Analytical and Bioanalytical Chemistry

, Volume 411, Issue 2, pp 537–544 | Cite as

Ratiometric fluorescence probe of MIPs@CdTe QDs for trace malachite green detection in fish

  • Hui Ran
  • Zheng-Zhong Lin
  • Qiu-Hong Yao
  • Cheng-Yi Hong
  • Zhi-Yong HuangEmail author
Research Paper


A facile and practical ratiometric fluorescence probe based on two CdTe quantum dots (QDs) coated with molecularly imprinted polymers (MIPs) was prepared for the detection of trace malachite green (MG) in fish. Two CdTe QDs coated with MIPs were fabricated by a one-pot method using MG, (3-aminopropyl) triethoxysilane (APTES) and tetraethyl orthosilicate (TEOS) as template, functional monomer, and cross-linker, respectively. CdTe QDs with λem 530 nm (gQDs) and 630 nm (rQDs) were used as the referential fluorophore and target sensitive fluorophore, respectively. The fluorescence intensity of gQDs remained unchanged in the presence of MG, while the fluorescence of rQDs could be quantitatively quenched by MG based on the strategy of fluorescence resonance energy transfer. The ratiometric fluorescence probe (MIPs@gQDs&rQDs) was characterized by transmission electron microscopy and Fourier transform infrared spectroscopy. The linear range of MG detection was 0.1–32 μmol L−1 with a detection limit of 8.8 μg kg−1. The constructed probe has been successfully applied to the detection of MG in fish with the recoveries of 92.3–109.1%, which were validated by the method of HPLC. The result indicated that the probe possessed rapid response, wide linear range, high sensitivity, and relatively high selectivity, and was low-cost and easy in operation in the detection of MG in fish samples.


CdTe quantum dots Ratiometric fluorescence probe Molecular imprinting polymer Malachite green Fish 


Funding information

This research was supported by the Foundation from the Science and Technology Planning Project of Fujian Province, China (2016Y0064), the Natural Science Foundation of Fujian Province of China (2018J01432, 2017J01633, 2017J01633), the Science and Technology Planning Project of Xiamen, China (3502Z20183031), Innovative Research Team of Jimei University, China (2010A007), and the National Undergraduate Training Programs for Innovation and Entrepreneurship, China (201610390042, 201710390022, 201810390071).

Compliance with ethical standards

The authors declare that they have no conflict of interest. This article does not contain any studies with human participants performed by any of the authors.

Supplementary material

216_2018_1479_MOESM1_ESM.pdf (408 kb)
ESM 1 (PDF 408 kb)


