Synthesis and application of a surface ionic imprinting polymer on silica-coated Mn-doped ZnS quantum dots as a chemosensor for the selective quantification of inorganic arsenic in fish


A novel room temperature phosphorescence chemosensor probe has been successfully developed and applied to the selective detection and quantification of inorganic arsenic (As(III) plus As(V)) in fish samples. The prepared material (IIP@ZnS:Mn QDs) was based on Mn-doped ZnS quantum dots coated with (3-aminopropyl) triethoxysilane and an As(III) ionic imprinted polymer. The novel use of vinyl imidazole as a complexing reagent when synthesizing the ionic imprinted polymer guarantees that both inorganic arsenic species (As(III) and As(V)) can interact with the recognition cavities in the ionic imprinted polymer. After characterization, several studies were performed to enhance the interaction between the targets (As(III) and As(V) ions) and the IIP@ZnS:Mn QDs nanoparticles. The optimization and validation process showed that the composite material offers high selectivity (high imprinting factor) for inorganic arsenic species. The limit of quantification for total inorganic As was 29.6 μg kg−1, value lower than the EU/EC regulation limits proposed for other foodstuffs than fish, such as rice. The proposed method is therefore simple, requires short analysis times and offers good sensitivity, precision (inter-day relative standard deviations lower than 10%), and quantitative analytical recoveries. The method has been successfully applied to assess total inorganic arsenic in several fishery products, showing good agreement with the total inorganic arsenic concentration (As(III) plus As(V)) found after applying other advanced and expensive methods such those based on high-performance liquid chromatography hyphenated to inductively coupled plasma-mass spectrometry.

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The authors thank to Dr. Bruno Dacuña-Mariño (Unidade de Raios X) at Rede de Infraestruturas de Apoio á Investigación e ao Desenvolvemento Tecnolóxico – University of Santiago de Compostela) for XRD technical support, to Eugenio Solla (Servicio de Microscopía Electrónica) at CACTI–University of Vigo for TEM/EDS technical support, and to Dr. María Celeiro (LIDSA, Department of Analytical Chemistry, Nutrition and Bromatology – University of Santiago de Compostela) for ASE technical assistance.


This work was supported by the Dirección Xeral de I+D – Xunta de Galicia Grupos de Referencia Competitiva (project number 6RC2014/2016 and ED431C2018/19), and Development of a Strategic Grouping in Materials - AEMAT (grant ED431E2018/08).

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Jinadasa, K.K., Peña-Vázquez, E., Bermejo-Barrera, P. et al. Synthesis and application of a surface ionic imprinting polymer on silica-coated Mn-doped ZnS quantum dots as a chemosensor for the selective quantification of inorganic arsenic in fish. Anal Bioanal Chem 412, 1663–1673 (2020).

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  • Silica-coated Mn-doped ZnS quantum dots
  • Ionic imprinted polymer
  • Room temperature phosphorescence
  • Inorganic arsenic
  • Fish
  • Chemosensor probe