Molecularly Imprinted Polymers with Dual Template and Bifunctional Monomers for Selective and Simultaneous Solid-Phase Extraction and Gas Chromatographic Determination of Four Plant Growth Regulators in Plant-Derived Tissues and Foods

  • Chengjun WangEmail author
  • Chuyuan Ding
  • Qiwei Wu
  • Xiyao Xiong


A highly selective and sensitive molecularly imprinted polymer (MIP)-based solid-phase extraction (SPE) combined with gas chromatographic (GC) detection method was developed for the simultaneous isolation and determination of four plant growth regulators (PGRs) including indole-3-acetic acid (IAA), indole-3-butyric acid (IBA), 1-naphthaleneacetic acid (NAA), and 2,4-dichlorophenoxyacetic acid (2,4-D) in plant tissues, fruits, and vegetables. The MIP composites, synthesized by application of dual template molecules (IAA and 2,4-D) and bifunctional monomers β-cyclodextrin (β-CD) and methacrylic acid (MAA), were characterized by FTIR, BET, XRD, SEM, and TGA techniques. The effects of the amount of adsorbent, sample pH, and eluent solvents on the SPE performance were investigated. Under the optimal SPE condition, the β-CD/MAA-MIPs exhibited higher selective capability and greater adsorption capacity toward target PGRs when compared with commercial SPE adsorbents, single template, and functional monomer MIPs. In addition, the stability and reusability studies demonstrated that the synthesized β-CD/MAA-MIPs were capable for reutilization with stable performance in sample pretreatment process. Finally, the proposed β-CD/MAA-MIPs-SPE-GC technique was successfully applied to analyze the interested PGRs in different plant tissues, fruits, and vegetable samples.


Plant growth regulators Binary monomers β-Cyclodextrin Solid-phase extraction Gas chromatography 



The work was jointly supported by the National Natural Science Foundation of China (21477088), Natural Science Foundation of Zhejiang Province (LY17B070001), and Start-up research funds of South-Central University for Nationalities.

Compliance with Ethical Standards

Conflict of Interest

Chengjun Wang declares that he has no conflict of interest. Chuyuan Ding declares that he has no conflict of interest. Qiwei Wu declares that he has no conflict of interest. Xiyao Xiong declares that he has no conflict of interest.

Ethical Approval

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

Informed Consent

Not applicable.

