Highly Sensitive Electrochemical Sensor for Mercury(II) Ions by Using a Mercury-Specific Oligonucleotide Probe and Gold Nanoparticle-Based Amplification

We report a highly sensitive electrochemical sensor for the detection of Hg2+ ions in aqueous solution by using a thymine (T)-rich, mercury-specific oligonucleotide (MSO) probe and gold nanoparticles (Au NPs)-based signal amplification. The MSO probe contains seven thymine bases at both ends and a mute spacer in the middle, which, in the presence of Hg2+, forms a hairpin structure via the Hg2+-mediated coordination of T-Hg2+-T base pairs. The thiolated MSO probe is immobilized on Au electrodes to capture free Hg2+ in aqueous media, and the MSO-bound Hg2+ can be electrochemically reduced to Hg+, which provides a readout signal for quantitative detection of Hg2+. This direct immobilization strategy leads to a detection limit of 1 mu M. In order to improve the sensitivity, MSO probe-modified Au NPs are employed to amplify the electrochemical signals. Au NPs are comodified with the MSO probe and a linking probe that is complementary to a capture DNA probe immobilized on gold electrodes. We demonstrated that this Au NPs-based sensing strategy brings about an amplification factor of more than 3 orders of magnitude, leading to a limit of detection of 0.5 nM (100 ppt), which satisfactorily meets the sensitivity requirement of U.S. Environmental Protection Agency (EPA). This Au NPs-based Hg2+ sensor also exhibits excellent selectivity over a spectrum of interference metal ions. Considering the high sensitivity and selectivity of this sensor, as well as the cost-effective and portable features of electrochemical techniques, we expect this Au NPs amplified electrochemical sensor will be a promising candidate for field detection of environmentally toxic mercury.