Skip to main content
SpringerLink
Log in

Combined host-guest complex with coffee-ring effect for constructing ultrasensitive SERS substrate for phenformin hydrochloride detection in healthcare products

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Phenformin hydrochloride (PHE), once used as a traditional anti-diabetic drug, has now been banned due to significant side effects. However, the phenomenon of the illegal addition of PHE to hypoglycemic healthcare products is still rampant. Thus, the detection of illegally added PHE is urgently needed. Surface-enhanced Raman scattering (SERS) is a promising candidate for this purpose, but the weak affinity between PHE and bare metal (Au or Ag) limits direct SERS detection of PHE. In this paper, we prepared Ag nanoparticles coated with β-cyclodextrin (AgNP@β-CD), which display the coffee-ring effect, that can be used for PHE sensing. β-CD-functionalized nanoparticles could capture the analyte and fix the molecular orientation in the hydrophobic cavity. The coffee-ring effect could improve the SERS effect through a higher concentration of the analyte, higher density of nanoparticles, and more hot spots. The SERS performance of the AgNP@β-CD substrate was characterized by using o-phenylenediamine dihydrochloride as a probe molecule. The excitation wavelength and pH value were optimized. A linear response for PHE detection is in the 7.0 × 10−8–1.0 × 10−6 mol L−1 concentration range, and the limit of detection is as low as 8.0 × 10−9 mol L−1. This AgNP@β-CD coffee-ring effect substrate was applied to the detection of PHE in healthcare products, with recoveries between 95.3 and 105.0% and relative standard deviations of less than 5.16%. It is anticipated that the AgNP@β-CD substrate will also have great potential for the monitoring of other aromatic drugs in healthcare products.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Si KJ, Guo P, Shi Q, Cheng W. Self-assembled nanocube-based plasmene nanosheets as soft surface-enhanced raman scattering substrates toward direct quantitative drug identification on surfaces. Anal Chem. 2015;87(10):5263–9.

    Article  CAS  Google Scholar 

  2. Lai EPC, Feng SY. Molecularly imprinted solid phase extraction for rapid screening of metformin. Microchem J. 2003;75(3):159–68.

    Article  CAS  Google Scholar 

  3. Chen Y, Zhao L, Lu F, Yu Y, Chai Y, Wu Y. Determination of synthetic drugs used to adulterate botanical dietary supplements using QTRAP LC-MS/MS. Food Addit Contam. 2009;26(5):595–603.

    Article  CAS  Google Scholar 

  4. Pang W, Yang H, Wu Z, Huang M, Hu J. LC-MS–MS in MRM mode for detection and structural identification of synthetic hypoglycemic drugs added illegally to ‘natural’ anti-diabetic herbal products. Chromatographia. 2009;70(9):1353–9.

    Article  CAS  Google Scholar 

  5. Cui M, Li N, Qin F, Li F, Xiong Z. Simultaneous determination of 14 illegal adulterants in Chinese proprietary medicines using reversed-phase ion-pair LC. Chromatographia. 2010;72(11):1189–94.

    Article  CAS  Google Scholar 

  6. Fang F, Qi Y, Lu F, Yang L. Highly sensitive on-site detection of drugs adulterated in botanical dietary supplements using thin layer chromatography combined with dynamic surface enhanced Raman spectroscopy. Talanta. 2016;146:351–7.

    Article  CAS  Google Scholar 

  7. Liu Z, Jia F, Wang W, Wang C, Liu Y. Determination of phenformin hydrochloride using molecular imprinting technology coupled with flow-injection chemiluminescence. Lumin J Biol Chem Lumin. 2012;27(4):297–301.

    Article  Google Scholar 

  8. Shi L, Xie J-H, Du L-M, Y-x C, Wu H. Determination of phenformin hydrochloride employing a sensitive fluorescent probe. Spectrochim Acta Part A. 2016;162:98–104.

