A dual-mode biosensor constructed based on photoelectrochemical (PEC) and electrochemical (EC) property was developed for assaying circulating tumor DNA (ctDNA), which is commonly used for triple-negative breast cancer diagnosis. Ionic liquid functionalized two-dimensional Nd-MOF nanosheets were successfully synthesized through a template-assisted reagent substituting reaction. Nd-MOF nanosheets integrated with gold nanoparticles (AuNPs) were able to improve photocurrent response and supply active sites for assembling sensing elements. To achieve selective detection of ctDNA, thiol-functionalized capture probes (CPs) were immobilized on the Nd-MOF@AuNPs modified glassy carbon electrode surface, thereby generating a "signal-off" photoelectrochemical biosensor for ctDNA under visible light irradiation. After the recognition of ctDNA, ferrocene-labeled signaling probes (Fc-SPs) were introduced into the biosensing interface. After hybridization between ctDNA and Fc-SPs, the oxidation peak current of Fc-SPs generated from square wave voltammetry can be employed as a "signal-on" electrochemical signal for ctDNA quantification. Under the optimized conditions, a linear relationship was obtained to the logarithm of ctDNA concentration in between 1.0 fmol L-1 to 10 nmol L-1 for the PEC model and 1.0 fmol L-1 to 1.0 nmol L-1 for the EC model. The dual-mode biosensor can provide accurate results for ctDNA assays, effectively eliminating the probable occurrence of false-positive or false-negative results in single-model assays. By switching DNA probe sequences, the proposed dual-mode biosensing platform can serve as a strategy for detecting other DNAs and possesses broad applications in bioassay and early disease diagnosis.
Keywords: Biosensor; Circulating tumor DNA; Electrochemical; Ionic liquid; MOFs; Photoelectrochemical.
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