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Plasmonic nanosensors with inverse sensitivity by means of enzyme-guided crystal growth

A Corrigendum to this article was published on 23 January 2018

An Addendum to this article was published on 23 January 2018

This article has been updated


Lowering the limit of detection is key to the design of sensors needed for food safety regulations1,2, environmental policies3,4,5 and the diagnosis of severe diseases6,7,8,9,10. However, because conventional transducers generate a signal that is directly proportional to the concentration of the target molecule, ultralow concentrations of the molecule result in variations in the physical properties of the sensor that are tiny, and therefore difficult to detect with confidence. Here we present a signal-generation mechanism that redefines the limit of detection of nanoparticle sensors by inducing a signal that is larger when the target molecule is less concentrated. The key step to achieve this inverse sensitivity is to use an enzyme that controls the rate of nucleation of silver nanocrystals on plasmonic transducers. We demonstrate the outstanding sensitivity and robustness of this approach by detecting the cancer biomarker prostate-specific antigen down to 10−18 g ml−1 (4 × 10−20 M) in whole serum.

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Figure 1: Scheme of the proposed signal-generation mechanism by means of enzyme-guided crystal growth.
Figure 2: Inverse sensitivity in plasmonic nanosensors.
Figure 3: TEM and XEDS analysis of silver-coated gold nanostars.
Figure 4: Immunoassay for the ultrasensitive detection of PSA with GOx-labelled antibodies.

Change history

  • 15 December 2017

    In the version of this Letter originally published, the x and y values of the data points in Fig. 2c were incorrect. The authors have also made some changes to the Supplementary Information: Fig. S9 has been replaced because the x values were incorrect; the value of the carbonate buffer concentration has been corrected to 10 mM; and the sentence on page 2 that read "Subsequently, non-reacted aldehyde sites were blocked with bovine serum albumin (BSA, 0.1 mg/mL) and ethanolamine (10 mM) in bicarbonate buffer for 1 h." has been changed to "When modifying nanostars with antibodies, non-reacted aldehyde sites were blocked with bovine serum albumin (BSA, 0.1 mg/mL) and ethanolamine (10 mM) in bicarbonate buffer for 1 h."

  • 23 January 2018

    Nature Materials 11, 604–607 (2012); published online 27 May 2012; corrected after print 15 December 2017. In the version of this Letter originally published, the x and y values of the data points in Fig. 2c were incorrect. The original and corrected versions are shown below. The authors have also made some changes to the Supplementary Information: Fig.


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B. Rodrı´guez-González is thanked for electron-microscopy analysis. M.M.S. thanks the EPSRC and ERC starting investigator grant ‘Naturale’ for financial support. This research was supported by a Marie Curie Intra European Fellowship within the 7th European Community Framework Programme (R.d.l.R.). L.M.L-M. acknowledges the ERC grant ‘Plasmaquo’ for financial support. L.R-L. acknowledges an FPU scholarship from Ministerio de Educación, Spain. R.A.A-P. acknowledges financial support from CTQ2011-23167 (Ministerio de Economíca y Competitividad, Spain).

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R.d.l.R. elaborated the concept and designed experiments. L.R-L. performed the experiments. M.M.S. and L.M.L-M. supervised the project. All of the authors participated in scientific discussions and wrote the paper.

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Correspondence to Roberto de la Rica or Molly M. Stevens.

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The authors declare no competing financial interests.

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Rodríguez-Lorenzo, L., de la Rica, R., Álvarez-Puebla, R. et al. Plasmonic nanosensors with inverse sensitivity by means of enzyme-guided crystal growth. Nature Mater 11, 604–607 (2012).

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