Abstract
A new method to increase the active area (A act) of nanoelectrode ensembles (NEEs) is described. To this aim, gold nanoparticles (AuNPs) are immobilized onto the surface of NEEs using cysteamine as a cross-linker able to bind the AuNPs to the heads of the nanoelectrodes to obtain the so-called AuNPs-NEEs. The analysis of the cyclic voltammograms recorded in pure supporting electrolyte showed that the presence of the nanoparticles reflects in an, approximately, ten-times increase in the electrochemically active area of the ensemble. The measurement of the amount of electroactive polyoxometalates, which can be adsorbed on the gold surface of NEEs vs. AuNPs-NEEs, confirmed a significant increase of active area for the latter. These evidences indicate that there is a good electronic connection between the AuNPs and the underlying nanoelectrodes. The possibility to exploit AuNPs-NEEs for biosensing application was tested for the case of DNA-hybridization detection. After immobilization on the gold surface of AuNPs-NEEs of a thiolated single-stranded DNA, the hybridization with complementary sequences labeled with glucose oxidase (GOx) was performed. The detection of the hybridization was achieved by adding to the electrolyte solution the GOx substrate (i.e., glucose) and a suitable redox mediator, namely the (ferrocenylmethyl) trimethylammonium (FA+) cation; when the hybridization occurs, an electrocatalytic increase of the oxidation current of FA+ is recorded. Comparison of electrocatalytic current recorded at DNA modified NEEs and AuNPs-NEEs indicate, for the latter, a significant increase in sensitivity in the detection of the DNA-hybridization event.
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Acknowledgments
This work was supported by MIUR (Rome), project: PRIN 2008MWHCP2 and by the Cross-Border Cooperation Italy–Slovenia Programme 2007–2013—Strategic Project TRANS2CARE. We thank Dr. Loredana Casalis (ELETTRA, Sincrotrone Trieste, Scuola Internazionale Superiore di Studi Avanzati) for helpful discussion and suggestions, Dr. Davide Cristofori (University Ca’ Foscari) for TEM measurements and Dr. Ljiljana Fruk (KIT—Karlsruhe Institute of Technology) for oligonucleotide stock solutions, and Dania Kendziora (KIT—Karlsruhe Institute of Technology) for D2-GOx conjugation.
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Published in the special issue Analytical Science in Italy with guest editor Aldo Roda.
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Silvestrini, M., Ugo, P. Ensembles of nanoelectrodes modified with gold nanoparticles: characterization and application to DNA-hybridization detection. Anal Bioanal Chem 405, 995–1005 (2013). https://doi.org/10.1007/s00216-012-6354-3
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DOI: https://doi.org/10.1007/s00216-012-6354-3