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Ultrasensitive detection of toxic cations through changes in the tunnelling current across films of striped nanoparticles

Abstract

Although multiple methods have been developed to detect metal cations, only a few offer sensitivities below 1 pM, and many require complicated procedures and sophisticated equipment. Here, we describe a class of simple solid-state sensors for the ultrasensitive detection of heavy-metal cations (notably, an unprecedented attomolar limit for the detection of CH3Hg+ in both standardized solutions and environmental samples) through changes in the tunnelling current across films of nanoparticles (NPs) protected with striped monolayers of organic ligands. The sensors are also highly selective because of the ligand–shell organization of the NPs. On binding of metal cations, the electronic structure of the molecular bridges between proximal NPs changes, the tunnelling current increases and highly conductive paths ultimately percolate the entire film. The nanoscale heterogeneity of the structure of the film broadens the range of the cation-binding constants, which leads to wide sensitivity ranges (remarkably, over 18 orders of magnitude in CH3Hg+ concentration).

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Figure 1: Experimental set-up and typical jE plots.
Figure 2: Sensitivity (left column) and selectivity (right column) of cation sensing by different types of Au NPs decorated by HT/EGn SAMs.
Figure 3: Selectivity of the films on exposure to cation mixtures and environmental samples.
Figure 4: Rationalizing the conductance through the molecular bridge between the striped NPs.
Figure 5: Percolation of Au NP films on cation binding.

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Acknowledgements

This work was supported by the Non-equilibrium Energy Research Center, which is an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under grant number DE-SC0000989. E.S.C. and F.S. acknowledge the support of ENI within the MIT Energy initiative for their work. E.S.C. is supported by a Samsung Scholarship from the Samsung Foundation of Culture. H.J., S.C.G. and F.S. acknowledge support from the Defense Threat Reduction Agency under Grant No. HDTRA1-09-1-0012. T.M.H. is financially supported by the Human Frontier Science Program. We acknowledge L. Meda for her X-ray photoelectron spectroscopy measurements, and R. Borrelli and P. Cesti for helpful discussions. We also thank the USGS for providing fish samples and for helpful discussions.

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E.S.C. synthesized the striped nanoparticles, performed all of their characterization before and after binding to ions, and helped with some of the solid-state work.; J.K. made and characterized all sensors, performed cation capture experiments, measured the conductivities of all sensors and analysed data; B.T. developed quantum-mechanical models and ran quantum-mechanical calculations; T.M.H. developed and validated the binding/percolation models; H.J. ran and analysed MD simulations; S.C.G. analysed and supervised the MD simulations; H.N. performed initial experiments with NP films; M.Y. performed the STM characterization of the particles; A.Z.P. helped with the theory of percolation phenomena; F.S. and B.A.G. conceived the ideas and supervised the research.

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Correspondence to Francesco Stellacci or Bartosz A. Grzybowski.

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Cho, E., Kim, J., Tejerina, B. et al. Ultrasensitive detection of toxic cations through changes in the tunnelling current across films of striped nanoparticles. Nature Mater 11, 978–985 (2012). https://doi.org/10.1038/nmat3406

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