Supplementary material

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  1. Alvarez-Lorenzo C, García-González CA, Concheiro A (2017) Cyclodextrins as versatile building blocks for regenerative medicine. J Control Release 268:269–281Google Scholar
  2. An X, Ingole PG, Choi WK, Lee HK, Hong SU, Jeon JD (2018) Development of thin film nanocomposite membranes incorporated with sulfated β-cyclodextrin for water vapor/N2 mixture gas separation. J Ind Eng Chem 59:259–265Google Scholar
  3. Astray G, Gonzalez-Barreiro C, Mejuto JC, Rial-Otero R, Simal-Gándara J (2009) A review on the use of cyclodextrins in foods. Food Hydrocoll 23:1631–1640Google Scholar
  4. 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 128:68–74Google Scholar
  5. Chen S, Qin X, Gu W, Zhu X (2016) Speciation analysis of Mn (II)/Mn (VII) using Fe3O4@ionic liquids-β-cyclodextrin polymer magnetic solid phase extraction coupled with ICP-OES. Talanta 161:325–332Google Scholar
  6. Chen J, Cao S, Zhu M, Xi C, Zhang L, Li X, Wang G, Zhou Y, Chen Z (2018a) Fabrication of a high selectivity magnetic solid phase extraction adsorbent based on β-cyclodextrin and application for recognition of plant growth regulators. J Chromatogr A 1547:1–13Google Scholar
  7. Chen J, Cao S, Xi C, Chen Y, Li X, Zhang L, Wang G, Chen Y, Chen Z (2018b) A novel magnetic β-cyclodextrin modified graphene oxide adsorbent with high recognition capability for 5 plant growth regulators. Food Chem 239:911–919Google Scholar
  8. Cheng L, Pan S, Ding C, He J, Wang C (2017) Dispersive solid-phase microextraction with graphene oxide based molecularly imprinted polymers for determining bis(2-ethylhexyl) phthalate in environmental water. J Chromatogr A 1511:85–91Google Scholar
  9. Egawa Y, Shimura Y, Nowatari Y, Aiba D, Juni K (2005) Preparation of molecularly imprinted cyclodextrin microspheres. Int J Pharm 293:165–170Google Scholar
  10. Guo TX, Bedane AH, Pan Y, Xiao H, Eić M (2016) Characteristics of carbon dioxide gas adsorption on β-cyclodextrin derivative. Mater Lett 189:114–117Google Scholar
  11. Gupta V, Kumar M, Brahmbhatt H, Reddy CRK, Seth A, Jha B (2011) Simultaneous determination of different endogenetic plant growth regulators in common green seaweeds using dispersive liquid-liquid microextraction method. Plant Physiol Biochem 49:1259–1263Google Scholar
  12. Hasanzadeh M, Shadjou N, Guardia MDL (2018) Cytosensing of cancer cells using antibody-based molecular imprinting: a short-review. TrAC Trends Anal Chem 99:129–134Google Scholar
  13. Hu Y, Li YW, Zhang Y, Li GK, Chen YQ (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 399:3367–3374Google Scholar
  14. Huang L, He M, Chen B, Hu B (2014) Membrane-supported liquid-liquid-liquid microextraction combined with anion-selective exhaustive injection capillary electrophoresis-ultraviolet detection for sensitive analysis of phytohormones. J Chromatogr A 1343:10–17Google Scholar
  15. Jeffery DW, Mercurio MD, Herderich MJ, Hayasaka Y, Smith PA (2008) Rapid isolation of red wine polymeric polyphenols by solid-phase extraction. J Agric Food Chem 56:2571–2580Google Scholar
  16. Jing T, Wang Y, Dai Q, Xia H, Niu J, Hao Q, Mei S, Zhou Y (2010) Preparation of mixed-templates molecularly imprinted polymers and investigation of the recognition ability for tetracycline antibiotics. Biosens Bioelectron 25:2218–2224Google Scholar
  17. Li L, Feng W, Pan K (2013) Immobilization of lipase on amino-cyclodextrin functionalized carbon nanotubes for enzymatic catalysis at the ionic liquid-organic solvent interface. Colloids Surf B: Biointerfaces 102:124–129Google Scholar
  18. Liang C, Boss PK, Jeffery DW (2018) Extraction properties of new polymeric sorbents applied to wine. J Agric Food Chem 66:10086–10096Google Scholar
  19. Lu Q, Wu J, Yu Q, Feng Y (2014) Using pollen grains as novel hydrophilic solid-phase extraction sorbents for the simultaneous determination of 16 plant growth regulators. J Chromatogr A 1367:39–1347Google Scholar
  20. Luo XT, Cai BD, Chen X, Feng YQ (2017) Improved methodology for analysis of multiple phytohormones using sequential magnetic solid-phase extraction coupled with liquid chromatography-tandem mass spectrometry. Anal Chim Acta 983:112–120Google Scholar