    Article  CAS  Google Scholar 

  9. Lin JH, Lin YT, huang YJ. Isolation and cytotoxicity of flavonoids from Daphnis genkwae flos. J Food Drug Anal. 2001;9(1):6–11.

    CAS  Google Scholar 

  10. Boeglin A, Fort A, Mager L, Combellas C, Thiébault A, Rodriguez V. Geometrical structure and nonlinear optical response of a zwitterionic push–pull biphenyl compound. Chem Phys. 2002;282(3):353–60.

    Article  CAS  Google Scholar 

  11. Patze S, Huebner U, Liebold F, Weber K, Cialla-May D, Popp J. SERS as an analytical tool in environmental science: the detection of sulfamethoxazole in the nanomolar range by applying a microfluidic cartridge setup. Anal Chim Acta. 2017;949:1–7.

    Article  CAS  Google Scholar 

  12. Yunker PJ, Still T, Lohr MA, Yodh AG. Suppression of the coffee-ring effect by shape-dependent capillary interactions. Nature. 2011;476:308.

    Article  CAS  Google Scholar 

  13. Yueksel S, Schwenke AM, Soliveri G, Ardizzone S, Weber K, Cialla-May D. Trace detection of tetrahydrocannabinol (THC) with a SERS-based capillary platform prepared by the in situ microwave synthesis of AgNPs. Anal Chim Acta. 2016;939:93–100.

    Article  CAS  Google Scholar 

  14. Wang W, Yin Y, Tan Z, Liu J. Coffee-ring effect-based simultaneous SERS substrate fabrication and analyte enrichment for trace analysis. Nanoscale. 2014;6(16):9588–93.

    Article  CAS  Google Scholar 

  15. Sun C, Chen T, Ruan W, Zhao B, Cong Q. Controlling the orientation of probe molecules on surface-enhanced Raman scattering substrates: a novel strategy to improve sensitivity. Anal Chim Acta. 2017;994:65–72.

    Article  CAS  Google Scholar 

  16. Zhang Y, Huang X, Liu W, Cheng Z, Chen C, Yin L. Analysis of drugs illegally added into Chinese traditional patent medicine using surface-enhanced Raman scattering. Anal Sci. 2013;29(10):985–90.

    Article  CAS  Google Scholar 

  17. Shi Y, Liu W, Chen C. Two-step centrifugation method for subpicomolar surface-enhanced Raman scattering detection. Anal Chem. 2016;88(9):5009–15.

    Article  CAS  Google Scholar 

  18. Yang K-H, Liu Y-C, Yu C-C. Simple strategy to improve surface-enhanced Raman scattering based on electrochemically prepared roughened silver substrates. Langmuir. 2010;26(13):11512–7.

    Article  CAS  Google Scholar 

  19. Xie Y, Wang X, Han X, Xue X, Ji W, Qi Z. Sensing of polycyclic aromatic hydrocarbons with cyclodextrin inclusion complexes on silver nanoparticles by surface-enhanced Raman scattering. Analyst. 2010;135(6):1389–94.

    Article  CAS  Google Scholar 

  20. Loftsson T, Brewster ME. Pharmaceutical applications of cyclodextrins. 1. Drug solubilization and stabilization. J Pharm Sci. 1996;85(10):1017–25.

    Article  CAS  Google Scholar 

  21. Loftsson T, Magnúsdóttir A, Másson M, Sigurjónsdóttir JF. Self-association and cyclodextrin solubilization of drugs. J Pharm Sci. 2002;91(11):2307–16.

    Article  CAS  Google Scholar 

  22. Stiles PL, Dieringer JA, Shah NC, Duyne RPV. Surface-enhanced Raman spectroscopy. Annu Rev Anal Chem. 2008;1(1):601–26.

    Article  CAS  Google Scholar 

  23. Halvorson RA, Vikesland PJ. Drop coating deposition Raman (DCDR) for microcystin-LR identification and quantitation. Environ Sci Technol. 2011;45(13):5644–51.

