Ultrasensitive and accurate detection of biomarkers in serum is of great importance for disease diagnosis and treatment. So far, the commonly used single-mode signal suffers from certain instinct drawbacks that restrict assay performances. Herein, we report the proof-of-concept fabrication of a split-type photoelectrochemical (PEC) and electrochemical (EC) dual-modal aptasensor for ultrasensitively tracing tumor necrosis factor-α, a noteworthy biological biomarker with essential clinical importance. By smart integrating molybdenum disulfide QDs/zeolitic imidazolate framework-8@ZnO nanorod arrays with a methylene blue-liposome-mediated signal amplification strategy, “dual signal-on” detection is accomplished based on a sandwich reaction of the target with aptamer-anchored carboxyl magnetic beads and an aptamer-confined MB liposome. Linear ranges of 5 fg/mL–5 μg/mL (detection limit 1.46 fg/mL) for PEC and 10 fg/mL–0.5 μg/mL (detection limit 6.14 fg/mL) for EC are obtained, respectively. An independent signal transduction mechanism supports the accuracy improvement, and a separate biological process from a translator enables convenient fabrication, short-time consumption, wider linearity, as well as outstanding reproducibility and stability in practical application. This work presents a universal bioassay route with prospects in biomedical and related areas.

In accurately diagnosing Alzheimer’s disease (AD) and distinguishing AD from other dementia, the concentration ratio of amyloid-beta 42 (Aβ42) to Aβ40 is more reliable than the concentration of Aβ42 alone. For the multiplex PEC assay, generating an independent photocurrent of multiple targets on a single interface is a great challenge. Herein, an i-motif-based switchable sensing approach is proposed to construct a pH-regulated multiplex PEC immunosensor for Aβ42 and Aβ40 by using Bi-TBAPy as an efficient photoactive cathode material. An independent photocurrent signal of Aβ42 and Aβ40 is produced through the regulation of the electron-transfer tunneling distance by a pH-dependent configuration transition of the i-motif DNA. In a 96-well plate, immunological recognition of Aβ42 (or Aβ40) coupled with an enzymatic catalytic reaction produces an acidic (or alkaline) lysis solution, which triggers the formation and unravelment of the i-motif structure. The above configuration transition regulates the distance between Au NPs labeled SH-DNA and Bi-TBAPy, leading to PEC signal switching. Smart integration of the pH-responsive switchable DNA probe with a high-efficiency photocathode enables the precise monitoring of Aβ42 and Aβ40 at a single interface in a wide detection range (10 fg/mL ∼ 1 μg/mL and 1 pg/mL ∼ 1 μg/mL) with detection limit of 4.5 fg/mL and 0.52 pg/mL, respectively. The proposed i-motif-based switchable sensing strategy paves a new avenue for a multiplex PEC assay on a single interface, showing great prospects in bioanalysis and early disease diagnosis.

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Ultrasensitive and accurate monitoring of ultralow-level biomarkers is imperiously needed in clinical diagnosis. So far, exploring high-performance photocathodes and developing new sensing strategies have remained central challenges in photoelectrochemical bioassays. Herein, a two-dimensional (2D) pyrene covalent organic framework (COF, PAF-130) is exemplified for the first time as a high-performance photocathode for precise immunosensing of α-synuclein (α-Syn) by integrating a DNAzyme-induced signal cycle amplification strategy with Ag nanoparticles (NPs)-mediated liposomal immunoassay. Through sequential immunobinding, lysis treatment, and acidolysis, numerous Ag+ ions are released, and then they activate the DNAzyme, which further recycles the cleavage of hairpin DNA (HDNA) on the photoelectrode and induces signal cycle amplification. As a result, an ultralow detection limit (3.6 fg/mL) and a wide linear range (10–5–103 ng/mL) are achieved, which surpass those of most methods reported so far. The proposed sensing approach can be readily extended to detect various biomarkers by substituting the biorecognition events, providing great promise for biomedical and related applications.

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For discriminating the signals of multi-targets, multiplexed photoelectrochemical (PEC) detection is generally accomplished by modulating the light source or voltage, which prospect is usually limited by expensive instrumentation, tedious operational steps, and time-consuming material screening. To realize multiplexed determination on single photoelectric interface using the routine technique, a non-instrument-assisted strategy for signal discrimination needs to be explored. Herein, we propose an exonuclease III-mediated multiple PEC signals resolution strategy and construct a self-cleaning recyclable multiplexed PEC sensor using a porphyrin-bipyridine-based covalent organic framework (Por-Bpy COF) photocathode. Specifically, following the dual-target recognition event, exonuclease III cleaves the DNA strand attached to the magnetic bead so that the two signal labels can be separated. Once the signal label binds to the DNA on the electrode surface (E-DNA), exonuclease III turns to excise the DNA strand of the signal label and consequently the E-DNA can repeatedly bind different signal labels. As a result, distinguishable photocurrent signals of different targets can be generated on a single photoelectric interface. The feasibility of this multiplexed sensor is verified by detecting two coexisting mycotoxins aflatoxin B1 and zearalenone. On account of eliminating the instrumentation constraints and simplifying the experimental procedures, the proposed sensing strategy may provide a brand-new idea for the exploration of portable multiplexed PEC sensing devices.

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