Integrating ratiometric photoelectrochemical (PEC) techniques with paper microfluidics to construct a ratiometric PEC paper analytical device for practical application is often restricted by the grave dependence of ratiometric assay on photoactive materials and low mass-transfer rates of the paper channel. Herein, a universal donor/acceptor-induced ratiometric PEC paper analytical device with a hollow double-hydrophilic-walls channel (HDHC) was fabricated for high-performance microRNA-141 (miRNA-141) quantification. Concretely, a photoanode and photocathode were integrated on the paper-based sensing platform in which the photocathode served as a biosensing site for the pursuit of higher selectivity. For formulation of a cascading signal amplification strategy, a unique duplex-specific nuclease-induced target recycling reaction was engineered for the output of a double amount of all useful DNA linkers instead of conventional output of only one available DNA product, which could guarantee the output of abundant DNA linkers with the initiation of a cascade of hybridization chain reaction on both the trunk and branch in the presence of miRNA-141. Then the formed dendriform polymeric DNA duplex structures were further decorated with glucose oxidase (GOx)-mimicking gold nanoparticles by the electrostatic interaction to form a branchy gold tree (BGT). Profiting from the perfect GOx-mimicking activity of BGT and high mass-transfer rates of HDHC, the cathodic photocurrent from Ag2S/Cu2O hybrid structure was in a “signal off” state while the anodic photocurrent from graphene quantum dots (GQDs) and Ag2Se QDs cosensitized ZnO nanosheets was in a “signal on” state because BGT-catalyzed glucose oxidation reaction evoked the consumption of dissolved O2 as an electron acceptor and the generation of H2O2 as an electron donor. With calculation of the ratio of two photocurrent intensities, the quantitative detection of miRNA-141 was achieved with high sensitivity, accuracy, and reliability.

In this work, a lab-on-paper cathode photoelectrochemical (PEC) sensing platform was constructed for ultrasensitive microRNA-141 (miRNA-141) assay using cascaded multiple photo-active structures as signal generators and hemin/Pt nanoparticle (Pt NP) trunk-branching-decorated DNA dendrimers as signal reinforcers. Specifically, pyramid-like Cu2O was first in situ grown on the Au nanoparticle-functionalized tangled cellulose fibers network, followed by the sensitization of trepang-like BiVO4–Bi2S3 heterostructures, forming the cascaded sensitization structures. Then, the DNA dendrimer was introduced into the photocathode sensing interface by coupling the duplex-specific-nuclease (DSN)-induced target recycling reaction with multiple-branched hybridization chain reaction (MHCR). The programmed target recycling procedures propelled using DSN guaranteed the highly amplified transduction of miRNA-141 to the exposed initiator strand, which triggered the cascaded MHCR accompanied by the formation of the DNA dendrimer with unique trunk-branching structures. Finally, the hemin/Pt NP trunk-branching-decorated DNA dendrimer (HPTD) was acquired by the assembly of Pt NPs and hemin on the trunk and branch, respectively. The resulting HPTD with the synergy catalysis of Pt NPs and hemin could efficiently catalyze the decomposition of H2O2 for in situ generation of O2 as the electron acceptor, leading to an enhanced photocurrent response. Based on the target-dependent photocurrent enhancement, ultrasensitive determination of miRNA-141 was realized with persuasive selectivity, high stability, and excellent reproducibility. Thus, the proposed paper-based cathode PEC sensing platform possessed promising application prospect in clinical miRNA diagnosis.

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