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Preparation and comparison of Fe3O4@graphene oxide nanoclusters for analysis of glimepiride in urine by surface-assisted laser desorption/ionization time-of-flight mass spectrometry

Abstract

Graphene oxide (GO) has the ability to absorb certain compounds, and it can be modified with functional groups for different purposes; for instance, iron oxide (IO) nanoparticles can be used to concentrate analyte by a magnet. Recently, many kinds of GO have been developed, such as single-layer GO (SLGO), two-to-four layers of GO (i.e., few-layer GO, FLGO2–4), and four-to-eight layers of GO (i.e., multi-layer GO, MLGO4–8). However, the abilities of these layered GO coated with IO nanoparticles have not been investigated. In this study, we conducted a novel analysis of glimepiride by using layered GO-coated magnetic clusters of IO nanoparticles that were synthesized through a simple and facile emulsion-solvent evaporation method. The methodology is based on (i) enrichment of glimepiride using the layered GO-coated magnetic clusters of IO nanoparticles (IO@SLGO, IO@FLGO2–4, and IO@MLGO4–8), and (ii) rapid determination using magnetic cluster–based surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOFMS). We found that IO@MLGO4–8, the magnetic cluster with the greatest number of GO layers, had the best limit of detection (28.6 pmol/μL for glimepiride). The number of GO layers played a significant role in increasing the sensitivity of the SALDI-MS, indicating that the size of GO in the magnetic clusters contributed to the desorption/ionization efficiency. To the best of our knowledge, this is the first study to enrich glimepiride using magnetic clusters of different GO types and to show that the glimepiride in HLB purified urine adsorbed by magnetic clusters can be analyzed by SALDI-TOFMS.

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Abbreviations

CNT:

Carbon nanotubes

MTT:

3-(4,5-Dimethylthiazol-2yl)-2,5-diphenyltetrazolium bromide

FLGO:

Few-layer graphene oxide

GO:

Graphene oxide

IO:

Iron oxide

MLGO:

Multi-layer graphene oxide

SLGO:

Single-layer graphene oxide

SALDI-TOFMS:

Surface-assisted laser desorption/ionization time-of-flight mass spectrometry

TEM:

Transmission electron microscope

References

  1. Novoselov KS, Geim AK, Morozov S, Jiang D, Katsnelson M, Grigorieva I, et al. Two-dimensional gas of massless Dirac fermions in graphene. Nature. 2005;438(7065):197.

    CAS  PubMed  Google Scholar 

  2. Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, et al. Electric field effect in atomically thin carbon films. Sci. 2004;306(5696):666–9.

    CAS  Google Scholar 

  3. Zhang Y, Tan YW, Stormer HL, Kim P. Experimental observation of the quantum Hall effect and Berry’s phase in graphene. Nature. 2005;438(7065):201.

    CAS  PubMed  Google Scholar 

  4. Chen D, Tang L, Li J. Graphene-based materials in electrochemistry. Chem Soc Rev. 2010;39(8):3157–80.

    CAS  PubMed  Google Scholar 

  5. Pumera M. Electrochemistry of graphene: new horizons for sensing and energy storage. Chem Rec. 2009;9(4):211–23.

    CAS  PubMed  Google Scholar 

  6. Yang W, Ratinac KR, Ringer SP, Thordarson P, Gooding JJ, Braet F. Carbon nanomaterials in biosensors: should you use nanotubes or graphene? Angew Chem Int Ed Eng. 2010;49(12):2114–38.

    CAS  Google Scholar 

  7. Geim AK, Novoselov KS. The rise of graphene. Nat Mater. 2007;6(3):183.

    CAS  PubMed  Google Scholar 

  8. McCreery RL. Advanced carbon electrode materials for molecular electrochemistry. Chem Rev. 2008;108(7):2646–87.

    CAS  PubMed  Google Scholar 

  9. Zhu Y, Murali S, Cai W, Li X, Suk JW, Potts JR, et al. Graphene and graphene oxide: synthesis, properties, and applications. Adv Mater. 2010;22(35):3906–24.

    CAS  Google Scholar 

  10. Tang LAL, Wang J, Loh KP. Graphene-based SELDI probe with ultrahigh extraction and sensitivity for DNA oligomer. J Am Chem Soc. 2010;132(32):10976–7.

    CAS  PubMed  Google Scholar 

  11. Min Q, Zhang X, Chen X, Li S, Zhu JJ. N-doped graphene: an alternative carbon-based matrix for highly efficient detection of small molecules by negative ion MALDI-TOF MS. Anal Chem. 2014;86(18):9122–30.

    CAS  PubMed  Google Scholar 

  12. Kim JI, Park JM, Noh JY, Kang MJ, Pyun JC. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of small volatile molecules using a parylene-matrix chip. Rapid Commun Mass Spectrom. 2014;28(21):2301–6.

    CAS  PubMed  Google Scholar 

  13. Kim YK, Min DH. The structural influence of graphene oxide on its fragmentation during laser desorption/ionization mass spectrometry for efficient small-molecule analysis. Chem Eur J. 2015;21(19):7217–23.

