A sandwich-type photoelectrochemical biosensor based on anthocyanin-sensitized ZnO/P5FIn heterojunction for the sensitive detection of CYFRA21-1.

. A sandwich-type photoelectrochemical (PEC) immunosensor based on a ZnO/poly(5-formylindole) (P5FIn)/anthocyanin heterostructure was developed to achieve sensitive background-free detection of the tumor marker CYFRA21-1. ZnO with good photovoltaic properties is combined with narrow bandgap P5FIn to form a p-n type heterojunction. This structure reduces the electron-hole pair recombination, thereby enhancing the photocurrent response of the composite. Anthocyanidins are environmentally friendly natural compounds with excellent antioxidant, redox properties, and remarkable electrochemical activity. After sensitization by anthocyanins, the absorption and utilization of visible light in the composites are enhanced, further improving the PEC luminescence efficiency of the materials. Additionally, boron nitride quantum dots (BN QDs) are combined with Ab2 via polydopamine (PDA) as a secondary antibody marker, enhancing its sensitivity. The biosensor exhibited a linear detection range of 0.001-100 ng mL-1 with a limit of detection (LOD) of 0.00033 ng mL-1. Furthermore, this biosensor demonstrates excellent selectivity, reproducibility, and stability, as well as successful results in analyzing actual human serum samples. This approach provides a feasible method for tumor marker detection.

A Label-Free Photoelectrochemical Biosensor Based on ZnO/Cs3MnBr5 Heterogeneous Films for Alpha-Fetoprotein Detection.

Highly sensitive and specific biomarker detection is of outstanding importance for the diagnosis and treatment of cancers. Herein, we developed robust photoelectrochemical (PEC) biosensors with low background noise and high sensitivity based on a heterojunction, which can improve semiconductor photoelectric properties by limiting the recombination of photogenerated electron-hole pairs and successfully widening the range of light absorption. Alpha-fetoprotein (AFP) was used as a target model to examine the analytical performances of the designed PEC biosensors. ZnO/Cs3MnBr5 heterogeneous film with a uniform porous structure and large surface area enhanced electron transfer and biomolecule immobilization, and significantly increased the photocurrent response. Under the optimal conditions, the designed PEC biosensor exhibited a linear detection range of 0.01-500 ng/mL and a detection limit of 12 pg/mL. In addition, this PEC biosensor performed well when testing human serum samples and exhibited good repeatability, stability over time, and specificity, showing enormous potential for the detection of cancer markers in future biological and clinical research.

Dual-modal biosensor for mercuric ion detection based on Cu2O@Cu2S/D-TA COF heterojunction with excellent catalase-like, electrochemical and photoelectrochemical properties.

In this study, a dual-mode biosensor based on the heterojunction of Cu2O@Cu2S/D-TA COF was constructed for ultra-sensitive detection of Hg2+ using both photoelectrochemical and electrochemical approaches. Briefly, a 2D ultra-thin covalent organic framework film (D-TA COF film) with excellent photoelectrochemical signals was prepared on ITO surfaces through an in situ growth method. Subsequently, the probe H1 was immobilized onto the biosensor via Au-S bonds. In the presence of Hg2+, the formation of T-Hg2+-T complexes triggered hybridization chain reactions (HCR), leading to the attachment of abundant Cu2O@Cu2S probes onto the biosensor. As a p-type semiconductor, Cu2O@Cu2S could form a heterojunction with the underlying D-TA COF films. Meanwhile, it exhibited catalase-like activity, and the O2 produced by its catalytic decomposition of H2O2 can interact with the D-TA COF films, thus achieving double amplification of the photocurrent signal. Benefiting from the excellent and inherent Cu2+/Cu+ redox pairs of Cu2O@Cu2S, satisfactory differential pulse voltammetry (DPV) signals were obtained. As expected, the dual-mode biosensor was realized with wider linear ranges and low detection limits. Additionally, the analytical performance for Hg2+ in real water samples was excellent. Briefly, this suggested approach offers a facile and highly efficient modality for monitoring heavy metal ions in aquatic environments.

Spatial-resolved and self-calibrated 3D-printed photoelectrochemical biosensor engineered by multifunctional CeO2/CdS heterostructure for immunoassay.

