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A fluorescent “on-off-on” assay for selective recognition of Cu(II) and glutathione based on modified carbon nanodots, and its application to cellular imaging

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Abstract

Carbon nanodots modified with triethylenetetramine (referred to as TCDs) are shown to be viable fluorescent probes for relay recognition of Cu(II) ion and glutathione (GSH). The assay is based on an “on-off-on” mechanism where the “on-off” effect, i.e. quenching by Cu(II) by up to 67%, is exploited to quantify it in concentrations as low as 3.4 nM. The unique quenching of fluorescence (measured at excitation/emission wavelengths of 380/470 nm; quantum yield 16%) is attributed to the fairly selective capture of Cu(II) by the amino and amide groups on the surface of the TCDs. On addition of GSH to the quenched TCD/Cu(II) complex, fluorescence is restored. This effect enables GSH to be quantified in the 0.2 to 175 μM concentration range, with a 0.11 μM detection limit. The turn-on response to GSH is highly selective over other natural amino acids and common anions. Furthermore, the TCDs were successfully applied to image Cu(II) and GSH in living yeast cells.

Carbon nanodots modified with triethylenetetramine show strong blue fluorescence which is quenched by Cu(II) but restored on addition of glutathione. Both Cu(II) (down to 3.4 nM) and glutathione (down to 110 nM) can be detected via these effects.

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (21176125), the Natural Science Foundation of Heilongjiang Province of China (B201313, B201419), and the Science Research Project of Heilongjiang Province Education Department, China (12541861, 1254G066).

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Authors and Affiliations

  1. Key Laboratory of Fine Chemicals, College of Heilongjiang Province, Qiqihar University, Qiqihar, 161006, China

    Rui Yang & Xiangfeng Guo

  2. College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar, 161006, China

    Xiangfeng Guo, Lihua Jia & Yu Zhang

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  1. Rui Yang
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  2. Xiangfeng Guo
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  3. Lihua Jia
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  4. Yu Zhang
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Correspondence to Xiangfeng Guo or Lihua Jia.

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Yang, R., Guo, X., Jia, L. et al. A fluorescent “on-off-on” assay for selective recognition of Cu(II) and glutathione based on modified carbon nanodots, and its application to cellular imaging. Microchim Acta 184, 1143–1150 (2017). https://doi.org/10.1007/s00604-017-2076-8

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  • DOI: https://doi.org/10.1007/s00604-017-2076-8

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