Self-shedding MOF-nanocarriers modulated CdS/MoSe2 heterojunction activity through in-situ ion exchange: An enhanced split-type photoelectrochemical sensor for deoxynivalenol.

Deoxynivalenol (DON), a mycotoxin produced by Fusarium, poses a significant risk to human health and the environment. Therefore, the development of a highly sensitive and accurate detection method is essential to monitor the pollution situation. In response to this imperative, we have devised an advanced split-type photoelectrochemical (PEC) sensor for DON analysis, which leverages self-shedding MOF-nanocarriers to modulate the photoelectric response ability of PEC substrate. The PEC sensing interface was constructed using CdS/MoSe2 heterostructures, while the self-shedding copper peroxide nanodots@ZIF-8 (CPNs@ZIF-8) served as the Cu2+ source for the in-situ ion exchange reaction, which generated a target-related signal reduction. The constructed PEC sensor exhibited a broad linear range of 0.1 pg mL-1 to 500 ng mL-1 with a low detection limit of 0.038 pg mL-1, demonstrating high stability, selectivity, and proactivity. This work not only introduces innovative ideas for the design of photosensitive materials, but also presents novel sensing strategies for detecting various environmental pollutants.

Starch nanoparticles with predictable size prepared by alternate treatments of ball milling and ultrasonication.

In this study, starch nanoparticles (SNPs) were prepared by alternate treatments of liquid nitrogen ball milling and ultrasonication. The impact, shear and friction forces produced by ball milling, and acoustic cavitation and shear effects generated by ultrasonication disrupted starch granules to prepare SNPs. The SNPs possessed narrow particle size distribution (46.91-210.52 nm) and low polydispersity index (0.28-0.45). Additionally, the SNPs exhibited the irregular fragments with good uniformity. The relative crystallinity decreased from 34.91 % (waxy corn starch, WCS) to 0-25.91 % (SNPs), and the absorbance ratios of R1047/1022 decreased from 0.81 (WCS) to 0.60-0.76 (SNPs). The SNPs had lower thermal stability than that of WCS, characterized by a decrease in Td (temperature at maximum weight loss) from 309.39 °C (WCS) to 300.39-305.75 °C (SNPs). Furthermore, the SNPs exhibited excellent swelling power (3.48-28.02 %) and solubility (0.34-0.97 g/g). Notably, oil absorption capacity of the SNPs (9.77-15.67 g/g) was rather greater than that of WCS (1.33 g/g). Furthermore, the SNPs possessed the lower storage modulus (G'), loss modulus (G″) and viscosity than that of WCS. The SNPs with predictable size and high dispersion capability prepared in this study lay a foundation for expanding the application of SNPs.

Zirconium­cerium modified polyvinyl alcohol/NaCMC biocomposite film: Synthesis of films through high-speed shear assisted technique and removal fluoride from water.

A new zirconium and cerium-modified polyvinyl alcohol (PVA) sodium carboxymethyl cellulose (NaCMC) film (PVA/CMC-Zr-Ce) was synthesized thru a high-speed shear-assisted method and its adsorption for the removal of fluoride was studied, in which the NaCMC provided -COONa for ion exchange between Na and Zr-Ce, thus the loading amount of Zr-Ce on films was accordingly increased. The morphology and structure of PVA/CMC-Zr-Ce were characterized using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). Besides, the mechanical properties, water contact angle, and swelling ratio of film were also evaluated. The addition of high-speed shear improved the dispersion of the emulsion system, and PVA/CMC-Zr-Ce film with good adsorption performance and film stability was prepared. While, it was found that the adsorption capacity could reach 67.25 mg/g and equilibrium time could reach 20 min. The adsorption mechanism of PVA/CMC-Zr-Ce revealed that ion exchange between hydroxide and fluoride, electrostatic interactions and complexation were the dominating influencing factors. Based on these findings, it can be concluded that PVA/CMC-Zr-Ce film- synthesized with high-speed shear assistance technique is a promising adsorbent for fluoride removal from water.

MOF-derived sandwich-structured dual Z-Scheme Co9S8@ZnIn2S4/CdSe hollow nanocages heterojunction: Target-induced ultrasensitive photoelectrochemical sensing of chlorpyrifos.