A spatial-resolved and self-calibrated photoelectrochemical (PEC) biosensor has been fabricated by a multifunctional CeO2/CdS heterostructure, achieving portable and sensitive detection of carcinoembryonic antigen (CEA) using a homemade 3D printing device. The CeO2/CdS heterostructure with matched band structure is prepared to construct the dual-photoelectrodes to improve the PEC response of CeO2. In particular, as the photoactive nanomaterial, the CeO2 also plays the role of peroxidase mimetic nanozymes. Therefore, the catalytic performance of CeO2 with different morphologies (e.g., nano-cubes, nano-rods and nano-octahedra) have been studied, and CeO2 nano-cubes (c-CeO2) achieve the optimal catalytic activity. Upon introducing CEA, the sandwich-type immunocomplex is formed in the microplate using GOx-AuNPs-labeled second antibody as detection antibody. As a result, H2O2 can be produced from the catalytic oxidization of glucose substrate by GOx, which is further catalyzed by CeO2 to form •OH, thus in situ etching CdS and decreasing the photocurrents. The self-calibration is achieved by the dual-channel photoelectrodes on the homemade 3D printing device to obtain the photocurrents ratio, thus effectively normalizing the fluctuations of external factors to enhance the accuracy. This integrated biosensor with a detection limit as low as 0.057 ng mL-1 provides a promising way for ultrasensitive immunoassay in clinic application in complex environments.

High-performance assaying cardiac troponin I using Bi-doped tin-based heterojunction in photoelectrochemical biosensing with the quencher of yolk-shell nanostructure.

Cardiac troponin I (cTnI), a protein regulating myocardial contraction, stands the premier biomarker for diagnosing acute myocardial infarction and stratifying heart disease risk. Photoelectrochemical (PEC) biosensing combines traditional PEC analysis with high bioconjugation specificity, rendering a prospective avenue for disease biomarker analysis. However, the performance of sensors often falls short due to inadequate photoelectric materials. Hence, designing heterojunctions with proper band alignment, effective transport and separation of photogenerated carriers is highly expected for PEC sensors. Meanwhile, doping as a synergistic strategy to tune the energy band edges and improve carrier transport in heterojunctions, can also enhance the sensing performance. In this work, bismuth-doped tin oxide and tin disulfide heterojunction (Bi-SnOS) was prepared via a simple one-step hydrothermal method and utilized as a highly sensitive platform. Integrating copper sulfide-coated nano-gold (Au@CuS), a yolk-shell shaped nanocomposites, as the double quenching probe, an excellent PEC biosensor was fabricated to assay cTnI via sandwich immunorecognition. Under optimal conditions, the proposed biosensor displayed a high-performance for cTnI in the range from 0.1 pg/mL to 5.0 ng/mL with a low detection limit (44.7 fg/mL, 3σ). The strong photocurrent response, high stability and suitable selectivity point out that the synergistic effect between heterojunction and doping provides a promising prospect for the design of new PEC materials.

A Novel Ratiometric Photoelectrochemical Biosensor Based on Front and Back Illumination for Sensitive and Accurate Glutathione Sensing.

The ratiometric detection method has a strong attraction for photoelectrochemical bioanalysis due to its high reliability and real-time calibration. However, its implementation typically depends on the spatial resolution of equipment and the pairing of wavelength/potential with photoactive materials. In this paper, a novel ratiometric photoelectrochemical biosensor based on front and back illumination was prepared for the detection of glutathione (GSH). Unlike traditional ratio methods, this ratiometric biosensor does not require voltage and wavelength modulation, thereby avoiding potential crosstalk caused by voltage and wavelength modulation. Additionally, the formation of a heterojunction between mTiO2 and Ag2S is conducive to enhancing light absorption and promoting charge separation, thereby boosting the photocurrent signal. Apart from forming a heterojunction with TiO2, Ag2S also shows a specific affinity towards GSH, thus enhancing the selectivity of the mTiO2/Ag2S ratiometric photoelectrochemical biosensor. The results demonstrate that the ratiometric photoelectrochemical biosensor exhibits a good detection range and a low detection limit for GSH, while also possessing significant interference elimination capability. The GSH detection range is 0.01-10 mmol L-1 with a detection limit of 6.39 × 10-3 mmol·L-1. The relative standard deviation of 20 repeated detections is 0.664%. Impressively, the proposed novel ratiometric PEC biosensor demonstrates enviable universality, providing new insights for the design and construction of PEC ratiometric sensing platforms.

