, Volume 81, Issue 6, pp 861–869 | Cite as

Development of Graphene Oxide Functionalized Cotton Fiber Based Solid Phase Extraction Combined with Liquid Chromatography-Fluorescence Detection for Determination of Trace Auxins in Plant Samples

  • Qiulian Zeng
  • Yuji Ruan
  • Lingshun Sun
  • Fuyou Du
  • Lin Guo
  • Zhenfang Cheng
  • Guihua Ruan
  • Jianping Li


In this work, a convenient and sensitive solid phase extraction (SPE) method was developed based on graphene oxide functionalized cotton fiber (GO-CF), a SPE sorbent followed by liquid chromatography-fluorescence detection (LC-FLD) for determination of trace indole acetic acid, indole propionic acid, indole butyric acid and naphthalene acetic acid. GO-CF was synthesized via covalent bonding method on the surface of cotton fiber, and exhibited higher extraction capacity in comparison with that of cotton fiber. The conditions affecting the extraction efficiency, including sample pH, elution solvent, elution volume, extraction time, and sample volume, were optimized to obtain high extraction recoveries. Under optimal conditions, the calibration curves were linear over the concentration ranging from 2 to 200 ng mL−1 with correlation coefficients between 0.9987 and 0.9998 for all the analytes. The limits of detection were lower than 0.371 ng mL−1 for the four auxins. The intra- and inter-day relative standard deviations (RSDs) were less than 3.5 and 7.1%, respectively. The mean recoveries ranged from 73.5 to 105.4% with RSDs lower than 12.6%. The developed GO-CF–SPE–LC-FLD method has been successfully applied to the analysis of four auxins in real plant samples, including mung bean stalk, mung bean sprout, and tobacco leaf samples.

Graphical abstract


Graphene oxide Cotton fiber Sample preparation Solid phase extraction Auxin 



This study was funded by the National Natural Science Foundation of China (Grant nos. 21465008, 21265004, and 21665006), the Natural Science Foundation from Guangxi Zhuang Autonomous Region (nos. 2015GXNSFAA139024 and 2015GXNSFFA139005), the Project of High Level Innovation Team and Outstanding Scholar in Guangxi Colleges and Universities (Guijiaoren[2014]49), and the Guangxi Colleges and Universities Key Laboratory of Food Safety and Detection.

Compliance with Ethical Standards

Conflict of interest

The authors declare no conflict of interest.

Ethical approval

This article does not contain any studies with human participants performed by any of the authors.

Informed consent

Informed consent was not applicable.

Supplementary material

10337_2018_3518_MOESM1_ESM.doc (116 kb)
Supplementary material 1 (DOC 115 kb)