Exploring efficient photoactive material presents an intriguing opportunity to enhance the analytical performance of photoelectrochemical (PEC) sensor in the environmental analysis. In this work, a sandwich-structured multi-interface Co9S8@ZnIn2S4/CdSe QDs dual Z-Scheme heterojunction, derived from metal-organic framework (MOF), was synthesized as a sensing platform for chlorpyrifos detection, by integrating with enzyme-induced in situ insoluble precipitates strategy. The meticulously designed Co9S8@ZnIn2S4/CdSe QDs exhibited enhanced charge separation efficiency and was proved to be a highly effective sensing platform for the immobilization of biomolecules, attributing to the intrinsic dual Z-Scheme heterojunction and the distinctive hollow structure. The proposed PEC sensing platform combined with enzyme-induced in situ precipitate signal amplification strategy achieved superior performance for sensing of chlorpyrifos (CPF), showing in wide linear range (1.0 pg mL-1-100 ng mL-1), with a limit of detection (0.6 pg mL-1), excellent selectivity, and stability. This work offers valuable insights for the design of novel advanced photoactive materials aimed at detecting environmental pollutants with low level concentration.

Dual amplification for PEC ultrasensitive aptasensing of biomarker HER-2 based on Z-scheme UiO-66/CdIn2S4 heterojunction and flower-like PtPdCu nanozyme.

As an important prognostic indicator in breast cancer, human epithelial growth factor receptor-2 (HER-2) is of importance for assessing prognosis of breast cancer patients, whose accurate and facile analysis are imperative in clinical diagnosis and treatment. Herein, photoactive Z-scheme UiO-66/CdIn2S4 heterojunction was constructed by a hydrothermal method, whose optical property and photoactivity were critically investigated by a range of techniques, combined by elucidating the interfacial charge transfer mechanism. Meanwhile, PtPdCu nanoflowers (NFs) were fabricated by a simple aqueous wet-chemical method, whose peroxidase (POD)-mimicking catalytic activity was scrutinized by representative tetramethylbenzidine (TMB) oxidation in H2O2 system. Taken together, the UiO-66/CdIn2S4 based photoelectrochemical (PEC) aptasensor was established for quantitative analysis of HER-2, where the detection signals were further magnified through catalytic precipitation reaction towards 4-chloro-1-naphthol (4-CN) oxidation (assisted by the PtPdCu NFs nanozyme). The PEC aptasensor presented a broader linear range within 0.1 pg mL-1-0.1 µg mL-1 and a lower limit of detection of 0.07 pg mL-1. This work developed a new PEC aptasensor for ultrasensitive determination of HER-2, holding substantial promise for clinical diagnostics.

Target-regulated photoactivities of CdS/Ni-MOF heterojunction with [Ru(bpy)2dppz]2+ intercalator: a bisphenol A photoelectrochemical aptasensor.

Bisphenol A (BPA), an important endocrine disrupting compound, has infiltrated human daily lives through electronic devices, food containers, and children's toys. Developing of novel BPA assay methods with high sensitivity holds tremendous importance in valuing the pollution state. Here, we constructed an ultrasensitive photoelectrochemical (PEC) aptasensor for BPA determination by regulating photoactivities of CdS/Ni-based metal-organic framework (CdS/Ni-MOF) with [Ru(bpy)2dppz]2+ sensitizer. CdS/Ni-MOF spheres exhibited excellent photocatalytic performance, serving as a potential sensing platform for the construction of target recognition process. [Ru(bpy)2dppz]2+ were embedded into DNA double-stranded structure, functioning as sensitizer for modulating the signal response of the developed PEC aptasensor. The proposed PEC sensor exhibited outstanding analytical performances, including a wide linear range (0.1 to 1000.0 nM), low detection limit (0.026 nM, at 3σ/m), excellent selectivity, and high stability. This work provides a perspective for the design of ideal photosensitive materials and signal amplification strategies and extends their application in environment analysis.

Investigation on chain segment motions of various starch molecules under different glycerol-water system.