CRISPR/Cas12a trans-cleavage mediated photoelectrochemical biosensor based on zeolitic imidazolate framework-67 for ATP determination.

An efficient PEC biosensor is proposed for ATP detection based on exciton energy transfer from CdTe quantum dots (CdTe QDs) to Au nanoparticles (AuNPs), integrating CRISPR/Cas12a trans-cleavage activity and specific recognition of ZIF-67 to ATP. Exciton energy transfer between CdTe QDs and AuNPs system is firstly constructed as photoelectrochemical (PEC) sensing substrate. Then, the activator DNAs, used to activate CRISPR/Cas12a, are absorbed on the surface of ZIF-67. In the presence of ATP, the activator DNAs are released due to more efficient adsorption of ZIF-67 to ATP. The released activator DNA activates trans-cleavage activity of CRISPR/Cas12a to degrade ssDNA on the electrode, leading to the recovery of photocurrent due to the interrupted energy transfer. Benefiting from the specific recognition of ZIF-67 to ATP and CRISPR/Cas12a-modulated amplification strategy, the sensor is endowed with excellent specificity and high sensitivity.

A smartphone-assisted photoelectrochemical POCT method via Z-scheme CuCo2S4/Fe3O4 for simultaneously detecting co-contamination with microplastics in food and the environment.

As emerging contaminants, microplastics threaten food and environmental safety. Dibutyl phthalate (DBP, released from microplastics) and benzo[a]pyrene (BaP, adsorbed on microplastics) coexisted in food and the environment, harming human health, requesting a sensitive and simultaneous testing method to monitor. To address current sensitivity, simultaneousness, and on-site portability challenges during dual targets in complex matrixes, CuCo2S4/Fe3O4 nanoflower was designed to develop a smartphone-assisted photoelectrochemical point-of-care test (PEC POCT). The carrier transfer mechanism in CuCo2S4/Fe3O4 was proven via density functional theory calculation. Under optimal conditions, the PEC POCT showed low detection limits of 0.126, and 0.132 pg/mL, wide linearity of 0.001-500, and 0.0005-50 ng/mL for DBP and BaP, respectively. The smartphone-assisted PEC POCT demonstrated satisfied recoveries (80.00%-119.63%) in real samples. Coherent results were recorded by comparing the PEC POCT to GC-MS (DBP) and HPLC (BaP). This novel method provides a practical platform for simultaneous POCT for food safety and environment monitoring.

Highly sensitive photoelectrochemical biosensing detection of early cardiac injury enabled by novel self-assembled Bi2O3/MgIn2S4 photoelectrode coupled with ZnSnO3 quencher.

The development of photoelectrochemical (PEC) biosensors plays a critical role in enabling timely intervention and personalized treatment for cardiac injury. Herein, a novel approach is presented for the fabrication of highly sensitive PEC biosensor employing Bi2O3/MgIn2S4 heterojunction for the ultrasensitive detection of heart fatty acid binding protein (H-FABP). The Bi2O3/MgIn2S4 heterojunction, synthesized through in-situ growth of MgIn2S4 on Bi2O3 nanoplates, offers superior attributes including a larger specific surface area and more homogeneous distribution, leading to enhanced sensing sensitivity. The well-matched valence and conduction bands of Bi2O3 and MgIn2S4 effectively suppress the recombination of photogenerated carriers and facilitate electron transfer, resulting in a significantly improved photocurrent signal response. And the presence of the secondary antibody marker (ZnSnO3) introduces steric hindrance that hinders electron transfer between ascorbic acid and the photoelectrode, leading to a reduction in photocurrent signal. Additionally, the competition between the ZnSnO3 marker and the Bi2O3/MgIn2S4 heterojunction material for the excitation light source further diminishes the photocurrent signal response. After rigorous repeatability and selectivity tests, the PEC biosensor exhibited excellent performance, and the linear detection range of the biosensor was determined to be 0.05 pg/mL to 100 ng/mL with a remarkable detection limit of 0.029 pg/mL (S/N = 3).

Surface Plasmon Resonance Enhanced Photoelectrochemical Sensing of Cysteine Based on Au Nanoparticle-Decorated ZnO@graphene Quantum Dots.

