DNAzyme-Mediated Biodeposition Coupling Adjustable Cascade Electric Fields for Photoelectrochemical Telomerase Activity Monitoring.

Telomerase, as a specialized reverse transcriptase, plays a vital role in early cancer diagnostics and prognosis; thus, developing efficient sensing technologies is of vital importance. Herein, an innovative "signal-on-off" photoelectrochemical (PEC) sensing platform was developed for ultrasensitive evaluation of telomerase activity based on an electron-transfer tunneling distance regulation strategy and DNAzyme-triggerable biocatalytic precipitation. Concretely, cascade internal electric fields between CuInS2 quantum dots (QDs), graphitic carbon nitride nanosheets (g-C3N4 NSs), and TiO2 nanorod arrays (NRAs) were developed to realize cascade electron extraction and hole transfer. Enabled by such a design, an effective "signal-on" state to gain a progressively enhanced PEC output was designed by suppressing the photogenerated electron-hole pair recombination. With the introduction of hairpin probe H2 and the subsequent extension of the primer sequence driven by the target telomerase, the CuInS2 QDs labeled with hairpin probe H1 were programmatically unfolded, resulting in CuInS2 QDs' close proximity to the working electrode away from the cascade interface, accompanied by the formation of G-quadruplex/hemin complexes. The gradual undermining of tunneling distance and implantation of DNAzyme-initiating biocatalytic precipitation tremendously induced the sluggish migration kinetics of the photoinduced charge, accompanied by the photocurrent intensity decrement, leading to the "signal-off" state. Under optimized conditions, the as-prepared PEC biosensor realizes ultrasensitive detection of telomerase activity from 10 to 105 cell·mL-1 with a detection limitation of 3 cells·mL-1. As a proof of concept, this well-designed method provides new insights into signal amplification for telomerase activity evaluation and also presents promising potential for further development in drug screening, healthcare diagnostics, and biological assays.

A Target-Driven Self-Feedback Paper-Based Photoelectrochemical Sensing Platform for Ultrasensitive Detection of Ochratoxin A with an In2S3/WO3 Heterojunction Structure.

Currently, developing versatile, easy-to-operate, and effective signal amplification strategies hold great promise in photoelectrochemical (PEC) biosensing. Herein, an ultrasensitive polyvinylpyrrolidone-treated In2S3/WO3 (In2S3-P/WO3)-functionalized paper-based PEC sensor was established for sensing ochratoxin A (OTA) based on a target-driven self-feedback (TDSF) mechanism enabled by a dual cycling tactic of PEC chemical-chemical (PECCC) redox and exonuclease III (Exo III)-assisted complementary DNA. The In2S3-P/WO3 heterojunction structure with 3D open-structure and regulable topology was initially in situ grown on Au nanoparticle-functionalized cellulose paper, which was served as a universal signal transducer to directly record photocurrent signals without complicated electrode modification, endowing the paper chip with admirable anti-interference ability and unexceptionable photoelectric conversion efficiency. With the assistance of Exo III-assisted cycling process, a trace amount of OTA could trigger substantial signal reporter ascorbic acid (AA) generated by the enzymatic catalysis of alkaline phosphatase, which could effectively provoke the PECCC redox cycling among the tris(2-carboxyethyl)phosphine acid, AA, and ferrocenecarboxylic at the In2S3-P/WO3 photoelectrode, initiating TDSF signal amplification. Based on the TDSF process induced by the Exo III-assisted recycling and PECCC redox cycling strategy, the developed paper-based PEC biosensor realized ultrasensitive determination of OTA with persuasive selectivity, high stability, and excellent reproducibility. It is believed that the proposed paper-based PEC sensing platform exhibited enormous potential for the detection of other targets in bioanalysis and clinical diagnosis.

AgInSe2-Sensitized ZnO Nanoflower Wide-Spectrum Response Photoelectrochemical/Visual Sensing Platform via Au@Nanorod-Anchored CeO2 Octahedron Regulated Signal.

Herein an ultrasensitive photoelectrochemical (PEC)/visual biosensor coupled with a multiple signal amplification strategy was proposed for the detection of nucleic acids. The initial signal amplification was achieved via ternary AgInSe2 quantum dot (QD)-sensitized ZnO nanoflowers (ZnO NFs) to form an excellent photoelectric layer. A gold-modified nanorod-anchored CeO2 (Au@NR-CeO2) octahedron was introduced as a multifunctional signal regulator via the formation of triple helix molecules. The Au@NR-CeO2 octahedron could not only quench the photocurrent signal due to the competitive capture of photon energy and electron donors with the photoelectric layer but could also act like a peroxidase to catalyze the formation of mimetic enzymatic catalytic precipitation (MECP) on the surface of the photoelectric layer. Furthermore, the steric hindrance effect from the Au@NR-CeO2 octahedron further reduced the output of the photocurrent signal. After incubation with t-DNA, the triple helix conformation was disassembled and the Au@NR-CeO2 octahedron was released from the electrode surface, leading to the significant increase of photocurrent signal. Meanwhile, the released Au@NR-CeO2 octahedron could flow into the colorimetric area of the lab-on-paper device to catalyze the occurrence of the color reaction, achieving a visual detection for t-DNA. On the basis of the multiple signal amplification strategy, t-DNA was detected specifically with a lower limit of detection of 0.28 fM and a wider linear range from 0.5 fM to 50 nM. The proposed method has the potential utility to detect a variety of nucleic acids and biomarkers.

