A laser-induced zinc oxide/graphene photoelectrode for a photocurrent-polarity-switching photoelectrochemical biosensor with bipedal DNA walker amplification.

A photocurrent-polarity-switching photoelectrochemical (PEC) biosensor was developed for the ultrasensitive detection of tobramycin (TOB) through bipedal DNA walker amplification with hemin-induced photocurrent-polarity-switching using a laser-induced zinc oxide/graphene (ZnO/LIG) photoelectrode. Specifically, the ZnO/LIG photoelectrode was synthesized in situ by a laser direct writing (LDW) technique. In the presence of TOB, it reacted with HP1 and HP2 and the DNA walker response was activated to form a stable hemin/G-quadruplex. Furthermore, hemin induced a polarity shift in the photocurrent signal. The developed analytical platform exhibited excellent photoelectron transport performance of ZnO/LIG, the signal amplification effect of the DNA walker strategy, and the photocurrent-polarity-switching ability of hemin. Therefore, it demonstrated satisfying photocurrent responses to the target TOB within the working range of 20 nM-1.0 μM at a low detection limit of 5.43 nM. The PEC platform exhibited good stability, reproducibility, sufficient sensitivity and high selectivity for complex experimental samples. Moreover, the photocurrent-polarity-switching PEC biosensor improved the anti-interference ability and avoided false positives or negatives.