Developing efficient strategies for sensitive detection of microRNAs, the noncoding bioactive molecules and wellestablished biomarkers, has aroused great interests due to its great potential values in genetic and pathological analyses. Herein, a highly selective and disposable paper-based photoelectrochemical (PEC) sensor was rationally designed for sensing microRNA based on simple self-assembly of a target-triggerable DNA motor and nanozyme-catalyzed multistage biocatalytic precipitation reaction. Specifically, a brand-new type II heterojunction of TiO 2 −CeO 2 nanotubes decorated with carbon fiber paper (CFP) was first prepared, which gave an enhanced photoreactive surface and realized fast electron transport and extraction, markedly accelerating photoelectric conversion efficiency of the sensor. For achieving target detection, cascade nanozyme centers of the CeO 2 and Au nanoparticles modified by cyclodextrin were drafted, greatly decreasing the photocurrent intensity and achieving an ultralow background signal. With target introduction, the DNA motor was activated and automatically moved along the predesigned route driven by an endonuclease cleavage reaction, resulting in more substrate probe digestion and nanozyme release from CFP. Consequently, the repressive inner enhancement mechanism was gradually renewed with constant advancement of the enzymatic reaction and walker probe walking progressively, eventually allowing multiple enzymatic factor output in each target import. As a proof-of-concept application, the developed PEC sensor successfully performed detection of miRNA-141, showing a low detection limit of 0.6 fM, and was further applied to real sample bioassays with satisfying results. This work proposes promising strategies to boost the catalytic cascade DNA-motor adhibition in biological samples analysis and also exhibits potential capability in detection of other targets.

Real-time monitoring of neonicotinoid pesticide residues is of great significance for food security and sustainable development of the ecological environment. Herein, a paper-based surface-enhanced Raman scattering (SERS) amplified approach was proposed by virtue of multilayered plasmonic coupling amplification. The unique plasmonic SERS multilayer was constructed using three-dimensional (3D) silver dendrite (SD)/electropolymerized molecular identifier (EMI)/silver nanoparticle (AgNP) sandwich hybrids with multiple hotspots and a strong electromagnetic field in nanogaps. Dendritelike 3D silver materials with remarkably high accessible surface areas and the lightning rod effect constituted the first-order enhancement of paper-based sensors. Molecular identifiers coated upon an SD layer as the interlayer were used for target capture and enrichment. Subsequently, AgNPs featuring rough surface and local plasma resonance decorated as the top layer formed the secondary enhancement of the amplification strategy. As the most brilliant part, dendritelike 3D silver coupled with AgNPs has established double Ag layers to accomplish a multistage enhancement of SERS signals based on the superposition of their electromagnetic fields. Owning to the distinctive design of the multiple coupling amplification strategy, the fabricated SERS paper chips demonstrated impressive specificity and ultrahigh sensitivity in the detection of imidacloprid (IMI), with a detection limit as low as 0.02811 ng mL −1 . More importantly, the multiple SERS enhancement paper chip holds great potential for automated screening of a variety of contaminants.

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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.

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