  1. 1.
    Shanmugam S, Ulaganathan P, Swaminathan K, Sadhasivam S, Wu YR. Enhanced biodegradation and detoxification of malachite green by Trichoderma asperellum laccase: degradation pathway and product analysis. Int Biodeterior Biodegrad. 2017;125:258–68.CrossRefGoogle Scholar
  2. 2.
    Srivastava S, Sinha R, Roy D. Toxicological effects of malachite green. Aquat Toxicol. 2004;66(3):319–29.CrossRefGoogle Scholar
  3. 3.
    Hidayah NAP, Faridah S, Azura NMS, Gayah AR, Othman M, Fatimah AB. Malachite green and leuco-malachite green detection in fish using modified enzyme biosensor. 11th Asian Conference on Chemical Sensors (ACCS), Penang, Malaysia. Procedia Chem. 2016;20:85–9.CrossRefGoogle Scholar
  4. 4.
    Lian Z, Wang J. Molecularly imprinted polymer for selective extraction of malachite green from seawater and seafood coupled with high-performance liquid chromatographic determination. Mar Pollut Bull. 2012;64(12):2656–62.CrossRefGoogle Scholar
  5. 5.
    Nebot C, Lglesias A, Barreiro R, Miranda JM, Vazquez B, Franco CM, et al. A simple and rapid method for the identification and quantification of malachite green and its metabolite in hake by HPLC-MS/MS. Food Control. 2013;31(1):102–7.CrossRefGoogle Scholar
  6. 6.
    Scherpenisse P, Bergwerff AA. Determination of residues of malachite green in finfish by liquid chromatography tandem mass spectrometry. Anal Chim Acta. 2005;529(1–2):173–7.CrossRefGoogle Scholar
  7. 7.
    Li L, Peng AH, Lin ZZ, Zhong HP, Chen XM, Huang ZY. Biomimetic ELISA detection of malachite green based on molecularly imprinted polymer film. Food Chem. 2017;229:403–8.CrossRefGoogle Scholar
  8. 8.
    Zhang YY, Huang YQ, Zhai FL, Du R, Liu YD, Lai KQ. Analyses of enrofloxacin, furazolidone and malachite green in fish products with surface-enhanced Raman spectroscopy. Food Chem. 2012;135(2):845–50.CrossRefGoogle Scholar
  9. 9.
    Qi L, Wei JR, Lv XJ, Huo Y, Zhang ZQ. A ratiometric fluorescence RRE RNA-targeted assay for a new fluorescence ligand. Biosens Bioelectron. 2016;86:287–92.CrossRefGoogle Scholar
  10. 10.
    Hao TF, Wei X, Nie YJ, Xu YQ, Lu K, Yan YS, et al. Surface modification and ratiometric fluorescence dual function enhancement for visual and fluorescent detection of glucose based on dual-emission quantum dots hybrid. Sensors Actuators B Chem. 2016;230:70–6.CrossRefGoogle Scholar
  11. 11.
    Chullasat K, Nurerk P, Kanatharana P, Davis F, Bunkoed O. A facile optosensing protocol based on molecularly imprinted polymer coated on CdTe quantum dots for highly sensitive and selective amoxicillin detection. Sensors Actuators B Chem. 2018;254:255–63.CrossRefGoogle Scholar
  12. 12.
    Li L, Lin ZZ, Chen XM, Zhang HY, Lin YD, Lai ZZ, et al. Molecularly imprinted polymers for extraction of malachite green from fish samples prior to its determination by HPLC. Microchim Acta. 2015;182(1–9):1791–6.CrossRefGoogle Scholar
  13. 13.
    Lin ZZ, Zhang HY, Li L, Huang ZY. Application of magnetic molecularly imprinted polymers in the detection of malachite green in fish samples. React Funct Polym. 2016;98:24–30.CrossRefGoogle Scholar
  14. 14.
    Lin ZZ, Zhang HY, Peng AH, Lin YD, Li L, Huang ZY. Determination of malachite green in aquatic products based on magnetic molecularly imprinted polymers. Food Chem. 2016;200:32–7.CrossRefGoogle Scholar
  15. 15.
    Wu L, Lin ZZ, Zhong HP, Peng AH, Chen XM, Huang ZY. Rapid determination of malachite green in water and fish using a fluorescent probe based on CdTe quantum dots coated with molecularly imprinted polymer. Sensors Actuators B Chem. 2017;239:69–75.CrossRefGoogle Scholar
  16. 16.