    Article  CAS  Google Scholar 

  24. Han W, Lin Z. Learning from “coffee-rings”: ordered structures enabled by controlled evaporative self-assembly. Angew Chem Int Ed. 2012;51(7):1534–46.

    Article  CAS  Google Scholar 

  25. Zhu Q, Yu X, Wu Z, Lu F, Yuan Y. Antipsychotic drug poisoning monitoring of clozapine in urine by using coffee-ring effect based surface-enhanced Raman spectroscopy. Anal Chim Acta. 2018;1014:64–1070.

    Article  CAS  Google Scholar 

  26. Andrade PF, de Faria AF, da Silva DS, Bonacin JA, Gonçalves MC. Structural and morphological investigations of β-cyclodextrin-coated silver nanoparticles. Colloids Surf B. 2014;118:289–97.

    Article  CAS  Google Scholar 

  27. Lee PC, Meisel D. Adsorption and surface-enhanced Raman of dyes on silver and gold sols. J Phys Chem. 1982;86:3391.

    Article  CAS  Google Scholar 

  28. Egyed O. Spectroscopic studies on β-cyclodextrin. Vib Spectrosc. 1990;1(2):225–7.

    Article  CAS  Google Scholar 

  29. Schneider H-J, Hacket F, Rüdiger V, Ikeda H. NMR studies of cyclodextrins and cyclodextrin complexes. Chem Rev. 1998;98(5):1755–86.

    Article  CAS  Google Scholar 

  30. Qiu B, Hu J, Yin L, Zhang Y. Study of phenformin hydrochloride by surface-enhanced Raman scattering. Chin Pharm. 2013;16(4):552–5.

    CAS  Google Scholar 

  31. Pan X, Dong J, Li Y, Sun X, Yuan C, Qian W. The strategy of two-scale interface enrichment for constructing ultrasensitive SERS substrates based on the coffee-ring effect of AgNP@β-CD. RSC Adv. 2016;6(35):29586–91.

    Article  CAS  Google Scholar 

  32. Kim DJ, Jeon TY, Park S-G, Han HJ, Im SH, Kim D-H. Uniform microgels containing agglomerates of silver nanocubes for molecular size-selectivity and high SERS activity. Small. 2017;13(23):1604048.

    Article  Google Scholar 

  33. Premkumar R, Premkumar S, Rekha TN, Parameswari A, Mathavan T, Benial AMF. Surface Enhanced Raman Spectroscopic Studies on Aspirin : An Experimental and Theoretical Approach. AIP Conference Proceedings, 2016; https://doi.org/10.1063/1.4946664

Download references

Funding

This work was financially supported by the Science-Technology Development Project of Jilin Province of China (No.20170101174JC) and the National Natural Science Foundation (Grants 21,327,803, 21,773,080, 21,711,540,292) of the People’s Republic of China.

Author information

Authors and Affiliations

  1. College of Chemistry, Jilin University, Changchun, 130012, Jilin, China

    Lixia Zhang, Xiangfeng Bu, Jiawei Wu & Yuan Tian

  2. Institute of Theoretical Chemistry, Jilin University, Changchun, 130012, Jilin, China

    Lixia Zhang

  3. State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun, 130012, Jilin, China

    Peng Li, Xiaolei Zhang & Bing Zhao

Authors
  1. Lixia Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Peng Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xiangfeng Bu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jiawei Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Xiaolei Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Bing Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yuan Tian
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yuan Tian.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Electronic supplementary material

ESM 1

(PDF 756 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, L., Li, P., Bu, X. et al. Combined host-guest complex with coffee-ring effect for constructing ultrasensitive SERS substrate for phenformin hydrochloride detection in healthcare products. Anal Bioanal Chem 410, 7599–7609 (2018). https://doi.org/10.1007/s00216-018-1399-6

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-018-1399-6

Keywords

Search

Navigation