  1. 1.
    Woodward AW, Bartel B (2005) Auxin: regulation, action, and interaction. Ann Bot 95:707–735CrossRefGoogle Scholar
  2. 2.
    Teale WD, Paponov I, Palme K (2006) Auxin in action: signalling, transport and the control of plant growth and development. Nat Rev Mol Cell Biol 7:847–859CrossRefGoogle Scholar
  3. 3.
    Rozov SM, Zagorskaya AA, Deineko EV, Shumny VK (2013) Auxin: regulation and its modulation pathways. Biol Bull Rev 3:423–430CrossRefGoogle Scholar
  4. 4.
    Bai Y, Du F, Liu H (2010) Determination strategies of phytohormones: recent advances. Anal Methods 2:1867–1873CrossRefGoogle Scholar
  5. 5.
    Du F, Ruan G, Liu H (2012) Analytical methods for tracing plant hormones. Anal Bioanal Chem 403:55–74CrossRefGoogle Scholar
  6. 6.
    Porfírio S, Silva MDRG, Peixe A, Cabrita MJ, Azadi P (2016) Current analytical methods for plant auxin quantification—a review. Anal Chim Acta 902:8–21CrossRefGoogle Scholar
  7. 7.
    Yang L, Chen Y, Zhao S, Zhang W, Du H, Deng Z, Zhang S (2016) Simultaneous determination of indole-3-acetic acid and indole-3-butyric acid in plant by field-amplified sample stacking open-tubular capillary electrochromatography based on solid-phase extraction with calixarene sorbent. Chromatographia 79:243–254CrossRefGoogle Scholar
  8. 8.
    Augusto F, Hantao LW, Mogollón NGS, Braga SCGN (2013) New materials and trends in sorbents for solid-phase extraction. Trends Anal Chem 43:14–23CrossRefGoogle Scholar
  9. 9.
    Płotka-Wasylka J, Szczepańska N, Guardia MDL, Namieśnik J (2016) Modern trends in solid phase extraction: new sorbent media. Trends Anal Chem 77:23–43CrossRefGoogle Scholar
  10. 10.
    Zhang Y, Li Y, Hu Y, Li G, Chen Y (2010) Preparation of magnetic indole-3-acetic acid imprinted polymer beads with 4-vinylpyridine and β-cyclodextrin as binary monomer via microwave heating initiated polymerization and their application to trace analysis of auxins in plant tissues. J Chromatogr A 1217:7337–7344CrossRefGoogle Scholar
  11. 11.
    Hu Y, Li Y, Zhang Y, Li G, Chen Y (2011) Development of sample preparation method for auxin analysis in plants by vacuum microwave-assisted extraction combined with molecularly imprinted clean-up procedure. Anal Bioanal Chem 399:3367–3374CrossRefGoogle Scholar
  12. 12.
    Wang M, Chang X, Wu X, Yan H, Qiao F (2016) Water-compatible dummy molecularly imprinted resin prepared in aqueous solution for green miniaturized solid-phase extraction of plant growth regulators. J Chromatogr A 1458:9–17CrossRefGoogle Scholar
  13. 13.
    Cao J, Yan H, Shen S, Bai L, Liu H, Qiao F (2016) Hydrophilic molecularly imprinted melamine–urea–formaldehyde monolithic resin prepared in water for selective recognition of plant growth regulators. Anal Chim Acta 943:136–145CrossRefGoogle Scholar
  14. 14.
    Campanella B, Pulidori E, Onor M, Passaglia E, Tegli S, Izquierdo CG, Bramanti E (2016) New polymeric sorbent for the solid-phase extraction of indole-3-acetic acid from plants followed by liquid chromatography-fluorescence detector. Microchem J 128:68–74CrossRefGoogle Scholar
  15. 15.
    Wang LH, Wang MY, Yan HY, Yuan Y, Tian J (2014) A new graphene oxide/polypyrrole foam material with pipette-tip solid-phase extraction for determination of three auxins in papaya juice. J Chromatogr A 1368:37–43CrossRefGoogle Scholar
  16. 16.
    Li N, Chen J, Shi YP (2016) Magnetic reduced graphene oxide functionalized with β-cyclodextrin as magnetic solid-phase extraction adsorbents for the determination of phytohormones in tomatoes coupled with high performance liquid chromatography. J Chromatogr A 1441:24–33CrossRefGoogle Scholar
  17. 17.
    Zhang X, Niu J, Zhang X, Xiao R, Lu M, Cai Z (2017) Graphene oxide–SiO2 nanocomposite as the adsorbent for extraction and preconcentration of plant hormones for HPLC analysis. J Chromatogr B 1046:58–64CrossRefGoogle Scholar
  18. 18.
    Liu L, Xia L, Wu C, Qu F, Li G (2016) Zirconium (IV)-based metal organic framework (UIO-67) as efficient sorbent in dispersive solid phase extraction of plant growth regulator from fruits coupled with HPLC fluorescence detection. Talanta 154:23–30CrossRefGoogle Scholar
  19. 19.
    Sheikhian L, Bina S (2016) Simultaneous extraction and HPLC determination of 3-indole butyricacid and 3-indole acetic acid in pea plant by using ionic liquid-modified silica as sorbent. J Chromatogr B 1009–1010:34–43CrossRefGoogle Scholar
  20. 20.
    Dreyer DR, Todd AD, Bielawski CW (2014) Harnessing the chemistry of graphene oxide. Chem Soc Rev 43:5288–5301CrossRefGoogle Scholar
  21. 21.
    Toffoli AL, Maciel EVS, Fumes BH, Lanças FM (2018) The role of graphene-based sorbents in modern sample preparation techniques. J Sep Sci 41:288–302CrossRefGoogle Scholar
  22. 22.
    Liu J, Chi Y, Jiang G, Tai C, Hu J (2004) Use of cotton as a sorbent for on-line precolumn enrichment of polycyclic aromatic hydrocarbons in waters prior to liquid chromatography determination. Microchem J 77:19–22CrossRefGoogle Scholar
  23. 23.
    Wang J, Liu S, Chen C, Zou Y, Hu H, Cai Q, Yao S (2014) Natural cotton fibers as adsorbent for solid-phase extraction of polycyclic aromatic hydrocarbons in water samples. Analyst 139:3593–3599CrossRefGoogle Scholar
  24. 24.
    Heidari N, Ghiasvand A, Abdolhosseini S (2017) Amino-silica/graphene oxide nanocomposite coated cotton as an efficient sorbent for needle trap device. Anal Chim Acta 975:11–19CrossRefGoogle Scholar
  25. 25.
    Montesinos I, Sfakianaki A, Gallego M, Stalikas CD (2015) Graphene-coated cotton fibers as a sorbent for the extraction of multiclass pesticide residues from water and their determination by gas chromatography with mass spectrometry. J Sep Sci 38:836–843CrossRefGoogle Scholar
  26. 26.
    Chen J, Yao B, Li C, Shi G (2013) An improved Hummers method for eco-friendly synthesis of graphene oxide. Carbon 64:225–229CrossRefGoogle Scholar
  27. 27.
    Ma Z, Ge L, Lee ASY, Yong JWH, Tana SN, Ong ES (2008) Simultaneous analysis of different classes of phytohormones in coconut (Cocos nucifera L.) water using high-performance liquid chromatography and liquid chromatography–tandem mass spectrometry after solid-phase extraction. Anal Chim Acta 610:274–281CrossRefGoogle Scholar
  28. 28.
    Kojima M, Kamada-Nobusada T, Komatsu H, Takei K, Kuroha T, Mizutani M, Ashikari M, Ueguchi-Tanaka M, Matsuoka M, Suzuki K, Sakakibara H (2009) Highly sensitive and high-throughput analysis of plant hormones using MS-probe modification and liquid chromatography–tandem mass spectrometry: an application for hormone profiling in Oryza sativa. Plant Cell Physiol 50:1201–1214CrossRefGoogle Scholar
  29. 29.
    Mao X, Tang L, Tan T, Wan Y (2014) Determination of plant growth regulators in pears by microwave-assisted extraction and liquid chromatography with electrospray ionization mass spectrometry. J Sep Sci 37:1352–1358CrossRefGoogle Scholar
  30. 30.
    Zhong Q, Qiu X, Lin C, Shen L, Huo Y, Zhan S, Yao J, Huang T, Kawano S, Hashi Y, Xiao L, Zhou T (2014) An automatic versatile system integrating solid-phase extraction with ultra-high performance liquid chromatography–tandem mass spectrometry using a dual-dilution strategy for direct analysis of auxins in plant extracts. J Chromatogr A 1359:131–139CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and BioengineeringGuilin University of TechnologyGuilinChina
  2. 2.School of Biomedical EngineeringSouthern Medical UniversityGuangzhouChina

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