    Wu L, Lin ZZ, Zhong HP, Peng AH, Chen XM, Huang ZY. Rapid detection of malachite green in fish based on CdTe quantum dots coated with molecularly imprinted silica. Food Chem. 2017;229:847–53.CrossRefGoogle Scholar
  17. 17.
    Wu L, Lin ZZ, Zeng J, Zhong HP, Chen XM, Huang ZY. Detection of malachite green in fish based on magnetic fluorescent probe of CdTe QDs/nano-Fe3O4@MIPs. Spectrochim Acta A. 2018;196:117–22.CrossRefGoogle Scholar
  18. 18.
    Yang J, Lin ZZ, Zhong HP, Chen XM, Huang ZY. Determination of leucomalachite green in fish using a novel MIP-coated QDs probe based on synchronous fluorescence quenching effect. Sensors Actuators B Chem. 2017;252:561–7.CrossRefGoogle Scholar
  19. 19.
    Amjadi M, Jalilia R. Molecularly imprinted polymer-capped nitrogen-doped graphene quantum dots as a novel chemiluminescence sensor for selective and sensitive determination of doxorubicin. RSC Adv. 2016;6(89):86736–43.CrossRefGoogle Scholar
  20. 20.
    Wei JR, Chen HY, Zhang W, Pan JX, Dang FQ, Zhang ZQ, et al. Ratiometric fluorescence for sensitive and selective detection of mitoxantrone using a MIP@rQDs@SiO2 fluorescence probe. Sensors Actuators B Chem. 2017;244:31–7.CrossRefGoogle Scholar
  21. 21.
    Qian J, Wang K, Wang CQ, Ren CC, Liu Q, Hao N, et al. Ratiometric fluorescence nanosensor for selective and visual detection of cadmium ions using quencher displacement-induced fluorescence recovery of CdTe quantum dots-based hybrid probe. Sensors Actuators B Chem. 2017;241:1153–60.CrossRefGoogle Scholar
  22. 22.
    Gui WY, Wang H, Liu Y, Ma Q. Ratiometric fluorescent sensor with molecularly imprinted mesoporous microspheres for malachite green detection. Sensors Actuators B Chem. 2018;266:685–91.CrossRefGoogle Scholar
  23. 23.
    Wei X, Meng M, Song ZL, Gao L, Li HJ, Dai JD, et al. Synthesis of molecularly imprinted silica nanospheres embedded mercaptosuccinic acid-coated CdTe quantum dots for selective recognition of λ-cyhalothrin. J Lumin. 2014;153:326–32.CrossRefGoogle Scholar
  24. 24.
    Livesey AK, Brochon JC. Analyzing the distribution of decay constants in pulse-fluorimetry using the maximum entropy method. Biophys J. 1987;52(5):693–706.CrossRefGoogle Scholar
  25. 25.
    Xie YJ, Guo LN, Liu S, Wang QF, Zhang SJ, Liu Y, et al. Study on the effect of deposition rate and concentration of Eu on the fluorescent lifetime of CsI: Tl thin film. Nucl Inst Methods Phys Res A. 2017;858:18–21.CrossRefGoogle Scholar
  26. 26.
    Xu ZS, Yan JH, Xu C, Cheng C, Jiang C, Liu XF, et al. Tunable near-infrared emission and fluorescent lifetime of PbSe quantum dot-doped borosilicate glass. J Alloys Compd. 2017;711:58–63.CrossRefGoogle Scholar
  27. 27.
    Liu J, Chen H, Lin Z, Lin JM. Preparation of surface imprinting polymer capped Mn-doped ZnS quantum dots and their application for chemiluminescence detection of 4-nitrophenol in tap water. Anal Chem. 2010;82(17):7380–6.CrossRefGoogle Scholar
  28. 28.
    Wang C, Ma Q, Dou WC, Kanwal S, Wang GN, Yuan PF, et al. Synthesis of aqueous CdTe quantum dots embedded silica nanoparticles and their applications as fluorescence probes. Talanta. 2009;77(4):1358–64.CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  • Hui Ran
    • 1
  • Zheng-Zhong Lin
    • 1
  • Qiu-Hong Yao
    • 2
  • Cheng-Yi Hong
    • 1
  • Zhi-Yong Huang
    • 1
    • 3
    Email author
  1. 1.College of Food and Biological EngineeringJimei UniversityXiamenChina
  2. 2.Xiamen Huaxia UniversityXiamenChina
  3. 3.Fujian Collaborative Innovation Center for Exploitation and Utilization of Marine Biological ResourcesXiamenChina

Personalised recommendations