The molecular motion of starch at different glycerol concentrations (0, 20, 50, and 80 %) was investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. Fourier-transform infrared (FTIR) spectroscopy and 1H nuclear magnetic resonance (1H NMR) spectroscopy confirmed that hydroxyl groups at the C2 and C3 positions of glucose units in corn starch (CS), waxy corn starch (WCS), and high amylose corn starch (HCS) were labeled with 4-amino-TEMPO. The crystallinities of CS, WCS, and HCS after spin-labeling decreased from 30.68 % to 3.21 %, 39.36 % to 1.65 %, and 28.54 % to 8.08 %, respectively. The pseudoplastic fluid properties of the spin-labeled starch remained shear-thin at different glycerol concentrations. EPR revealed the fast- and slow-motion components of the spin-labeled starch molecules dispersed in water. At a glycerol concentration of 20 %, the slow-motion component disappeared, indicating a faster rotational motion of the starch chain segments. As the glycerol concentration increased to 50 and 80 %, the rotational motion slowed because of high viscosity. In particular, the mobility of the spin-labeled WCS chains increased owing to easier access of glycerol and water to the branched structure. This study directly observed the dynamics of the molecular behavior of starch in glycerol-water systems.

The anti-digestibility mechanism of soy protein isolate hydrolysate on natural starches with different crystal types.

The effects of soy protein isolate hydrolysate (SPIH) on the physicochemical properties and digestive characteristics of three starch types (wheat, potato, and pea) were investigated. Fourier-transform infrared spectroscopy and molecular dynamics simulations showed that hydrogen bonds were the driving force of the interaction between SPIH and starch. Furthermore, the SPIH was predicted to preferentially bind to the terminal region of starch using molecular dynamics simulations. Compared to pure starch, adding 20 % SPIH to wheat starch, potato starch, and pea starch, the content of resistant starch increased by 39.71 %, 125.66 % and 37.83 %, respectively. Both the radial distribution function (RDF) and low field-nuclear magnetic resonance (LF-NMR) showed that SPIH reduced the flow of water molecules in starch, indicating that SPIH competed with starch for water molecules. Multiple characterization experiments and molecular dynamics simulations confirmed that the anti-digestibility mechanism of SPIH on natural starches with different crystal types could be attributed to the interaction between starch and SPIH, which decreased the catalytic efficiency of amylase. This study clarified the anti-digestibility mechanism of SPIH on natural starches, which provides new insights into the production of low-glycemic index foods for the diabetic population.

The structural properties and resistant digestibility of maize starch-glyceride monostearate complexes.

This study investigated the effects of pullulanase debranching on the structural properties and digestibility of maize starch (MS)-glyceryl monostearate (GMS) complexes. According to our results, the apparent amylose content of MS increased from 36.34 % to 95.55 % and complex index reached 93.09 % after 16 h of pullulanase debranching. The crystallinity of prepared MS-GMS complexes increased to 33.24 % with a blend of B-type and V-type crystals. The surface of prepared MS-GMS complexes granules emerged more small lamellar crystals tightly adhering to the surface of granules. The Fourier transforms infrared spectroscopy analysis showed that debranching pretreatment MS-GMS complexes exhibited higher levels of short-range orders structure. These results indicated that maize starch was favorable to form more ordered starch-lipid complexes structure after debranching pretreatment, which resulted in the restriction of starch hydrolysis. In vitro digestion data implied that resistant starch (RS) content increased with the extension of the debranching time, and the highest RS content (69.58 %) appeared with 16 h pullulanase debranching. This work suggests that debranching pretreatment could be an efficient way to produce ordered starch-lipid complexes with controllable structure and anti-digestibility.

Label-free "signal-off" PEC aptasensor for determination of kanamycin based on 3D nanoflower-like FeIn2S4/CdS Z-scheme heterostructures.

Highly photoactive 3D nanoflower-like FeIn2S4/CdS heterostructures were synthesized by hydrothermal treatment and low-temperature cation exchange. The FeIn2S4/CdS displayed 14.5 times signal amplification in contrast to FeIn2S4 alone. It was applied as a photoactive substrate to construct a label-free photoelectrochemical (PEC) aptasensor for ultrasensitive determination of kanamycin (KAN). Under the optimal conditions, the constructed PEC aptasensor displayed a wide linear range (5.0 × 10-4 ~ 5.0 × 101 ng mL-1) and a low detection limit (S/N = 3) of 40.01 fg mL-1. This study provides some constructive insights for preparation of advanced photoactive materials and exhibits great potential for quantitative determination of antibiotics in foods and environmental samples.

Magnetic-assisted exciton-plasmon interactions modulated Bi2S3 nanorods@MoS2 nanosheets heterojunction: towards a split-type photoelectrochemical sensing of profenofos.

