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Graphene quantum dots–terbium ions as novel sensitive and selective time-resolved luminescent probes

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Abstract

We propose an alternative approach for the development of analytical methods based on terbium-sensitized luminescence (TSL). TSL is based on the complexation between Tb(III) ions and fluorescent organic compounds that have appropriate functional groups to complex with Tb(III). We report the use of graphene quantum dot (GQDs) nanoparticles to improve the sensitivity and selectivity of TSL detection. GQDs can react with terbium ions through the carboxylic groups present in their structure. These Tb(III)–GQD complexes, formed in situ in aqueous solution, can be used as time-resolved luminescent probes. Ascorbic acid was selected as a target analyte to demonstrate the suitability of the proposed method. The selectivity of the TSL method was highly improved for most of the interferences tested. Under the optimum conditions [Tb(III) concentration 5 × 10-4 mol L-1, GQD concentration 4 mg L-1], a minimum 100% increase in selectivity was observed for several vitamins and common cations that may be present in the samples to be analyzed. In addition, the analytical signal showed a 30% enhancement with the use of GQDs compared with the use of merely Tb(III) ions, with a detection limit of 0.12 μg mL-1. The repeatability and intermediate precision were lower than 3% and 5%, respectively. From the results obtained, the implementation of GQDs in TSL can lead to the development of novel time-resolved luminescent probes with high analytical potential.

Quenching of Tb(III)–graphene quantum dot (GQD) luminescence by ascorbic acid (AA). TBL terbium-sensitized luminescence

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Acknowledgements

The following funding is acknowledged: CTQ2016-78793-P and CTQ2016-7511-R (Spanish Ministry of Economy and Competitiveness, MINECO), PEIC-2014-001-P (Junta de Comunidades de Castilla-La Mancha, JCCM) and DIPUCR-16-LLORENTMARTINEZ (Diputación de Ciudad Real). EJLM also acknowledges the financial support from the University of Castilla-La Mancha Research and Mobility Plans.

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Authors and Affiliations

  1. Department of Analytical Chemistry and Food Technology, University of Castilla-La Mancha, Camilo José Cela Av., 13071, 13071, Ciudad Real, Spain

    Eulogio J. Llorent-Martínez, Gema M. Durán & Ángel Ríos

  2. Regional Institute for Applied Chemistry Research (IRICA), Camilo José Cela Av., 13071, Ciudad Real, Spain

    Eulogio J. Llorent-Martínez, Gema M. Durán & Ángel Ríos

  3. Department of Physical and Analytical Chemistry, Faculty of Experimental Sciences, University of Jaén, Campus Las Lagunillas, 23071, Jaén, Spain

    Antonio Ruiz-Medina

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  1. Eulogio J. Llorent-Martínez
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  2. Gema M. Durán
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  3. Ángel Ríos
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  4. Antonio Ruiz-Medina
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Correspondence to Antonio Ruiz-Medina.

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Llorent-Martínez, E.J., Durán, G.M., Ríos, Á. et al. Graphene quantum dots–terbium ions as novel sensitive and selective time-resolved luminescent probes. Anal Bioanal Chem 410, 391–398 (2018). https://doi.org/10.1007/s00216-017-0728-5

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  • DOI: https://doi.org/10.1007/s00216-017-0728-5

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