technology Commission (grant no. 11431922502). The authors wish to thank Mr Zhang Zhonghu from the Shandong Institute for Food and Drug Control for kindly providing all the real BDS samples. The opinions, findings, and conclusions or recommendations expressed in this publication are those of the authors and do not necessarily reflect those of the Department of Justice.

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Correspondence to Feng Lu.

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Zhu, Q., Cao, Y., Cao, Y. et al. Rapid on-site TLC–SERS detection of four antidiabetes drugs used as adulterants in botanical dietary supplements. Anal Bioanal Chem 406, 1877–1884 (2014). https://doi.org/10.1007/s00216-013-7605-7

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  • DOI: https://doi.org/10.1007/s00216-013-7605-7

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