A split-type photoelectrochemical (PEC) sensor was designed for the detection of profenofos (PFF) depending on the magnetic-assisted exciton-plasmon interactions (EPI) between the semiconductor substrate and Au NPs. The core-shell Bi2S3 nanorods@MoS2 nanosheets (Bi2S3 NRs@MoS2 NSs) heterostructure nanomaterial with fascinating performance was synthesized and used as the photovoltaic conversion substrate and signal molecules absorption platform. The PEC sensor is operated by co-incubating with the released Au NPs-cDNA from the surface of magnetic beads, originating from the target-triggered DNA double-stranded structure opening event. Due to the strong EPI effects, the photocurrent of Bi2S3 NRs@MoS2 NSs decreased and varied with the PFF concentrations. The proposed PEC sensor exhibited outstanding analytical performances, including a wide linear range (1.0 pg mL-1~1.0 µg mL-1), low detection limitation (0.23 pg mL-1, at 3 σ/m), excellent specificity, high stability, and applicability. Overall, this work provides a new signal strategy for PEC biosensors and extends its application in environmental analysis.

Self-checking dual-modal aptasensor based on hybrid Z-scheme heterostructure of Zn-defective CdS/ZnS for oxytetracycline detection.

Electrochemical detection methods have been widely used for trace target detection with satisfactory results. However, most of the existing electrochemical sensors rely only on single signal output, which inevitably suffer from the interference of the complex matrix of real samples. Herein, we proposed a dual-modal aptasensor for oxytetracycline assay with self-checking function by integrating photoelectrochemical (PEC) and electrochemical (EC) signal outputs in one analysis system. Zn-defective CdS/ZnS heterostructure was synthesized and served as the photo-electroactive substrate for constructing the biorecognition process, while methylene blue (MB) was used as a dual-functional probe to enhance both PEC and EC signals. Due to the high activity of Zn-defective CdS/ZnS heterojunction and the unique dual-modal signal readout strategy, the biosensing platform exhibits superior analytical performance with the relatively wide linear range (0.01-50 ng mL-1), lower detection limits of 1.86 pg mL-1 (PEC mode) and 3.08 pg mL-1 (EC mode), as well as good selectivity, stability and reproducibility. The proposed dual-model analytical system with self-checking function is envisioned to provide a new approach for sensitive and reliable biosensing.

Zirconium/lanthanum-modified chitosan/polyvinyl alcohol composite adsorbent for rapid removal of fluoride.

A novel and easily separable adsorbent in the shape of a membrane for the rapid removal of fluoride from water was prepared after testing Zr, La and LaZr to modify a chitosan/polyvinyl alcohol composite adsorbent (CS/PVA-Zr, CS/PVA-La, CS/PVA-LA-Zr). The CS/PVA-La-Zr composite adsorbent can remove a large amount of fluoride within 1 min of contact time, and the adsorption equilibrium can be reached within 15 min. The fluoride adsorption behavior of the CS/PVA-La-Zr composite can be described by pseudo-second-order kinetics and Langmuir isotherms models. The morphology and structure of the adsorbents were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The adsorption mechanism was studied using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), and which showed that ion exchange occurred mainly with hydroxide and fluoride ions. This study showed that an easily operable, low-cost and environmentally friendly CS/PVA-La-Zr has the potential to remove fluoride effectively from drinking water in a short time.

Nanozyme-assisted ratiometric photoelectrochemical aptasensor over Cu2O nanocubes mediated photocurrent-polarity-switching based on S-scheme FeCdS@FeIn2S4 heterostructure.

The controllable modulation of the response mode is highly attractive for the construction of photoelectrochemical (PEC) sensors with improved sensitivity and anti-interference ability in complex real samples matrix. Here, we present a charming proof-of-concept ratiometric PEC aptasensor of enrofloxacin (ENR) analysis via the controllable signal transduction. Different with the traditional sensing mechanism, this ratiometric PEC aptasensor integrates the anodic PEC signal induced by PtCuCo nanozyme-catalyzed precipitation reaction and the polarity-switching cathodic PEC response mediated by Cu2O nanocubes on S-scheme FeCdS@FeIn2S4 heterostructure. Taking advantages of the photocurrent-polarity-switching signal response model and the superior performance of the photoactive substrate material, the proposed ratiometric PEC aptasensor displays a good detection linear range for ENR analysis from 0.01 pg mL-1 to 10 ng mL-1, with a detection limit of 3.3 fg mL-1. This study provides a general platform for detecting interested trace analytes in real samples and expands the diversity of sensing strategy design.

