This article demonstrates the feasibility of an alternative strategy for producing temperature sensitive molecularly imprinted microspheres (MIMs) for solid-phase dispersion extraction of malachite green, crystal violet and their leuko metabolites. Thermo-sensitive MIMs can change their structure following temperature stimulation. This allows capture and release of target molecules to be controlled by temperature. The fabrication technique provides surface molecular imprinting in acetonitrile using vinyl modified silica microspheres as solid supports, methacrylic acid and N-isopropyl acrylamide as the functional monomers, ethyleneglycol dimethacrylate as the cross-linker, and malachite green as the template. After elution of the template, the MIMs can be used for fairly group-selective solid phase dispersion extraction of malachite green, crystal violet, leucomalachite green, and leucocrystal violet from homogenized fish samples at a certain temperature. Following centrifugal separation of the microspheres, the analytes were eluted with a 95:5 mixture of acetonitrile and formic acid, and then quantified by ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) with isotope internal calibration. The detection limits for malachite green, crystal violet and their metabolites typically are 30 ng·kg−1. Positive samples were identified by UHPLC-MS/MS in the positive ionization mode with multiple reaction monitoring. The method was applied to the determination of the dyes and the respective leuko dyes in fish samples, and accuracy and precision were validated by comparative analysis of the samples by using aluminum neutral columns.
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We gratefully acknowledge financial support from the National Natural Science Foundation of China (No: 21505026), Science and Technology Planning Project of Guangdong Province (No: 2016 A020215020), Medical Science Foundation of Guangdong Province (No: A2016141), and the Project for Key Medicine Discipline Construction of Guangzhou Municipality (No: 2017-2019-04).
The author (s) declare that they have no competing interests.
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Tan, L., Chen, K., He, R. et al. Temperature sensitive molecularly imprinted microspheres for solid-phase dispersion extraction of malachite green, crystal violet and their leuko metabolites. Microchim Acta 183, 2991–2999 (2016). https://doi.org/10.1007/s00604-016-1947-8
- Molecular imprinting
- Silica microspheres
- Malachite green
- Crystal violet
- Solid-phase dispersion extraction
- Thermal modulation
- Drug residues