A sensitive electrochemical immunosensor based on high-efficiency catalytic cycle amplification strategy for detection of cardiac troponin I.

An electrochemical immunosensor based on the novel high efficiency catalytic cycle amplification strategy for the sensitive detection of cardiac troponin I (cTnI). With its variable valence metal elements and spiny yolk structure, the Cu2O/CuO@CeO2 nanohybrid exhibits high speed charge mobility and exceptional electrochemical performance. Notably, fluorite-like cubic crystal CeO2 shell would undergo redox reaction with Cu2O core, which successfully ensures the continuous recycling occurrence of "fresh" Cu (II)/Cu (I) and Ce (Ⅳ)/Ce (Ⅲ) pairs at the electrode interface. The "fresh" active sites continue to emerge constantly, resulting in a significant increase in the current signal. In light of the electrochemical characterization, the electron transfer pathway and catalytic cycle mechanism among CeO2, Cu2O and CuO were further discussed. The developed electrochemical immunosensor detected cTnI from 100 fg/mL to 100 ng/mL with a LOD of 15.85 fg/mL under optimal conditions. The analysis results indicate that the immunosensor would hold promise for broad application prospects in the biological detection for other biomarkers.

An ultrasensitive electrochemical immunosensor based on meso-PdN NCs and Au NPs/N-CNTs for quantitative cTnI detection.

Electrochemical immunosensors have gained considerable attention in detecting human disease markers due to their excellent specificity, high sensitivity, and facile operation. Herein, a rational-designed sandwich-type electrochemical immunosensor is constructed for the sensitive detection of cardiac troponin I (cTnI) using nitrogen-doped carbon nanotubes loaded with gold nanoparticles (Au NPs/N-CNTs) as substrate and highly active mesoporous palladium-nitrogen nanocubes (meso-PdN NCs) as secondary antibody markers. Benefitting from its large specific surface area (638.04 m2 g-1) and high nitrogen content, novel polydopamine (PDA)/ halloysite nanotubes (HNTs) hybrid derived one-dimensional (1D) N-CNTs can provide more binding sites for the in-situ growth of Au NPs to connect Ab1. Furthermore, as an ideal substrate material, Au NPs/N-CNTs exhibit finely tuned mesoporous structures and outstanding conductivity, which facilitate the mass and electron transfer during the electrocatalysis process. Besides, highly concave surfaces and crystalline mesopores of meso-PdN NCs expose more surfaces and crevices, providing abundant reactive sites for H2O2 reduction. Remarkably, the as-obtained immunosensor presented a wide linear range (from 10 fg mL-1 to 100 ng mL-1) and an excellent low detection limit (9.85 fg mL-1). This study may offer new insights into the precise fabrication of efficient electrochemical immunosensors for various clinical diagnosis applications.

Ternary BiOI/Bi2S3/Au Nanosheet Arrays as a Photoelectrochemical Signal Converter for the Detection of Cardiac Troponin I.

Nanosheet arrays with stable signal output have become promising photoactive materials for photoelectrochemical (PEC) immunosensors. However, an essential concern is the facile recombination of carriers in one-component nanoarrays, which cannot be readily prevented, ultimately resulting in weak photocurrent signals. In this study, an immunosensor using gold nanoparticle-anchored BiOI/Bi2S3 nanosheet arrays (BiOI/Bi2S3/Au) as a signal converter was fabricated for sensitive detection of cardiac troponin I (cTnI). The ternary nanosheet arrays were prepared by a simple method in which Bi2S3 was well-coated on the BiOI surface by in situ growth, whereas the addition of Au further improved the photoelectric conversion efficiency and could link more antibodies. The three-dimensional (3D) ordered sheet-like network array structure and BiOI/Bi2S3/Au ternary nanosheet arrays showed stable and high photoelectric signal output and no significant difference in signals across different batches under visible light excitation. The fabricated immunosensor has a sensitive response to the target detection marker cTnI in a wide linear range of 500 fg/mL to 50 ng/mL, and the detection limit was 32 fg/mL, demonstrating good stability and selectivity. This work not only shows the great application potential of ternary heterojunction arrays in the field of PEC immunosensors but also provides a useful exploration for improving the stability of immunosensors.

An electrochemiluminescence sensor based on lanthanide bimetallic MOFs with a "cascade sensitization mechanism" for the sensitive detection of CA242.