In this work, Au nanoparticle-decorated ZnO@graphene core-shell quantum dots (Au-ZnO@graphene QDs) were successfully prepared and firstly used to modify an ITO electrode for the construction of a novel photoelectrochemical biosensor (Au-ZnO@graphene QDs/ITO). Characterization of the prepared nanomaterials was conducted using transmission electron microscopy, steady-state fluorescence spectroscopy and the X-ray diffraction method. The results indicated that the synthesized ternary nanomaterials displayed excellent photoelectrochemical performance, which was much better than that of ZnO@graphene QDs and pristine ZnO quantum dots. The graphene and ZnO quantum dots formed an effective interfacial electric field, enhancing photogenerated electron-hole pairs separation and leading to a remarkable improvement in the photoelectrochemical performance of ZnO@graphene QDs. The strong surface plasmon resonance effect achieved by directly attaching Au nanoparticles to ZnO@graphene QDs led to a notable increase in the photocurrent response through electrochemical field effect amplification. Based on the specifical recognition between cysteine and Au-ZnO@graphene QDs/ITO through the specificity of Au-S bonds, a light-driven photoelectrochemical sensor was fabricated for cysteine detection. The novel photoelectrochemical biosensor exhibited outstanding analytical capabilities in detecting cysteine with an extremely low detection limit of 8.9 nM and excellent selectivity. Hence, the Au-ZnO@graphene QDs is a promising candidate as a novel advanced photosensitive material in the field of photoelectrochemical biosensing.

A signal-switchable photoelectrochemical biosensor for ultrasensitive detection of long non-coding RNA in cancer cells.

Long non-coding RNA (LncRNA) as an emerging tumor biomarker plays a key factor in the early diagnosis of cancer. Herein, an innovative signal-switchable photoelectrochemical (PEC) biosensor based on ZrO2@CuO bimetallic oxides and T7 Exo-assisted signal amplification is reported for the ultrasensitive and selective detection of lncRNA (HOX gene antisense intergenic RNA, HOTAIR) in cancer cells. Firstly, MOFs-derived TiO2 nanodisks as an excellent photoactive material show an anodic background signal. When target lncRNA exists, the abundant auxiliary DNA1 is freed from T7 Exo-assisted cycle signal amplification, and then competitively hybridizes with auxiliary DNA2 on the electrode. Subsequently, bimetallic MOFs-derived ZrO2@CuO octahedra with a high specific surface area and porous structure are introduced into TiO2 nanodisks-modified biosensor, which appears a cathodic photocurrent and achieves a switchable signal. The developed signal-switchable PEC biosensor shows ultrasensitive detection of lncRNA HOTAIR with a detection limit of 0.12 fM, and can eliminate the false interference. Importantly, the established PEC biosensor has good correlation with RT-qPCR analysis (P < 0.05) for the quantification of lncRNA HOTAIR in cancer cells, which has great potential application for biomarker detection in the early diagnosis of cancer.

A Photoelectrochemical Sensor for the Sensitive Detection of Cysteine Based on Cadmium Sulfide/Tungsten Disulfide Nanocomposites.

In this work, a CdS-nanoparticle-decorated WS2 nanosheet heterojunction was successfully prepared and first used to modify ITO electrodes for the construction of a novel photoelectrochemical sensor (CdS/WS2/ITO). The thin-film electrode was fabricated by combining electrophoretic deposition with successive ion layer adsorption and reaction techniques. The results indicated that the synthesized heterojunction nanomaterials displayed excellent photoelectrochemical performance which was much better than that of pristine CdS nanoparticles and 2D WS2 nanosheets. Owing to the formation of the surface heterojunction and the effective interfacial electric field, the enhanced separation of photogenerated electron-hole pairs led to a remarkable improvement in the photoelectrochemical activity of CdS/WS2/ITO. This heterojunction architecture can protect CdS against photocorrosion, resulting in a stable photocurrent. Based on the specific recognition between cysteine and CdS/WS2/ITO, through the specificity of Cd-S bonds, a visible-light-driven photoelectrochemical sensor was fabricated for cysteine detection. The novel photoelectrochemical biosensor exhibited outstanding analytical capabilities in detecting cysteine, with an extremely low detection limit of 5.29 nM and excellent selectivity. Hence, CdS-WS2 heterostructure nanocomposites are promising candidates as novel advanced photosensitive materials in the field of photoelectrochemical biosensing.

