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Polystyrenesulfonate-coated nanoparticles with low cytotoxicity for determination of copper(II) via the luminescence of Tb(III) complexes with new calix[4]arene derivatives

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Abstract

The authors describe new ligands with two 1,3-diketone groups and two heteroaromatic (pyridyl or quinolyl) moieties embedded to the upper and lower rims of dibromo-substituted calix[4]arene scaffold. The ligands bind Tb(III) ions in alkaline DMF solutions to form 1:1 complexes. The strong Tb(III)-centered luminescence (with excitation/emission peaks at 330/545 nm) of the complexes results from efficient ligand-to-metal energy transfer. The complexes were incorporated into polystyrenesulfonate (PSS) colloids by diluting a DMF solution of the complex with aqueous solution of PSS. The luminescence of the colloids is quenched by copper(II), and this was used to develop a method for its fluorometric determination in nanomolar concentrations. The lower limit of detection is 0.88 nM. Quenching is a result of (a) ion exchange which converts the terbium complexes into their copper counterparts, and (b) energy transfer from Tb(III) to Cu(II) complexes. The low cytotoxicity of the colloidal nanoprobe conceivably makes it a promising tool for use in cellular imaging.

New calix[4]arene derivative provide efficient binding sites for Tb(III) and Cu(II) ions. The Tb(III) complexes were embedded to core-shell nanoparticles by solvent-mediated aggregation followed by polystryrenesulfonate deposition. The nanoparticles exhibit luminescence response on copper ions in nanomolar concentration range.

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Authors and Affiliations

  1. Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov str., 8, Kazan, Russian Federation, 420088

    Rustem R. Zairov, Svetlana N. Sudakova, Victor V. Syakaev, Alexandra D. Voloshina, Irek R. Nizameev, Aida I. Samigullina, Aidar T. Gubaidullin, Sergey N. Podyachev & Asiya R. Mustafina

  2. Kazan National Research Technological University, K. Marks Str., 68, 420015, Kazan, Russia

    Rinas N. Nagimov, Gulnaz Sh. Gimazetdinova & Irek R. Nizameev

  3. Zavoisky Physical-Technical Institute, Federal Research Center “Kazan Scientific Center of RAS”, Sibirsky tract, 10/7, 420029, Kazan, Russia

    Dmitry V. Lapaev

  4. Division of Mathematical Sciences, Luleå University of Technology, SE-971 87, Luleå, Sweden

    Mykola Shykula

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  1. Rustem R. Zairov
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Correspondence to Rustem R. Zairov.

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Zairov, R.R., Nagimov, R.N., Sudakova, S.N. et al. Polystyrenesulfonate-coated nanoparticles with low cytotoxicity for determination of copper(II) via the luminescence of Tb(III) complexes with new calix[4]arene derivatives. Microchim Acta 185, 386 (2018). https://doi.org/10.1007/s00604-018-2923-2

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