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A ratiometric fluorescent core-shell nanoprobe for sensing and imaging of zinc(II) in living cell and zebrafish

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Abstract

A zinc(II)-responsive ratiometric fluorescent core-shell nanoprobe (referred to as QPNPs) is described. It consist of an optimized combination of an internal reference dye (TBAP) encapsulated in the core, and a Zn(II)-specific indicator dye (PEIQ) in the shell. The nanoprobe was synthesized via single-step graft copolymerization induced by tert-butyl hydroperoxide at 80 °C. QPNPs exhibit a well-defined core-shell nanostructure and well-resolved dual emissions after photoexcitation at 380 nm. After exposure to Zn(II), the QPNPs display a green fluorescence peaking at ~500 nm that increases with the concentration of Zn(II), while the pink fluorescence of the porphine-derived reference dye peaking at ~650 nm remains unchanged. This results in color change from pink to green and thus enables Zn(II) to be detected both spectroscopically and with bare eyes. Zn(II) can be quantified with a 3.1 nM detection limit. The core-shell structured nanoprobe was also applied to real-time imaging of Zn(II) in living HeLa cells and in zebrafish. This work establishes a reliable approach to synthesize ratiometric fluorescent nanoprobes. It enables such nanoprobes to be prepared also by those not skilled in nanomaterial synthesis.

A zinc(II)-responsive core-shell nanoprobe (referred to as QPNP) is synthesized via single-step graft copolymerization. Zn(II) can be quantitated with a 3.1 nM detection limit by the QPNPs through ratiometric fluorescence strategy (PEIQ as the Zn(II) indicator and TBAP as the reference dye).

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Acknowledgements

The financial support from Guangdong-HongKong Technology Cooperation Funding Scheme (2016A050503027), Tip-top Scientific and Technical Innovative Youth Talents of Guangdong special support program (2014TQ01R417), and the Fundamental Research Funds for the Central Universities (Grant No. 17lgjc09) is gratefully acknowledged.

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Author notes

  1. Wandi Chen and Qin Wang contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Sensing Technology and Biomedical Instruments (Guangdong Province), School of Biomedical Engineering, Sun Yat-Sen University, Guangzhou, 510006, People’s Republic of China

    Wandi Chen, Qin Wang, Junping Ma & Changqing Yi

  2. Institute of Chinese Medical Sciences, University of Macau, Macau, People’s Republic of China

    Junping Ma & Cheuk-Wing Li

  3. Department of Biomedical Engineering, the Hong Kong Polytechnic University, Hong Kong, People’s Republic of China

    Mo Yang

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  1. Wandi Chen
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Correspondence to Changqing Yi.

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Electronic supplementary material

ESM 1

The experimental details for PEIQ synthesis and QPNPs selectivity, 1HNMR spectra, TEM image of QPNPs and QNPs, FTIR and the deconvoluted XPS spectra of QPNPs, the stability of QPNPs and photostability of QPNPs, TBAP release from QPNPs, the response time curve of QPNPs upon reacting Zn(II), the pH effects on the ratio I500/I657 of QPNPs, photostability of QPNPs in the absence and presence of Zn(II), the cytotoxicity and hemolytic potential of QPNPs, superposition of phase-contrast as well as fluorescence images of HeLa cells upon incubation with QPNPs in the presence of Zn(II), tabulating comparison of different optical sensors for Zn(II) determination, and analytical results of the quantitation of Zn(II) in spiked cell extract samples, are supplied as Supporting Information. (DOCX 1121 kb)

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Chen, W., Wang, Q., Ma, J. et al. A ratiometric fluorescent core-shell nanoprobe for sensing and imaging of zinc(II) in living cell and zebrafish. Microchim Acta 185, 523 (2018). https://doi.org/10.1007/s00604-018-3066-1

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