A multiple signal amplification photoelectrochemical biosensor based on biotin-avidin system for kanamycin sensing in fish and milk via synergism of g-C3N4 and Ru@SiO2.

BACKGROUND: The residues of kanamycin can accumulate in the human body for a long time and pose serious health risks, including hearing loss, kidney poisoning, and drug allergic reactions. Therefore, it is crucial to develop a rapid, highly sensitive, and low-cost method for detecting kanamycin residues in foods. However, the current methods have limitations such as low sensitivity, expensive instruments, and multiple steps, which make them impractical for use in resource-limited environments and emergencies. In this study, the creation of a multiple-signal amplification photoelectrochemical biosensor to address these aforementioned issues is discussed. RESULTS: Herein, we proposed a multiple signal amplification photoelectrochemical (PEC) biosensor based on carboxylated g-C3N4 and avidin functionalized Ru@SiO2 for the ultrasensitive detection of kanamycin. The carboxylated g-C3N4 was a highly efficient photoactive substance for amplifying photoelectric signals and a substrate for aptamer immobilization. The DOS and PDOS of g-C3N4 were studied by simulation, and the sensing mechanism of the probe at the molecular level was revealed. Meanwhile, using Ru@SiO2 as a signal amplifying unit, through the cooperative work between Ru@SiO2 and g-C3N4, the photoelectric signal could be double amplified to produce an excellent photocurrent response. Under optimized conditions, the photocurrent response of the PEC biosensor to kanamycin was obtained at concentrations from 0.1 nM to 1000 nM with a lower detection limit of 4.1052 × 10-11 mol L-1. This protocol demonstrates high sensitivity, brilliant specific recognition ability, excellent reproducibility, and acceptable stability. SIGNIFICANCE: The first combination of g-C3N4 and avidin-Ru@SiO2 as photocurrent materials greatly enhanced the sensitivity of the PEC biosensors. Moreover, the specificity and sensitivity of the PEC biosensor were further improved through the specific interaction between kanamycin and aptamer. The photoelectric conversion mechanism based on g-C3N4 and two pathways for enhancing the photocurrent by Ru(byp)32+ were proposed. Through simulations of the DOS and PDOS of g-C3N4, the sensing mechanism of the probe at the molecular level was revealed. Under the optimum conditions, the PEC biosensor exhibited a wide linear concentration range and a low detection limit.

High performance photoelectrochemical immunosensing platform based on front-illuminated Mo:BiVO4 photoelectrodes for procalcitonin assay.

The outstanding photoactive materials are the imperative for the construction of a front-illuminated photoelectrochemical (PEC) biosensor, which is crucial step for improving the detection sensitivity. Yet, the weak and unstable initial PEC signals of the photoelectrodes have limited evidently the detection performance. Herein, a front-illuminated "on-off" PEC immunosensor was constructed based on Mo:BiVO4 as photoactive matrix and Au/CeO2 as signal quencher for sensitive detection of procalcitonin (PCT). Systematic studies reveal that the Mo doped BiVO4 can increase the charge carrier density of BiVO4, leading to much higher initial signal under front illumination than back illumination. Moreover, Mo:BiVO4 was directly grown on conducting substrates, which effectively overcomes the loose combination of sensing substrate ensuring good electrical contact and continuity. Upon coupling with Au/CeO2 as signal quencher, the initial photocurrent signal can be significantly quenched. As a result, the proposed PEC immunosensor presents a wide linear range from 10 fg mL-1 to 50 ng mL-1 with a detection limit of 2.45 fg mL-1. Impressively, this study will open a new avenue for the construction of highly efficient and stable photoelectrode, as well as extend the application of PEC biosensor for biomarkers detection in early disease diagnosis.

Ascorbic Acid Induced the Improved Oxygen Vacancy Defects of Bi4O5Br2 and Its Application on Photoelectrochemical Detection of DNA Demethylase MBD2 with Improved Detection Sensitivity.