    CAS  PubMed  Google Scholar 

  14. Zhang J, Zheng X, Ni Y. Selective enrichment and MALDI-TOF MS analysis of small molecule compounds with vicinal diols by boric acid-functionalized graphene oxide. J Am Soc Mass Spectrom. 2015;26(8):1291–8.

    CAS  PubMed  Google Scholar 

  15. Liu P, Hu Y, Chen J, Yang Q. Direct detection of the anti-cancer drug 9-phenylacridine in tissues by graphite rod laser desorption vacuum-ultraviolet post-ionization mass spectrometry. Rapid Commun Mass Spectrom. 2015;29(14):1328–34.

    CAS  PubMed  Google Scholar 

  16. Zhou D, Guo S, Zhang M, Liu Y, Chen T, Li Z. Mass spectrometry imaging of small molecules in biological tissues using graphene oxide as a matrix. Anal Chim Acta. 2017;962:52–9.

    CAS  PubMed  Google Scholar 

  17. Lee J, Kim YK, Min DH. Laser desorption/ionization mass spectrometric assay for phospholipase activity based on graphene oxide/carbon nanotube double-layer films. J Am Chem Soc. 2010;132(42):14714–7.

    CAS  PubMed  Google Scholar 

  18. Liu CW, Chien MW, Su CY, Chen HY, Li LJ, Lai CC. Analysis of flavonoids by graphene-based surface-assisted laser desorption/ionization time-of-flight mass spectrometry. Analyst. 2012;137(24):5809–16.

    CAS  PubMed  Google Scholar 

  19. Liu Y, Liu J, Yin P, Gao M, Deng C, Zhang X. High throughput identification of components from traditional Chinese medicine herbs by utilizing graphene or graphene oxide as MALDI-TOF-MS matrix. J Mass Spectrom. 2011;46(8):804–15.

    CAS  PubMed  Google Scholar 

  20. Lu M, Lai Y, Chen G, Cai Z. Matrix interference-free method for the analysis of small molecules by using negative ion laser desorption/ionization on graphene flakes. Anal Chem. 2011;83(8):3161–9.

    CAS  PubMed  Google Scholar 

  21. Shi C, Meng J, Deng C. Enrichment and detection of small molecules using magnetic graphene as an adsorbent and a novel matrix of MALDI-TOF-MS. Chem Commun. 2012;48(18):2418–20.

    CAS  Google Scholar 

  22. Korpany KV, Habib F, Murugesu M, Blum AS. Stable water-soluble iron oxide nanoparticles using Tiron. Mater Chem Phys. 2013;138(1):29–37.

    CAS  Google Scholar 

  23. Chang SY, Zheng NY, Chen CS, Chen CD, Chen YY, Wang CC. Analysis of peptides and proteins affinity-bound to iron oxide nanoparticles by MALDI MS. J Am Soc Mass Spectrom. 2007;18(5):910–8.

    CAS  PubMed  Google Scholar 

  24. Sha Y, Huang D, Zheng S, Deng C. Development of magnetic graphene as an adsorbent and matrix for selective enrichment and detection of crotonaldehyde in saliva by MALDI-TOF-MS. Anal Methods. 2013;5(18):4585–90.

    CAS  Google Scholar 

  25. Zhang H, Cha S, Yeung ES. Colloidal graphite-assisted laser desorption/ionization MS and MS n of small molecules. 2. Direct profiling and MS imaging of small metabolites from fruits. Anal Chem. 2007;79(17):6575–84.

    CAS  PubMed  Google Scholar 

  26. Sleno L, Volmer DA. Some fundamental and technical aspects of the quantitative analysis of pharmaceutical drugs by matrix-assisted laser desorption/ionization mass spectrometry. Rapid Commun Mass Spectrom. 2005;19(14):1928–36.

    CAS  PubMed  Google Scholar 

  27. Dattelbaum AM, Iyer S. Surface-assisted laser desorption/ionization mass spectrometry. Expert Rev Proteomics. 2006;3(1):153–61.

    CAS  PubMed  Google Scholar 

  28. Sunner J, Dratz E, Chen YC. Graphite surface-assisted laser desorption/ionization time-of-flight mass spectrometry of peptides and proteins from liquid solutions. Anal Chem. 1995;67(23):4335–42.

    CAS  PubMed  Google Scholar 

  29. Chen WY, Chen YC. Affinity-based mass spectrometry using magnetic iron oxide particles as the matrix and concentrating probes for SALDI MS analysis of peptides and proteins. Anal Bioanal Chem. 2006;386(3):699–704.

    CAS  PubMed  Google Scholar 

  30. Ren SF, Guo YL. Oxidized carbon nanotubes as matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometric analysis of biomolecules. Rapid Commun Mass Spectrom. 2005;19(2):255–60.

    CAS  PubMed  Google Scholar 

  31. Xu S, Li Y, Zou H, Qiu J, Guo Z, Guo B. Carbon nanotubes as assisted matrix for laser desorption/ionization time-of-flight mass spectrometry. Anal Chem. 2003;75(22):6191–5.

