Skip to main content
Log in

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

  • Published:
Food Analytical Methods Aims and scope Submit manuscript

Abstract

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.

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

Access this article

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

  • Alvarez-Lorenzo C, García-González CA, Concheiro A (2017) Cyclodextrins as versatile building blocks for regenerative medicine. J Control Release 268:269–281

    Article  CAS  PubMed  Google Scholar 

  • 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 59:259–265

    Article  CAS  Google Scholar 

  • 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 23:1631–1640

    Article  CAS  Google Scholar 

  • 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 128:68–74

    Article  CAS  Google Scholar 

  • 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 161:325–332

    Article  CAS  PubMed  Google Scholar 

  • 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 1547:1–13

    Article  CAS  PubMed  Google Scholar 

  • 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 239:911–919

    Article  CAS  PubMed  Google Scholar 

  • 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 1511:85–91

    Article  CAS  PubMed  Google Scholar 

  • Egawa Y, Shimura Y, Nowatari Y, Aiba D, Juni K (2005) Preparation of molecularly imprinted cyclodextrin microspheres. Int J Pharm 293:165–170

    Article  CAS  PubMed  Google Scholar 

  • Guo TX, Bedane AH, Pan Y, Xiao H, Eić M (2016) Characteristics of carbon dioxide gas adsorption on β-cyclodextrin derivative. Mater Lett 189:114–117

    Article  CAS  Google Scholar 

  • 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 49:1259–1263

    Article  CAS  PubMed  Google Scholar 

  • Hasanzadeh M, Shadjou N, Guardia MDL (2018) Cytosensing of cancer cells using antibody-based molecular imprinting: a short-review. TrAC Trends Anal Chem 99:129–134

    Article  CAS  Google Scholar 

  • 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 399:3367–3374

    Article  CAS  PubMed  Google Scholar 

  • 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 1343:10–17

    Article  CAS  PubMed  Google Scholar 

  • 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 56:2571–2580

    Article  CAS  PubMed  Google Scholar 

  • 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 25:2218–2224

    Article  CAS  PubMed  Google Scholar 

  • 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 102:124–129

    Article  CAS  PubMed  Google Scholar 

  • Liang C, Boss PK, Jeffery DW (2018) Extraction properties of new polymeric sorbents applied to wine. J Agric Food Chem 66:10086–10096

    Article  CAS  PubMed  Google Scholar 

  • 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 1367:39–1347

    Article  CAS  PubMed  Google Scholar 

  • 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 983:112–120

    Article  CAS  PubMed  Google Scholar 

  • 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 77:84–91

    Article  CAS  Google Scholar 

  • 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 766:261–266

    Article  CAS  Google Scholar 

  • 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 212:322–332

  • 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 26:637–648

    Article  CAS  PubMed  Google Scholar 

  • 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 129:363–367

    Article  CAS  Google Scholar 

  • 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

  • Seeley SD, Powell LE (1974) Gas chromatography and detection of microquantities of gibberellins and indoleacetic acid as their fluorinated derivatives. Anal Biochem 58:39–46

  • 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 258:1682–1688

    Article  CAS  Google Scholar 

  • 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 184:173–183

    Article  CAS  PubMed  Google Scholar 

  • 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 1374:23–30

    Article  CAS  PubMed  Google Scholar 

  • 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 974:1–26

    Article  CAS  PubMed  Google Scholar 

  • Szejtli J (1998) Introduction and general overview of cyclodextrin chemistry. Chem Rev 98:1743–1754

    Article  CAS  PubMed  Google Scholar 

  • Topuz F, Uyar T (2017) Cyclodextrin-functionalized mesostructured silica nanoparticles for removal of polycyclic aromatic hydrocarbons. J Colloid Interface Sci 497:233–241

    Article  CAS  PubMed  Google Scholar 

  • Wang Z, Cao X (2015) Preparation of core-shell molecular imprinting polymer for lincomycin a and its application in chromatographic column. Process Biochem 50:1136–1145

    Article  CAS  Google Scholar 

  • Wulff G, Sarhan A (1972) The use of polymers with enzyme-analogous structures for the resolution of racemates. Angew Chem Int Ed 11:341–346

    CAS  Google Scholar 

  • 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 137:2884–2890

    Article  CAS  PubMed  Google Scholar 

  • 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 62:11130–11137

    Article  CAS  PubMed  Google Scholar 

  • 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 112:54–71

    Article  CAS  PubMed  Google Scholar 

  • 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 1217:7337–7344

    Article  CAS  PubMed  Google Scholar 

  • 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 1046:58–64

    Article  CAS  Google Scholar 

Download references

Funding

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.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Chengjun Wang.

Ethics declarations

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.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

ESM 1

(PDF 1082 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, C., Ding, C., Wu, Q. et al. 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. Food Anal. Methods 12, 1160–1169 (2019). https://doi.org/10.1007/s12161-019-01455-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12161-019-01455-1

Keywords

Navigation