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The development of accurate and reliable sensor for on-site detection of microcystin-LR (MC-LR), one of hazardous environmental pollutants, is highly required. Herein, a laser induced graphene (LIG)-based electrochemical aptasensor for sensitive on-site detection of MC-LR was reported. LIG electrode, the substrate of aptasensor, was prepared via thermal transfer with ethylene-vinyl acetate copolymer, and LIG acted as quasi-reference electrode to replace conventional Ag/AgCl electrode for better operability and robustness. LIG electrode provided large surface area to assemble tetrahedral DNA to absorb methylene blue (MB) for the signal amplification. For detection, the specific recognition of MC-LR with aptamer led to the stripping of tetrahedral DNA complex and further the decreased redox current of MB (I MB). Consequently, the fabricated aptasensor offered high analytical performance for MC-LR detection with a linear range of 1 × 10-2-1 × 105 pM and a detection limit of 3 × 10-3 pM, which was successfully used for water sample analysis with comparable reliability and accuracy of standard method. Furthermore, a portable detection platform by coupling of LIG-based electrochemical aptasensor with electrochemical workstation was constructed for on-site detection of MC-LR. This work offers a novel method for the on-site monitoring of MC-LR, which promotes the investigation of LIG-based electrochemical biosensing in the field of environmental analysis. [ABSTRACT FROM AUTHOR]

Efficient signal amplification using light irradiation in electrochemistry-based sensing attracts growing interest; however, the modulation of electrochemical and photoelectrochemical behaviors of bifunctional probes remains challenging for the better analytical performance. Here, we found that the bifunctional probe methylene blue (MB) under irradiation followed two routes, i.e., photoelectrochemistry (PEC)-driven and electrochemistry (EC)-driven route, while plasmon-modulated competition between PEC-driven and EC-driven routes efficiently enhanced the analytical performance of aptasensor. Ferrocene-labeled aptamer (Fc-apt) was applied to tune the interaction between MB labeled complementary DNA (MB-cDNA) and plasmonic gold nanoparticles (AuNPs). Under visible light illumination, the aptasensor output a weak current of MB (I MB) for the depressed EC-driven redox. The binding of Fc-apt with target led to its stripping from electrode and released MB-cDNA to approach AuNPs, and an increase in I MB was observed due to the synergy of the depressed PEC-driven redox while the restored EC-driven redox. In this way, the amplified response for target could be obtained by depressing background signal while enlarging response signal of I MB under visible light. Consequently, the developed model ratiometric aptasensor offered a higher sensitivity for the determination of aflatoxin B1. Our observation should be favorable to shed light on photo-induced electrochemical mechanism, and the proposed amplification strategy is valuable for the construction of efficient sensors. [ABSTRACT FROM AUTHOR]