Microchimica Acta

, 185:208 | Cite as

Magnetic nanoparticles coated with a molecularly imprinted polymer doped with manganese-doped ZnS quantum dots for the determination of 2,4,6-trichlorophenol

  • Xiao Wei
  • Miaomiao Yu
  • Chen Li
  • Xinghui Gong
  • Fang Qin
  • Zhenhong Wang
Original Paper


The authors describe a multifunctional magnetic molecularly imprinted phosphorescent nanoparticle probe for the selective determination of 2,4,6-trichlorophenol (2,4,6-TCP). The probe consists of a magnetite (Fe3O4) core that is coated with a molecularly imprinted polymer doped with Mn-doped ZnS quantum dots (QDs). The MIP was obtained by copolymerization of acrylamide, ethylene glycol dimethacrylate, and 2,4,6-TCP. The resulting nanoprobe shows strong phosphorescence (with excitation/emission peaks at 320/594 nm) due to the presence of the QDs, good magnetism, and high selectivity for 2,4,6-TCP. Under optimal detection condition, response is linear in the 0.1–30 μmol L−1 2,4,6-TCP concentration range. The imprinting factor is 8.84, and the detection limit is 35 nmol L−1. The method was successfully applied to the determination of 2,4,6-TCP in spiked river water and waste water.

Graphical abstract

Schematic of a multifunctional phosphorescent probe for 2,4,6-trichlorophenol. It consists of a magnetic core coated with a molecularly imprinted polymer shell containing Mn(II) doped ZnS quantum dots whose room-temperature phosphorescence is quenched by 2,4,6-trichlorophenol.


Molecular imprinting Precipitation polymerization Room temperature phosphorescence Composite material Quenching Stern-Volmer plot Selective recognition Chlorophenols 



This research has been supported by the National Postdoctoral Science Foundation (No. 2017 M610618), Fundamental Research Funds for the Central Universities of Chang’an University (No. 310829173601, No. 310829172002, No. 310829171004, No. 310829171003, No. 310829161013).

Compliance with ethical standards

The author(s) declare that they have no competing interests.

Supplementary material

604_2018_2742_MOESM1_ESM.doc (132 kb)
ESM 1 (DOC 131 kb)


  1. 1.
    Valizadeh A, Mikaeili H, Samiei M, Farkhani SM, Zarghami N, Kouhi M, Akbarzadeh A, Davaran S (2012) Quantum dots: synthesis, bioapplications, and toxicity. Nanoscale Res Lett 7:480CrossRefGoogle Scholar
  2. 2.
    Wei X, Zhou ZP, Hao TF, Li HJ, Yan YS (2015) Molecularly imprinted polymer nanospheres based on Mn-doped ZnS QDs via a precipitation polymerization for room-temperature phosphorescence probing of 2,6-dichlorophenol. RSC Adv 5:19799–19806CrossRefGoogle Scholar
  3. 3.
    Yan H, Wang HF (2011) Turn-on room temperature phosphorescence assay of heparin with tunable sensitivity and detection window based on target-induced self-assembly of polyethyleneimine capped Mn-doped ZnS quantum dots. Anal Chem 83:8589–8595CrossRefGoogle Scholar
  4. 4.
    Haupt K, Mosbach K (2000) Molecularly imprinted polymers and their use in biomimetic sensors. Chem Rev 100:2495–2504CrossRefGoogle Scholar
  5. 5.
    Liang RN, Song DA, Zhang RM, Qin W (2010) Potentiometric sensing of neutral species based on a uniform-sized molecularly imprinted polymer as a receptor. Angew Chem Int Ed 49:2556–2559CrossRefGoogle Scholar
  6. 6.
    Dan L, Wang HF (2013) Mn-doped ZnS quantum dot imbedded two-fragment imprinting silica for enhanced room temperature phosphorescence probing of domoic acid. Anal Chem 85:4844–4848CrossRefGoogle Scholar
  7. 7.
    Zhao YY, Ma YX, Li H, Wang LY (2012) Composite QDs@MIP nanospheres for specific recognition and direct fluorescent quantification of pesticides in aqueous media. Anal Chem 84:386–395CrossRefGoogle Scholar
  8. 8.
    Wei X, Zhou ZP, Hao TF, Li HJ, Xu YQ, Lu K, Wu YL, Dai JD, Pan JM, Yan YS (2015) Highly-controllable imprinted polymer nanoshell at the surface of silica nanoparticles based room-temperature phosphorescence probe for detection of 2,4-dichlorophenol. Anal Chim Acta 870:83–91CrossRefGoogle Scholar
  9. 9.
    Guan GJ, Liu RY, Mei QS, Zhang ZP (2012) Molecularly Imprinted Shells from Polymer and Xerogel Matrices on Polystyrene Colloidal Spheres. Chem Eur J 18:4692–4698CrossRefGoogle Scholar
  10. 10.
    Gonzato C, Courty M, Pasetto P, Haupt K (2011) Magnetic molecularly imprinted polymer nanocomposites via surface-initiated RAFT polymerization. Adv Funct Mater 21:3947–3953CrossRefGoogle Scholar
  11. 11.
    Yao GH, Liang RP, Huang CF, Wang Y, Qiu JD (2013) Surface plasmon resonance sensor based on magnetic molecularly imprinted polymers amplification for pesticide recognition. Anal Chem 85:11944–11951CrossRefGoogle Scholar
  12. 12.
    Gao L, Wang JX, Li XY, Yan YS, Li CX, Pan JM (2014) A core-shell surface magnetic molecularly imprinted polymers with fluorescence for λ-cyhalothrin selective recognition. Anal Bioanal Chem 406:7213–7220CrossRefGoogle Scholar
  13. 13.
    Jin X, Zha J, Xu Y, Wang Z, Kumaran SS (2011) Derivation of aquatic predicted no-effect concentration (PNEC) for 2,4-dichlorophenol: Comparing native species data with non-native species data. Chemosphere 84:1506–1511CrossRefGoogle Scholar
  14. 14.
    USEPA, 8EHQ-14302 (2001)Google Scholar
  15. 15.
    Chao YY, Tu YM, Jian ZX, Wang HW, Huang YL (2013) Direct determination of chlorophenols in water samples through ultrasound-assisted hollow fiber liquid-liquid-liquid microextraction on-line coupled with high-performance liquid chromatography. J Chromatogr A 1271:41–49CrossRefGoogle Scholar
  16. 16.
    Guo L, Lee HK (2012) Electro membrane extraction followed by low-density solvent based ultrasound-assisted emulsification microextraction combined with derivatization for determining chlorophenols and analysis by gas chromatography-mass spectrometry. J Chromatogr A 1243:14–22CrossRefGoogle Scholar
  17. 17.
    Liu J, Niu JF, Yin LF, Jiang F (2011) In situ encapsulation of laccase in nanofibers by electrospinning for development of enzyme biosensors for chlorophenol monitoring. Analyst 136:4802–4808CrossRefGoogle Scholar
  18. 18.
    Sharma OP, Bhat TK, Singh B (1998) Thin-layer chromatography of gallic acid, methyl gallate, pyrogallol, phloroglucinol, catechol, resorcinol, hydroquinone, catechin, epicatechin, cinnamic acid, p-coumaric acid, ferulic acid and tannic acid. J Chromatogr A 822:167–171CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Key Laboratory of Subsurface Hydrology and Ecological Effects in Arid Region, Ministry of EducationChang’an UniversityXi’anChina
  2. 2.School of Environmental Science and EngineeringChang’an UniversityXi’anChina

Personalised recommendations