Hollow SnO2/CdS QDs/CdCO3 heterostructured nanocubes coupled with hollow PtPd/MnCo-CeO2 nanozyme-mediated synergistic amplification for ultrasensitive PEC immunoanalysis of lung cancer biomarker.

Nowadays, lung cancer is one of the most dangerous cancers threatening human life all over the world. As a crucial biomarker, cytokeratin 19 fragment 21-1 (CYFRA 21-1) is extraordinary important for diagnosis of non-small cell lung cancer (NSCLC). In this work, we synthesized hollow SnO2/CdS QDs/CdCO3 heterostructured nanocubes with high and stable photocurrents, which applied to construction of a sandwich-typed photoelectrochemical (PEC) immunosensor for detection of CYFRA 21-1, integrated by in-situ catalytic precipitation strategy with home-built PtPd alloy anchored MnCo-CeO2 (PtPd/MnCo-CeO2) nanozyme for synergistic amplification. The interfacial electron transfer mechanism upon visible-light irradiation was investigated in details. Further, the PEC responses were seriously quenched by the specific immunoreaction and precipitation catalyzed by the PtPd/MnCo-CeO2 nanozyme. The established biosensor showed a wider linear range of 0.001-200 ng mL-1 and a lower limit of detection (LOD = 0.2 pg mL-1, S/N = 3), coupled by exploring such analysis even in diluted human serum sample. This work opens a constructive avenue to develop ultrasensitive PEC sensing platforms for detecting diverse cancer biomarkers in clinic.

Hollow cage-like PtCu nanozyme-regulated photo-activity of porous CdIn2S4/SnO2 heterojunctions for ultrasensitive PEC sensing of streptomycin.

Streptomycin (STR) is extensively employed for preventive and curative purposes in animals, which is accumulated in human body through food chain and induces serious health problems. Herein, highly photoactive type II heterojunctions of porous CdIn2S4/SnO2 microspheres were initially prepared, which can effectively inhibit the recombination of the charge-hole pairs. Besides, the peroxidase-mimicking catalytic property of the hollow PtCu nanocages (PtCu NCs) was carefully investigated by UV-vis spectroscopy, where catalytic oxidation of tetramethylbenzidine behaved as the benchmarked reaction. On such basis, a highly selective photoelectrochemical (PEC) aptasensor was established with the CdIn2S4/SnO2 heterojunctions for bioanalysis of streptomycin, coupled by the PtCu NCs nanozyme-catalyzed biocatalytic precipitation to achieve signal magnification. Specifically, the home-made nanozyme was applied for catalytic oxidation of 3,3'-diaminobenzidine to generate insulating precipitate in aqueous H2O2 system and thereby block the light harvesting on the photoanode, showing steeply declined PEC responses. The as-built aptasensor showed a broad linear range of 0.01-200 nM with a low limit of detection of 7.50 pM (S/N = 3) for such analysis, combined by exploring its practical detection in milk samples. This work shows excellent nanozyme-catalyzed signal amplification for fabrication of ultrasensitive PEC biosensors towards other antibiotics detection.

Bimetallic AuPt alloy/rod-like CeO2 nanojunctions with high peroxidase-like activity for colorimetric sensing of organophosphorus pesticides.

Organophosphorus pesticides (OP) have extensive applications in agriculture, while their overuse causes inevitable residues in food, soil, and water, ultimately being harmful to human health and even causing diverse dysfunctions. Herein, a novel colorimetric platform was established for quantitative determination of malathion based on peroxidase mimic AuPt alloy decorated on CeO2 nanorods (CeO2@AuPt NRs). The synthesized nanozyme oxidized colorless 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2. Besides, the oxidized TMB was inversely reduced by ascorbic acid (AA), which were originated from hydrolysis of L-ascorbic acid-2-phosphate (AA2P) with the assistance of acid phosphatase (ACP). Based upon this observation ACP analysis was explored by colorimetry, showing a wid linear range of 0.2 ~ 3.5 U L-1 and a low limit of detection (LOD = 0.085 U L-1, S/N = 3). Furthermore, malathion present in the colorimetric system inhibited the activity of ACP and simultaneously affected the generation of AA, in turn promoting the recovery of the chromogenic reaction. Based on this, the LOD was decreased to 1.5 nM (S/N = 3) for the assay of malathion with a wide linear range of 6 ~ 100 nM. This simple colorimetric platform provides some informative guidelines for determination of other pesticides and disease markers.

