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A novel signal amplification strategy based on the use of copper nanoclusters for ratiometric fluorimetric determination of o-phenylenediamine

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Abstract

Copper nanoclusters (CuNCs) were synthesized starting from glutathione and copper(II) nitrate. They show blue fluorescence peaking at 432 nm when excited at 334 nm. In the presence of o-phenylenediamine (OPD), the blue fluorescence is decreased, but a yellow fluorescence appears with a peak at 557 nm. UV-visible absorptiometry, fluorometry and fluorescence lifetime measurements were used to show that OPD is oxidized by the small fraction of copper(II) ions present in the CuNCs to form the oxidized form of o-phenylenediamine (oxOPD) which displays weak yellow fluorescence, while the blue fluorescence decreases. The ratio of fluorescences at 557 and 432 nm increases linearly in the 0.15 to 110 μg·L−1 OPD concentration range, and the detection limit is 93 ng·L−1. Compared to the method based on the use of dissolved Cu(II), the employment of CuNCs reduces the detection limit by a factor of 40. The method was applied to the determination of OPD in spiked environmental water and industrial wastewater samples. Recoveries ranged from 96.8 to 100.3%.

Schematic presentation of a ratiometric fluorometric method for detection of o-phenylenediamine (OPD) based on copper nanoclusters (CuNCs). OPD is oxidized by Cu2+ present in CuNCs to form the oxidized form of o-phenylenediamine (oxOPD). FRET occurred between oxOPD and CuNCs, and the F557/F432 value is amplified.

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (Nos. 21575043, 21275056, 21605052, 51478196); and the Platform Construction Project of Guangzhou Science Technology and Innovation Commission (No. 15180001).

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Authors and Affiliations

  1. School of Chemistry and Environment, Guangzhou Key Laboratory of Analytical Chemistry for Biomedicine, South China Normal University, No. 378 Waihuan West Road, University City, Guangzhou, 510006, Guangdong, China

    Yujun Ma, Ying Yu, Bixia Lin, Li Zhang, Yujuan Cao & Manli Guo

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Ma, Y., Yu, Y., Lin, B. et al. A novel signal amplification strategy based on the use of copper nanoclusters for ratiometric fluorimetric determination of o-phenylenediamine. Microchim Acta 186, 206 (2019). https://doi.org/10.1007/s00604-019-3327-7

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