Lanthanide metal-organic frameworks (Ln-MOFs) broaden the optical sensing applications of lanthanide ions due to the antenna effect between organic ligands and metals. However, the sensitization ability of the ligand to metal ions is limited, and maximizing the sensitization of the electrochemiluminescence behavior of Eu3+ is still a challenge for the application of Ln-MOFs. Therefore, under the guidance of the "cascade sensitization mechanism" based on the antenna effect sensitizing the electrochemiluminescence of bimetallic Ln-MOFs, we proposed Eu/Tb-MOFs with high luminescence intensity as a signal probe. According to the antenna effect, the conjugated structure and high extinction coefficient of the benzene ring of 2-amino terephthalic acid (NH2-BDC) can enhance the ECL luminescence intensity of Eu/Tb-MOFs. Tb3+ can act as an energy bridge between NH2-BDC and Eu3+, buffering the energy gap. The bimetallic sensitization is formed between Tb3+ and Eu3+, which can inhibit the reverse internal flow of energy and ensure the high luminous efficiency of Eu3+. In addition, the nanosphere mixed valence Fe3O4 as a co-reactant accelerator promotes the formation of transient free radical SO4•- through the valence change of Fe2+/Fe3+. The ECL immunosensor constructed by luminophores Eu/Tb-MOFs and nanosphere Fe3O4 provided a new explanation for the ECL self-luminous of Eu/Tb-MOFs.

Magnetic-controlled capsule endoscopy performance in aging patients.

BACKGROUND: The increasing elderly population and wide use of magnetic capsule endoscopy (MCE) have led to more attention to elderly patients. AIM: The aim of this study was to assess the performance (including transit time, cleanliness score, positive findings and safety) of MCE in aging patients (≥ 60 years), especially patients over 80 years old. METHODS: Consecutive patients of ≥ 60 years undergoing MCE at our center from August 2017 to August 2022 were classified into the oldest (≥ 80 years) and the older (60-79 years) groups. Esophageal transit time (ETT), gastric examination time (GET), small bowel transit time (SITT), and the quality of gastric preparation were compared. Information on examination indications, subjective discomforts, adverse events, and MCE outcomes were compared. RESULTS: Of 293 enrolled patients, 128 patients were in the oldest group and 165 patients were in the older group. ETT and GET were longer in the oldest group, whereas SITT was slightly longer in the oldest patients. Visualization scores were significantly lower in the body and antrum in the oldest patients. The total visualization score was lower in the older group compared with the oldest group; however, the difference was not significant. Cleanliness scores at the fundus and antrum and total cleanliness scores were lower in the oldest patients compared with the older patients. Positive findings and ulcers and erosions in the small intestine were more common in the oldest group. One patient had nausea during the gastric examination. Capsule retention in the cecum occurred in one case. CONCLUSION: MCE was feasible and safe for aging patients. ETT and GET were markedly longer and gastric cleanliness and visualization were worse, while overall small intestine-positive findings were higher in the oldest patients compared with the older patients.

Triple signal-enhancing sandwich-type electrochemical immunosensor based on Au@SNHC and PtPdCu/BNC for detection of Cardiac Troponin I.

A novel multiple amplification strategy for electrochemical immunoassay was developed elaborately. The realization of this strategy is based on the high efficiency catalysis of boron nitrogen double-doped carbon loaded trimetallic PtPdCu mulberry-like nanospheres (PtPdCu/BNC) and the satisfactory conductivity of gold nanoparticles modified with sulfur nitrogen co-doped hollow porous carbon (Au@SNHC). Single crystal anisotropic Pt octahedral seeds were synthesized with sodium citrate as shape-directing agent, and then three metals were grown in situ to prepare the trimetallic PtPdCu mulberry nanospheres, which had excellent utilization of atoms and a significant number of catalytic active centers. Boron nitrogen double-doped carbon (BNC) with abundant free electrons and high electron density micro-mesoporous can be used as the supported dispersion material of PtPdCu MBNSs, further catalytically enrich H2O2. Moreover, the etching vulcanization of small ZIF template and the co-doping of sulfur and nitrogen endow sulfur nitrogen co-doped hollow porous carbon (SNHC) with shorter the diffusion distance of charge carrier and lower mass transfer resistance. Under optimal conditions, the developed immunosensor exhibits good sensing performance with a detection limit of 4.27 fg⋅mL-1, and the wide linear dynamic range (10 fg⋅mL-1-100 ng⋅mL-1). This study provides a possible strategy for early diagnosis and postoperative monitoring of AMI.

A ZnIn2S4/Ag2CO3 Z-scheme heterostructure-based photoelectrochemical biosensor for neuron-specific enolase.