Z-scheme Cu2MoS4/CdS/In2S3 nanocages heterojunctions-based PEC aptasensor for ultrasensitive assay of fumonisin B1 via signal amplification with hollow PtPd-CoSnO3 nanozyme.

Fumonisin B1 (FB1), the most prevalent and highest toxicity mycotoxins among fumonisins family, poses threats to human especially children and infants even at a trace level. Therefore, its facile and sensitive detection is of importance. Herein, Z-scheme Cu2MoS4/CdS/In2S3 nanocage-like heterojunctions (labeled Cu2MoS4/CdS/In2S3) were synthesized, whose photoelectrochemical (PEC) property and electron transfer mechanism were strictly investigated. The Cu2MoS4/CdS/In2S3 behaved as photoactive substrate for building a PEC sensing platform for detection of FB1, integrated with PtPd alloy modified hollow CoSnO3 nanoboxes (labeled PtPd-CoSnO3) nanozyme. By virtue of the stronger affinity between the target FB1 and its aptamer (FB1-Apt), the photocurrent was recovered by releasing the CoSnO3-PtPd3 modified FB1-Apt (FB1-Apt/PtPd-CoSnO3) from the photoanode, which can terminate the catalytic precipitation reaction for its peroxidase-like property. The resultant PEC aptasensor exhibited a wider dynamic linear range from 1 × 10-4 to 1 × 102 ng mL-1 with a lower limit of detection (0.0723 pg mL-1). Thus, this research provides a feasible PEC sensing platform for routine analysis of other mycotoxins in practice.

Integration of phosphate functionalized Pt/TiO2 and Ru(bpy)32+ sensitization for ultrasensitive assay of adenosine deaminase activity on a novel split-typed PEC aptasensor.

To date, it is still a challenge for high-performance photoelectrochemical (PEC) assay of low-abundance adenosine deaminase (ADA) in fundamental research and clinical diagnosis. Herein, phosphate-functionalized Pt/TiO2 (termed PO43-/Pt/TiO2) was prepared as ideal photoactive material to develop a split-typed PEC aptasensor for detection of ADA activity, coupled by a Ru(bpy)32+ sensitization strategy. We critically studied the effects of the PO43- and Ru(bpy)32+ on the detection signals, and discussed the signal-amplified mechanism. Specifically, hairpin-structured adenosine (AD) aptamer was splited into single chain via ADA-induced catalytic reaction, and subsequently hybridized with complementary DNA (cDNA, initially coating on magnetic beads). The in-situ formed double-stranded DNA (dsDNA) was further intercalated by more Ru(bpy)32+ to amplify the photocurrents. The resultant PEC biosensor showed a broader linear range of 0.05-100 U L-1 and a lower limit of detection (0.019 U L-1), which can fill the blank for analysis of ADA activity. This research would provide some valuable insights for building advanced PEC aptasensors in ADA-related research and clinical diagnosis.

Bifunctional photoelectrochemical aptasensor based on heterostructured Ag3PO4/Ag/TiO2 nanorod array for determination of two tumor markers.

Constructing of heterostructures can significantly improve the photoelectrical (PEC) response signal by promoting the migration and suppressing the recombination of photogenerated carries. A bifunctional PEC sensing platform was designed for simultaneous high-performance detection of mucin-1 (MUC1) and carcinoembryonic antigen (CEA), which was based on generated Z-scheme heterostructured Ag3PO4/Ag/TiO2 nanorod arrays (NAs) and enzyme-mediated catalytic precipitation by alkaline phosphatase (ALP) and Au/hollow Co3O4 polyhedron. The proposed aptasensor displayed linear ranges of 1.0-100 ng mL-1 and 0.1-50 ng mL-1 for MUC1 and CEA with limit of detections of 0.430 and 0.058 ng mL-1, respectively. This strategy offers potential applications for early diagnosis, monitoring progression, and even evaluating the prognosis of breast cancer in practice.