A triply amplified electrochemical lead(II) sensor by using a DNAzyme and via formation of a DNA-gold nanoparticle network induced by a catalytic hairpin assembly


An amplified electrochemical biosensing scheme is described for lead(II) ions. It is making use of DNAzyme-assisted target recycling and catalytic hairpin assembly (CHA). The hairpin strand (substrate probe for the Pb2+-based DNAzyme; referred to as SP) is composed of trigger probe (TP) and a capture probe 1 attached to gold nanoparticles (AuNP). In the presence of the enzyme probe that partially hybridizes with SP, the introduction of Pb2+ triggers target recycling and drives the highly amplified translation of target Pb(II) to TP. The CHA reaction is further initiated by TP. The modified AuNP act as the connecting unit, and this leads to the formation of a 3D DNA-AuNP network on the electrode (which is the third amplification step). It can bind the positively charged redox mediator RuHex via electrostatic interaction for electrochemical detection. This biosensor has a low detection limit (95 pM) and any analytical range that covers the 100 pM to 5 μM Pb(II) concentration range. It is selective over other divalent metal ions. It was applied to the determination of Pb2+ in spiked real-world samples.

Schematic presentation of the electrochemical biosensor. The triply amplified electrochemical assay is based on the use of DNAzyme-assisted target recycling with catalytic hairpin assembly (CHA) reaction for sensitive and selective determination of lead ion (Pb2+). AuNP: gold nanoparticles; SP: substrate probe; EP: enzyme probe.

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This work was supported by National Natural Science Foundation of China (31471644), the Primary Research & Development Plan of Shandong Province (2017GSF220009), the Program for Taishan Scholer of Shandong Province (TS201712048), University of Jinan Scientific Research Fund (Youth Project XKY1421) and Doctoral Fundation of University of Jinan (XBS1431).

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Correspondence to Su Liu.

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Song, X., Wang, Y., Liu, S. et al. A triply amplified electrochemical lead(II) sensor by using a DNAzyme and via formation of a DNA-gold nanoparticle network induced by a catalytic hairpin assembly. Microchim Acta 186, 559 (2019). https://doi.org/10.1007/s00604-019-3612-5

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  • Lead ion
  • Electrochemical
  • Biosensor
  • DNAzyme
  • Hairpin-shaped substrate probe
  • Triple signal amplification
  • Catalytic hairpin assembly
  • 3D DNA-AuNP network
  • RuHex
  • Real water samples