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Optical observation of single atomic ions interacting with plasmonic nanorods in aqueous solution

Abstract

Plasmonic nanoparticles provide the basis for a multitude of applications in chemistry, health care and optics because of their unique properties. Nanoparticle-based techniques have evolved into powerful tools for studying molecular interactions with single-molecule resolution. Here we show that this sensing capability can be used to detect single atomic ions in aqueous medium. We monitored interactions of single zinc and mercury ions with plasmonic gold nanorods (NRs) resonantly coupled to our whispering gallery mode sensor. Our system's ability to discern permanent binding and transient interaction allows us to study the different interaction kinetics of both ion species. The detection of transient interactions enables us to confirm statistically that the sensor signals originate from single ions. Furthermore, we reveal how the ion–NR interactions evolve with respect to the medium's ionic strength as mercury ions amalgamate with gold and zinc ions eventually turn into probes of highly localized surface potentials.

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Figure 1: Experimental method and extraction of transient events.
Figure 2: Dependence of spike rates on the analyte-ion concentration, additional electrolyte concentration and the presence of EDTA.
Figure 3: Statistics of spike properties and theoretical detection probabilities for short interactions.
Figure 4: Ionic-strength dependence of the mercury ion–NR interaction.
Figure 5: Ionic-strength dependence of the zinc ion–NR interaction.
Figure 6: Model of three interaction regimes.

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Acknowledgements

The authors acknowledge financial support for this work from the Max Planck Society. M.D.B. thanks M. R. Foreman and E. Kim for their feedback on the manuscript.

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M.D.B. developed the experimental set-up, performed the experiments and data analysis, and wrote the manuscript. F.V. commented on the manuscript and supervised the project.

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Correspondence to Martin D. Baaske or Frank Vollmer.

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Baaske, M., Vollmer, F. Optical observation of single atomic ions interacting with plasmonic nanorods in aqueous solution. Nature Photon 10, 733–739 (2016). https://doi.org/10.1038/nphoton.2016.177

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