Paper-Based Constant Potential Electrochemiluminescence Sensing Platform with Black Phosphorus as a Luminophore Enabled by a Perovskite Solar Cell.

Exploring efficient luminophores in the electrochemiluminescence (ECL) system is highly desired to pursue a sensitive ECL sensing platform. Herein, the black phosphorus nanosheets (BP NSs) with excellent ECL properties are investigated and serve as the luminophore with the coreactant of peroxydisulfate (S2O82-) solution. Moreover, owing to the overlapping of emission and absorbance spectra, effective resonance energy transfer (RET) is realized between the BP NSs and the introduced Au nanoparticles. In order to achieve the portable and miniaturized developing trends for the paper-based ECL sensing platform, a paper-based perovskite solar cell (PSC) device is designed to act as the power source to replace the commonly utilized expensive and cumbersome electrochemical workstation. Benefiting from that, a PSC driven paper-based constant potential ECL-RET sensing platform is constructed, thereby realizing sensitive microRNAs (miRNAs) detection. What's more, to attain the preferable analytical performance, the duplex-specific nuclease (DSN) is also introduced to assist the target recycling signal amplification strategy. Based on this, highly sensitive detection of miRNA-107 with a range from 0.1 pM to 15 nM is achieved by this designed sensing platform. Most importantly, this work not only pioneers a precedent for developing a high-sensitivity PSC triggered ECL sensing platform but also explores the application prospect of BP nanomaterial in the field of bioanalysis.

Graphene-palladium nanowires based electrochemical sensor using ZnFe2O4-graphene quantum dots as an effective peroxidase mimic.

We proposed an electrochemical DNA sensor by using peroxidase-like magnetic ZnFe2O4-graphene quantum dots (ZnFe2O4/GQDs) nanohybrid as a mimic enzymatic label. Aminated graphene and Pd nanowires were successively modified on glassy carbon electrode, which improved the electronic transfer rate as well as increased the amount of immobilized capture ssDNA (S1). The nanohybrid ZnFe2O4/GQDs was prepared by assembling the GQDs on the surface of ZnFe2O4 through a photo-Fenton reaction, which was not only used as a mimic enzyme but also as a carrier to label complementary ssDNA (S3). By synergistically integrating highly catalytically activity of nano-sized GQDs and ZnFe2O4, the nanohybrid possessed highly-efficient peroxidase-like catalytic activity which could produce a large current toward the reduction of H2O2 for signal amplification. Thionine was used as an excellent electron mediator. Compared with traditional enzyme labels, the mimic enzyme ZnFe2O4/GQDs exhibited many advantages such as environment friendly and better stability. Under the optimal conditions, the approach provided a wide linear range from 10(-16) to 5×10(-9) M and low detection limit of 6.2×10(-17) M. The remarkable high catalytic capability could allow the nanohybrid to replace conventional peroxidase-based assay systems. The new, robust and convenient assay systems can be widely utilized for the identification of other target molecules.

Using "dioscorea batatas bean"-like silver nanoparticles based localized surface plasmon resonance to enhance the fluorescent signal of zinc oxide quantum dots in a DNA sensor.

We reported here the preparation of "dioscorea batatas bean"-like silver nanoparticles (AgNPs) and the unique structure provided the AgNPs good localized surface plasmon resonance (LSPR) property. In addition, zinc oxide quantum dots (ZnO QDs) were also synthesized and found with good fluorescent property. Furthermore, the ZnO QDs decorated exfoliated graphene oxide (EGO-ZnO) was prepared via electrostatic interaction. The named nanomaterials were applied in a LSPR-induced fluorescent DNA sensor. To fabricate the DNA sensor, the EGO-ZnO was modified on the silica glass as the supporter for the capture probe ssDNA, and the complementary ssDNA was labeled on the surface of the AgNPs. After the hybridization step by step, the AgNPs was fastened on the surface of the EGO-ZnO, and the fluorescent intensity of the EGO-ZnO increased as a result. The prepared DNA sensor enabled the target ssDNA to be detected in the concentration range of 10(-19)-10(-14)M, and the limit of detection was 4.3 × 10(-20)M.