Oxygen vacancy defects (OVs) are one of the main strategies for nanomaterials modification to improve the photoactivity, but current methods for fabricating OVs are usually complicated and harsh. It is important to develop simple, rapid, safe, and mild methods to fabricate OVs. By studying the effects of different weak reducing agents, the concentration of the reducing agent and the reaction time on fabrication of OVs, it is found that L-ascorbic acid (AA) gently and rapidly induces the increase of OVs in Bi4O5Br2 at room temperature. The increased OVs not only improve the adsorption of visible light, but also enhance the photocurrent response. Based on this, the preparation of OVs in Bi4O5Br2 is employed to the development of a photoelectrochemical biosensor for the detection of DNA demethylase of methyl-CpG binding domain protein 2 (MBD2). The biosensor shows a wide linear range of 0.1-400 ng mL-1 and a detection limit as low as 0.03 ng mL-1 (3σ). In addition, the effect of plasticizers on MBD2 activity is evaluated using this sensor. This work not only provides a novel method to prepare OVs in bismuth rich materials, but also explores a new novel evaluation tool for studying the ecotoxicological effects of contaminants.

NAD+ mediated photoelectrochemical biosensor for histone deacetylase Sirt1 detection based on CuO-BiVO4-AgNCs heterojunction and hybridization chain reaction amplification.

BACKGROUND: Histone deacetylate Sirt1 has been involved in many important biological processes and is closely related to the occurrence and development of many diseases. Therefore, the accurate detection of Sirt1 is of great significance for the diagnosis and treatment of diseases caused by Sirt1 and the development of related drugs. RESULTS: In this work, a photoelectrochemical biosensor was developed for Sirt1 detection based on the NAD + mediated Sirt1 recognition and E. Coli DNA ligase activity. CuO-BiVO4p-n heterojunction was employed as the photoactive material, rolling circle amplification (RCA), hybridization chain reaction (HCR) and AgNCs were used as triple signal amplifications. As a bifunctional cofactor, NAD+ played a crucial role for Sirt1 detection, where the peptide deacetylation catalyzed by Sirt1 consumed NAD+, and the decreased amount of NAD + inhibited the activity of E. Coli DNA ligase, leading to the failure on RCA reaction, and improving the HCR reaction. Finally, AgNCs were generated using C-rich DNA as carrier. The surface plasmon effect of AgNCs and its heterojunction with CuO and BiVO4 accelerated the transfer rate of photogenerated carriers and improved the photocurrent signal. When the detection range was 0.001-200 nM, the detection limit of the biosensor was 0.76 pM (S/N = 3). SIGNIFICANCE: The applicability of the method was evaluated by studying the effects of known inhibitors nicotinamide and environmental pollutant halogenated carbazole on Sirt1 enzyme activity. The results showed that this method can be used as a new platform for screening Sirt1 enzyme inhibitors, and also provided a new biomarker for evaluating the ecotoxicological effects of environmental pollutants.

Femtomolar endogenous adenosine triphosphate-responded photoelectrochemical biosensor based on Au@Cu2O core-shell nanocubes for the ultrasensitive determination of Escherichia coli O157:H7 in foods.

Sensitive and precise determination of virulent foodborne pathogens is significant for food safety. Herein, an ultrasensitive photoelectrochemical (PEC) bioanalysis was developed using the endogenous adenosine triphosphate (ATP)-responded Au@Cu2O core-shell nanocubes (Au@Cu2O NCs) to measure Escherichia coli O157: H7 (E. coli O157:H7) in food. Briefly, the phage-functionalized gold wire was used to specifically recognize the target pathogen. With the bacteriolysis of lysozyme, the endogenous ATP molecules were emitted from the captured target bacteria and enriched by another ATP aptamer-modified gold wire. Following the exchange with complementary DNA (cDNA) chains, the bonded ATP would be released. It could simultaneously etch the Au@Cu2O NCs and compete with external circuit electrons to combine photogenerated holes on the Au@Cu2O NCs-modified screen-printed electrode. With the synergy of the two signal amplification mechanisms, a significant attenuation of photocurrent signal appeared even with femtomolar ATP. Therefore, the purpose of ultrasensitive determination of E. coli O157:H7 was realized, which depended on the endogenous ATP rather than exogenous signal probes. The proposed biosensor presented a good analysis performance within 10-106 CFU/mL with a detection limit of 5 CFU/mL. Besides, its specificity, repeatability, and stability were also investigated and acceptable. The detection results for food samples matched well with the results detected by the plate counting method. This work gives an innovative and sensitive signal amplification strategy for PEC bioassays in foodborne pathogens detection.

