A homogeneous electrochemical DNA sensor on the basis of a self-assembled thiol layer on a gold support and by using tetraferrocene for signal amplification.

: An unmodified electrochemical biosensor has been constructed, which can directly detect DNA in homogeneous solution. The synthesized new compound tetraferrocene was used for signal amplification. The dual-hairpin probe DNA was tagged with a tetraferrocene at the 3' terminal and a thiol at the 5' terminal. Without being hybridized with target DNA, the loop of probe prevented the thiol from contacting the exposed gold electrode surface with an applied potential. After hybridization with the target DNA, the loop-stem structure of the probe was opened, which led to the formation of the hairpin DNA structure. Afterwards, the thiol easily contacted the electrode and accomplished potential-assisted Au-S self-assembly. Its current signal depends on the concentration of target DNA in the 1.8 × 10-13 to 1.8 × 10-9 M concentration range, and the detection limit is 0.14 pM. The technique is a meaningful study because of its high selectivity and sensitivity. Graphical abstract Schematic diagram of the electrochemical DNA sensor operation. Target DNA and probe DNA hybridization, resulting in the disappearance of the steric hindrance of the probe stem ring. A higher signal was generated when tetraferrocene reached the electrode. The electrochemical signals were determined by differential voltammetric pulses (DPV).