  21. Mao C, Xie X, Liu X, Cui Z, Yang X, Yeung KWK, Pan H, Chu PK, Wu S (2017) The controlled drug release by pH-sensitive molecularly imprinted nanospheres for enhanced antibacterial activity. Mater Sci Eng C 77:84–91Google Scholar
  22. Mazur H, Kosakowska A, Pazdro K (1997) Determination of indole-3-acetic acid in the Gulf of Gdansk by high-performance liquid chromatography of its 4-methyl-7-methoxycoumarin derivative. J Chromatogr A 766:261–266Google Scholar
  23. Moretti ES, Oliveira FM, Scheel GL, DalĺAntônia LH, Borsato D, Kubota LT, Segatelli MG, Tarley CRT (2016) Synthesis ofsurface molecularly imprinted poly(methacrylic acid-hemin) on carbon nanotubes forthe voltammetricsimultaneousdetermination of antioxidants from lipid matrices and biodiesel. Electrochim Acta 212:322–332Google Scholar
  24. Pu CH, Lin SK, Chuang WC, Shyu TH (2018) Modified QuEChERS method for 24 plant growth regulators in grapes using LC-MS/MS. J Food Drug Anal 26:637–648Google Scholar
  25. Sanderson KJ, Jameson PE, Zabkiewicz JA (1987) Auxin in a seaweed extract: identification and quantitation of indole-3-acetic acid by gas chromatography-mass spectrometry. J Plant Physiol 129:363–367Google Scholar
  26. Say R, Erdem M, Ersöz A, Türk H, Denizli A (2005) Biomimetic catalysis of an organophosphate by molecularly surface imprinted polymers. Appl Catal A-Gen 286:221–225 Google Scholar
  27. Seeley SD, Powell LE (1974) Gas chromatography and detection of microquantities of gibberellins and indoleacetic acid as their fluorinated derivatives. Anal Biochem 58:39–46Google Scholar
  28. Shao L, Mu C, Du H, Czech Z, Du H, Bai Y (2011) Covalent marriage of multi-walled carbon nanotubes (MWNTs) and β-cyclodextrin (β-CD) by silicon coupling reagents. Appl Surf Sci 258:1682–1688Google Scholar
  29. Silva PHRD, Diniz MLV, Pianetti GA, César IDC, Freitas RFDS, Sousa RGD, Fernandes C (2018) Molecularly imprinted polymer for determination of lumefantrine in human plasma through chemometric-assisted solid-phase extraction and liquid chromatography. Talanta 184:173–183Google Scholar
  30. Song X, Ha W, Chen J, Shi Y (2014) Application of β-cyclodextrin-modified, carbon nanotube-reinforced hollow fiber to solid-phase microextraction of plant hormones. J Chromatogr A 1374:23–30Google Scholar
  31. Speltini A, Scalabrini A, Maraschi F, Sturini M, Profumo A (2017) Newest applications of molecularly imprinted polymers for extraction of contaminants from environmental and food matrices: a review. Anal Chim Acta 974:1–26Google Scholar
  32. Szejtli J (1998) Introduction and general overview of cyclodextrin chemistry. Chem Rev 98:1743–1754Google Scholar
  33. Topuz F, Uyar T (2017) Cyclodextrin-functionalized mesostructured silica nanoparticles for removal of polycyclic aromatic hydrocarbons. J Colloid Interface Sci 497:233–241Google Scholar
  34. Wang Z, Cao X (2015) Preparation of core-shell molecular imprinting polymer for lincomycin a and its application in chromatographic column. Process Biochem 50:1136–1145Google Scholar
  35. Wulff G, Sarhan A (1972) The use of polymers with enzyme-analogous structures for the resolution of racemates. Angew Chem Int Ed 11:341–346Google Scholar
  36. Yan H, Wang F, Han D, Yang G (2012) Simultaneous determination of four plant hormones in bananas by molecularly imprinted solid-phase extraction coupled with high performance liquid chromatography. Analyst 137:2884–2890Google Scholar
  37. Yang Y, Yu J, Yin J, Shao B, Zhang J (2014) Molecularly imprinted solid-phase extraction for selective extraction of bisphenol analogues in beverages and canned food. J Agric Food Chem 62:11130–11137Google Scholar
  38. Yang Q, Li J, Wang X, Peng H, Xiong H, Chen L (2018) Strategies of molecular imprinting-based fluorescence sensors for chemical and biological analysis. Biosens Bioelectron 112:54–71Google Scholar
  39. 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 1217:7337–7344Google Scholar
  40. 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 1046:58–64Google Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of Resources and Environmental ScienceSouth-Central University for NationalitiesWuhanChina
  2. 2.College of Chemistry and Materials EngineeringWenzhou UniversityWenzhouChina

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