Small-Molecule Probe-Induced In Situ-Sensitized Photoelectrochemical Biosensor for Monitoring α-Glucosidase Activity.

Semiconductor-based photoelectrochemical (PEC) biosensors have garnered significant attention in the field of disease diagnosis and treatment. However, the recognition units of these biosensors are mainly limited to bioactive macromolecules, which hinder the photoelectric response due to their insulating characteristics. In this study, we develop an in situ-sensitized strategy that utilizes a small-molecule probe at the interface of the photoelectrode to accurately detect α-glucosidase (α-Glu) activity. Silane, a prototype small-molecule probe, was surface-modified on graphitic carbon nitride to generate Si nanoparticles upon reacting with hydroquinone, the enzymatic product of α-Glu. The in situ formed heterojunction enhances the light-harvesting property and photoexcited carrier separation efficiency. As a result, the in situ-sensitized PEC biosensor demonstrates excellent accuracy, a low detection limit, and outstanding anti-interference ability, showing good applicability in evaluating α-Glu activity and its inhibitors in human serum samples. This novel in situ sensitization approach using small-molecule probes opens up new avenues for developing simple and efficient PEC biosensing platforms by replacing conventional biorecognition elements.

A cathodic photoelectrochemical biosensor based on CRISPR/Cas12a trans-cleavage mediated p-n heterojunction quenching mode for microRNA determination.

In this study, a cathodic photoelectrochemical (PEC) bioanalysis for sensitive determination of microRNA (miRNA) has been constructed based on CRISPR/Cas12a trans-cleavage mediated [(C6)2Ir(dcbpy)]+PF6- (C6 represents coumarin-6 and dcbpy represents 4,4'-dicarboxyl-2,2'-bipyridine)-sensitized NiO photocathode and p-n heterojunction quenching mode. The [(C6)2Ir(dcbpy)]+PF6--sensitized NiO photocathode exhibits a stable and dramatically improved photocurrent signal due to highly effective photosensitization of [(C6)2Ir(dcbpy)]+ PF6-. Then Bi2S3 quantum dots (Bi2S3 QDs) is captured on the photocathode, resulting in markedly quenching of the photocurrent. When target miRNA is specifically recognized by the hairpin DNA to stimulate the trans-cleavage activity of CRISPR/Cas12a, leading to the leave of the Bi2S3 QDs. The photocurrent is gradually recovered with the increasing target concentration. Thus, the quantitative signal response to target is achieved. Benefiting from excellent performance of NiO photocathode, intense quenching effect of p-n heterojunction and accurate recognition ability of CRISPR/Cas12a, the cathodic PEC biosensor shows a wider linear range over 0.1 fM-10 nM, with a low detection limit of 36 aM. Also, the biosensor exhibits satisfying stability and selectivity.

Photoactive conjugated microporous polymer@C60 with quencher on tailed Y-triangular DNA structure for high-performance signal-off photoelectrochemical biosensing.

Herein, we synthesized a conjugated microporous polymer (CMP) decorated C60 (CMP@C60) with high photoelectric conversion efficiency, in which continuously repeated donor-acceptor (D-A) π electron unit within one molecule of CMP on C60 could not only effectively increase the mobility of photogenerated carriers with improved electron transmission, but also constitute the cascade energy band matching with reduced electron-hole recombination. Based on the high-performance of CMP@C60 for producing exciting initial photoelectrochemical (PEC) signal, a sensitive signal-off sensing platform was designed for lead ion (Pb2+) assay by coupling with quencher methylene blue (MB) interacting on efficient long tailed Y-triangular DNA structure (LYTD). The proposed LYTD with a tripod structure could generate six long tails in situ on its side at the same time via a simple hybridization chain reaction (HCR), providing notably grooves on electrode to accommodate quencher MB to significantly depress the signal for sensitive detection of Pb2+. As a result, the proposed PEC biosensor revealed excellent analysis capability with a low detection limit of 0.3 fM (S/N = 3). Additionally, it also showed satisfactory stability in the detection of tap water samples, lake water samples and clinical serum samples, manifesting great application prospect in the areas of environmental pollutant detection.