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Ratiometric determination of copper(II) using dually emitting Mn(II)-doped ZnS quantum dots as a fluorescent probe

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Abstract

A ratiometric probe is described for the fluorometric determination of Cu(II) ions based on their quenching effect on the luminescence of dually-emitting quantum dots (QDs). ZnS QDs were doped with Mn(II) and subsequently modified with mercaptopropionic acid to give the QD probe which consists of a  sole fluorophore but has two emission peaks (at 430 and 590 nm under 310 nm excitation, respectively). On addition of Cu(II) ions, the 590 nm band is quenched while the 430 nm band exhibits a little change. The changes in the intensity ratios of the yellow and the purple bands increases linearly in the 0 to 3.0 μM Cu(II) concentration range, and the detection limit reached 14 nM. The QD probe was validated and successfully applied to the determination of Cu(II) in spiked real water samples.

Mn-doped ZnS (ZnS:Mn(II)) quantum dots were synthesized with yellow fluorescence. After the modification of 3-mercaptopropionic acid (MPA), ZnS:Mn(II) was transferred to aqueous phase and became MPA modified Mn-doped ZnS (MPA- ZnS:Mn(II)). The fluorescence was changed to purple upon the addition of copper ions because the yellow band was largely quenched while the purple band only changed a little.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (61603001, 21776002, 21675158, 81773684, 21505053), Guangdong Natural Science Funds for Distinguished Young Scholars (2018B030306033), Pearl River S&T Nova Program of Guangzhou (201806010060), Science and Technology Planning Project of Guangdong Province, China (2016A030310089), Medical Scientific Research Foundation of Guangdong Province of China (A2018133), the Fundamental Research Funds for the Central Universities (21618407), and the Basic Research Project of Knowledge Innovation Program of Shenzhen City (JCYJ20160229165250876).

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  1. Lifang He and Zhijun Bao contributed equally to this work.

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Anhui University of Technology, Ma’anshan, 243032, Anhui, China

    Lifang He, Kui Zhang, Cheng Zhang & Ping Cui

  2. Institute of Pharmaceutical Analysis, College of Pharmacy, Jinan University, Guangzhou, 510632, Guangdong, China

    Zhijun Bao, Bingbing Sheng, Rui Huang, Ting Zhao, Xiaochen Liang, Xingjie Yang, Annan Yang & Haibo Zhou

  3. Department of Preventative Medicine, Zhejiang Provincial Key Laboratory of Pathological and Physiological Technology, Medical School of Ningbo University, Ningbo, Zhejiang, 315211, China

    Danting Yang

  4. Center of Super-Diamond and Advanced Films (COSDAF) & Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, SAR, China

    Juan Antonio Zapien

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  1. Lifang He
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Correspondence to Cheng Zhang, Ping Cui or Haibo Zhou.

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He, L., Bao, Z., Zhang, K. et al. Ratiometric determination of copper(II) using dually emitting Mn(II)-doped ZnS quantum dots as a fluorescent probe. Microchim Acta 185, 511 (2018). https://doi.org/10.1007/s00604-018-3043-8

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