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Electrochemiluminescent (ECL) [Ru(bpy)3]2+/PAMAM dendrimer reactions: coreactant effect and 5-fluorouracil/dendrimer complex formation

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Abstract

Electrogenerated chemiluminescence (ECL) reactions between tris(2,2′-bipyridine)ruthenium(II) and PAMAM dendrimers of the full (G1.0) and half (G1.5) generations were carried out in an aqueous medium at pH 6.1 and 10.0. In the absence of 5-fluoro-1H,3H-pyrimidine-2,4-dione (5-fluorouracil, 5-Fu) (coreactant effect study), the ECL efficiency trends as a function of [G1.0] and [G1.5] at pH 6.1 and 10.0 revealed that PAMAM dendrimers are about 100 (G1.5, pH 6.1), 60 (G1.5, pH 10.0), 26 (G1.0, pH 10.0) and 13 (G1.0, pH 6.1) times more efficient as ECL coreactants than oxalate anion is. Moreover, ECL reactions were done in the presence of several solutions of 5-Fu at a fixed concentration of the G1.0 and G1.5 dendrimers at pH 6.1 and 10.0 (binding study). The ECL efficiency trends as a function of [5-Fu] highlighted a dendrimer/5-Fu binding. Therefore, one of the most remarkable and novel findings of this work is the potential of PAMAM dendrimers to be used as both sensors and biosensors in an aqueous medium in the presence of a suitable sensitizer. Redox potentials of the [Ru(bpy)3]3+/2+ couple were also determined in the absence and presence of 5-Fu at both pHs. In the absence of 5-Fu the positive or negative shift of redox potentials showed the influence of the repulsive or attractive electrostatic long-range and short-range interactions between the charged dendrimer surface and the oxidized and reduced forms of the couple. In the presence of 5-Fu the trends of redox potentials highlighted the existence of a charged dendrimer/5-Fu species.

ECL emission for the [Ru(bpy)3]2+/ G1.0 dendrimer reaction in the presence of the 5-Fu at pH 6.1

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Scheme 1
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Notes

  1. CV experiments and ECL emissions were recorded simultaneously from a Potentiostat /Galvanostat (Biologic SP-50) synchronized to a PTI fluorescence spectrometer. A Peltier system interfaced to the instrument set was employed to maintain a constant temperature of 298.15 ± 0.01 K inside the spectro-electrochemical cell. The reading and handling of voltammograms and ECL emissions was done with a PC using EC-Lab Express and Felix32 software, respectively. The software allowed for the subtraction of the files and the integration of both current–time and ECL intensity–time curves.

  2. Given that the end groups of the dendrimers (–COO− for G1.5 and –NH2 for G1.0) are responsible for the ECL effect we assume that the reaction ECL mechanisms are similar to those corresponding to [Ru(bpy)3]2+ + C2O4 2− and [Ru(bpy)3]2+ + TPA in aqueous solutions (see, e.g., [9, 16]). In the case of the first reaction, the first electron transfer corresponds to a catalytic reaction, Ru(bpy)3 3+ + C2O4 2− ⇌ Ru(bpy)3 2+ + CO2 •− + CO2, and the second one produces Ru(II)*, Ru(bpy)3 3+ + CO2 •− → Ru(bpy)3 2+* + CO2.

  3. To generate Ru(II)* several steps are involved in a given ECL mechanism (see, e.g., [1, 2, 9]).

  4. The electrostatic repulsion between the positively charged Ru(II) species and the electric field arising from the surface of the G1.0 dendrimer at pH 6.1 can be accounted for by studying the shift of the redox potentials of the [Ru(bpy)3]3+/2+ couple. In this case, E peak − E 0 = (RT/F) ln(γox /γred), where E peak and E 0 are the peak and standard potentials, respectively, γox and γred refer to the activity coefficients of the oxidized and reduced species of the pair, and RT/F have the usual meaning. In the presence of a positively charged dendrimer surface both γox and γred increase as a result of destabilization of both the oxidized and reduced forms of the couple [Ru(bpy)3]3+/2+, but the increase in γox will be greater than the one corresponding to γred as a result of the [Ru(bpy)3]3+ form bearing a higher positive charge. This effect results in a positive shift of redox potentials.

  5. Several experiments were carried out to check the dendrimer/5-Fu complex formation. They refer to quenching photoluminescent measurements of the dendrimer species by 5-Fu as a quencher (see ESM, Fig. S3 and Table S2). According to these data, it is evident that an interaction dendrimer/5-Fu exists.

  6. In fact, we have determined the redox potentials of 5-Fu in the presence of Ru(II) complex and in their absence, the values obtained being 1.372 and 1.426 V vs. SHE, respectively. It should be noted that both redox processes were practically not reversible; thus, the previous values refer to the anodic wave peaks.

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Acknowledgements

This work was financed by the Consejería de Educación y Ciencia de la Junta de Andalucía (FQM-03623).

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  1. Department of Physical Chemistry, Faculty of Chemistry, University of Seville, C/ Profesor García González s/n, 41012, Seville, Spain

    Aila Jimenez-Ruiz, Elia Grueso, Pilar Perez-Tejeda, Fernando Muriel-Delgado & Concepcion Torres-Marquez

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  1. Aila Jimenez-Ruiz
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  2. Elia Grueso
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  3. Pilar Perez-Tejeda
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  4. Fernando Muriel-Delgado
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Correspondence to Pilar Perez-Tejeda.

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Published in the topical collection Analytical Electrochemiluminescence with guest editors Hua Cui, Francesco Paolucci, Neso Sojic, and Guobao Xu.

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Jimenez-Ruiz, A., Grueso, E., Perez-Tejeda, P. et al. Electrochemiluminescent (ECL) [Ru(bpy)3]2+/PAMAM dendrimer reactions: coreactant effect and 5-fluorouracil/dendrimer complex formation. Anal Bioanal Chem 408, 7213–7224 (2016). https://doi.org/10.1007/s00216-016-9816-1

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