    CAS  PubMed  Google Scholar 

  32. Kinumi T, Saisu T, Takayama M, Niwa H. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry using an inorganic particle matrix for small molecule analysis. J Mass Spectrom. 2000;35(3):417–22.

    CAS  PubMed  Google Scholar 

  33. Kim JH, Gang WG. Use of graphite plate for homogeneous sample preparation in matrix/surface-assisted laser desorption and ionization of polypropyleneglycol and polystyrene. Bull Kor Chem Soc. 2000;21(4):401–4.

    CAS  Google Scholar 

  34. Pan XY, Chen CH, Chang YH, Wang DY, Lee YC, Liou CC, et al. Osteoporosis risk assessment using multilayered gold-nanoparticle thin film via SALDI-MS measurement. Anal Bioanal Chem. 2019;411(13):2793–802.

    CAS  PubMed  Google Scholar 

  35. Kuo TR, Chen YC, Wang CI, Shen TH, Wang HY, Pan XY, et al. Highly oriented Langmuir–Blodgett film of silver cuboctahedra as an effective matrix-free sample plate for surface-assisted laser desorption/ionization mass spectrometry. Nanoscale. 2017;9(31):11119–25.

    CAS  PubMed  Google Scholar 

  36. Noh K, Kim E, Jeong T, Na M, Baek MC, Liu KH, et al. Simultaneous determination of glimepiride and its metabolites in human plasma by liquid chromatography coupled to a tandem mass spectrometry. Arch Pharm Res. 2011;34(12):2073–8.

    CAS  PubMed  Google Scholar 

  37. Mistri HN, Jangid AG, Shrivastav PS. Liquid chromatography tandem mass spectrometry method for simultaneous determination of antidiabetic drugs metformin and glyburide in human plasma. J Pharm Biomed Anal. 2007;45(1):97–106.

    CAS  PubMed  Google Scholar 

  38. Dotsikas Y, Kousoulos C, Tsatsou G, Loukas YL. Development of a rapid method for the determination of glimepiride in human plasma using liquid-liquid extraction based on 96-well format micro-tubes and liquid chromatography/tandem mass spectrometry. Rapid Commun Mass Spectrom. 2005;19(14):2055–61.

    CAS  PubMed  Google Scholar 

  39. Hoizey G, Lamiable D, Trenque T, Robinet A, Binet L, Kaltenbach ML, et al. Identification and quantification of 8 sulfonylureas with clinical toxicology interest by liquid chromatography–ion-trap tandem mass spectrometry and library searching. Clin Chem. 2005;51(9):1666–72.

    CAS  PubMed  Google Scholar 

  40. Ho EN, Yiu KC, Wan TS, Stewart BD, Watkins KL. Detection of anti-diabetics in equine plasma and urine by liquid chromatography–tandem mass spectrometry. J Chromatogr B. 2004;811(1):65–73.

    CAS  Google Scholar 

  41. Kundlik M, Zaware B, Kuchekar S. Rapid and specific approach for direct measurement of glimepiride in human plasma by LC–ESI-MS–MS employing automated 96 well format: application to a bioequivalence study. J Chromatogr Sci. 2012;50(1):64–70.

    CAS  PubMed  PubMed Central  Google Scholar 

  42. Sun S, Zeng H. Size-controlled synthesis of magnetite nanoparticles. J Am Chem Soc. 2002;124(28):8204–5.

    CAS  PubMed  Google Scholar 

  43. Lai SM, Hsiao JK, Yu HP, Lu CW, Huang CC, Shieh MJ, et al. Polyethylene glycol-based biocompatible and highly stable superparamagnetic iron oxide nanoclusters for magnetic resonance imaging. J Mater Chem. 2012;22(30):15160–7.

    CAS  Google Scholar 

  44. Zhang L, Li X, Huang Y, Ma Y, Wan X, Chen Y. Controlled synthesis of few-layered graphene sheets on a large scale using chemical exfoliation. Carbon. 2010;48(8):2367–71.

    CAS  Google Scholar 

  45. Kim YK, Min DH. Mechanistic study of laser desorption/ionization of small molecules on graphene oxide multilayer films. Langmuir. 2014;30(42):12675–83.

    CAS  PubMed  Google Scholar 

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Acknowledgments

This work was financially supported by the Ministry of Science and Technology and the Advanced Plant Biotechnology Center from The Featured Areas Research Center Program within the framework of the Higher Education Sprout Project by the Ministry of Education (MOE) in Taiwan, R.O.C.

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Chien, HJ., Lai, SM., Wang, WC. et al. Preparation and comparison of Fe3O4@graphene oxide nanoclusters for analysis of glimepiride in urine by surface-assisted laser desorption/ionization time-of-flight mass spectrometry. Anal Bioanal Chem 412, 4057–4065 (2020). https://doi.org/10.1007/s00216-020-02611-x

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Keywords

  • SALDI
  • Nanocluster
  • Iron oxide
  • Graphene oxide
  • Mass spectrometry
  • Glimepiride