An efficient photo-to-electrical signal is pivotal to photoelectrochemical (PEC) biosensors. In our work, a novel PEC biosensor was fabricated for the detection of neuron-specific enolase (NSE) based on a ZnIn2S4/Ag2CO3 Z-scheme heterostructure. Due to the overlapping band potentials of the ZnIn2S4 and Ag2CO3, the formed Z-scheme heterostructure can promote the charge separation and photoelectric conversion efficiency. And the concomitant Ag nanoparticles in Ag2CO3 provided multiple functions to enhance the PEC response of the Z-scheme heterostructure. It acts not only as a bridge for the transfer of carriers between ZnIn2S4 and Ag2CO3, promoting the constructed Z-scheme heterostructure, but also as electron mediators to accelerate the transfer of photogenerated carriers and improve the capture of visible light of the Z-scheme heterostructure by surface plasmon resonance (SPR). Compared with single Ag2CO3 and ZnIn2S4, the photocurrent of the designed Z-scheme heterostructure increased more than 20 and 60 times respectively. The fabricated PEC biosensor based on a ZnIn2S4/Ag2CO3 Z-scheme heterostructure exhibits sensitive detection to NSE, and presents a linear range of 50 fg·mL-1 ~ 200 ng·mL-1 with a limit of detection of 4.86 fg·mL-1. The proposed PEC biosensor provides a potential approach for clinical diagnosis.

Sandwich-type electrochemical immunosensor based on CuFe2O4-Pd for cardiac troponin I detection.

A sandwich-type electrochemical immunosensor was designed by highly efficient catalytic cycle amplification strategy of CuFe2O4-Pd for sensitive detection of cardiac troponin I. CuFe2O4 with coupled variable valence metal elements exhibited favorable catalytic performance through bidirectional cycling of Fe2+/Fe3+ and Cu+/Cu2+ redox pairs. More importantly, Cu+ acted as the intermediate product of the catalytic reaction, promoted the regeneration of Fe2+ and ensured the continuous recycling occurrence of the double redox pairs, and significantly amplified the current signal response. Pd nanoparticles (Pd NPs) loaded on the surface of amino-functionalized CuFe2O4 (CuFe2O4-NH2) served as electrochemical mediators to capture labeled antibodies (Ab2), and also as co-catalysts of CuFe2O4 to further enhance the catalytic efficiency, thus improving the sensitivity of the electrochemical immunosensor. Under the optimal experimental conditions, the linear range was 0.001 ~ 100 ng/mL, and the detection limit was 1.91 fg/mL. The electrochemical immunosensor has excellent analytical performance, giving a new impetus for the sensitive detection of cTnI.

Design of a Double-Photoelectrode Sensing System with a Metal-Organic Framework-Based Antenna-like Strategy for Highly Sensitive Detection of PD-L1.

Currently, the construction of heterojunctions as a method to enhance photoelectrochemical (PEC) activity has shown prospective applications in the analytical field. Restricted by carrier separation at the interface, developing a heterojunction sensing platform with high sensitivity remains challenging. Here, a double-photoelectrode PEC sensing platform was fabricated based on an antenna-like strategy by integrating MIL-68(In)-NH2, a p-type metal-organic framework (MOF) photocatalyst, as a photocathode with the type-II heterojunction of CdSe/MgIn2S4 as a photoanode synchronously. According to the ligand-to-metal charge transition (LMCT), the photo-generated carriers of MIL-68(In)-NH2 transferred from the organic ligand to the metal cluster, which provides an efficient antenna-like transfer path for the charge at the heterojunction interface. In addition, the sufficient Fermi energy difference between the double photoelectrode provides the continuous internal driving force required for rapid carrier separation at the anode detection interface, significantly improving the photoelectric conversion efficiency. Hence, compared with the traditional heterojunction single electrode, the photocurrent response of the double-photoelectrode PEC sensing platform developed using the antenna-like strategy is 2.5 times stronger. Based on this strategy, we constructed a PEC biosensor for the detection of programed death-ligand 1 (PD-L1). The elaborated PD-L1 biosensor exhibited sensitive and precise detection capability with a detection range of 1 × 10-5 to 1 × 103 ng/mL and a lower detection limit of 3.26 × 10-6 ng/mL and demonstrated the feasibility of serum sample detection, providing a novel and viable approach for the unmet clinical need of PD-L1 quantification. More importantly, the charge separation mechanism at the heterojunction interface proposed in this study provides new creative inspiration for designing sensors with high-sensitivity PEC performance.

An enzymatic activity regulation-based clusterzyme sensor array for high-throughput identification of heavy metal ions.

The accurate identification and sensitive quantification of heavy metal ions are of great significance, considering that pose a serious threat to environment and human health. Most array-based sensing platforms, to date, utilize nanozymes as sensing elements, but few studies have explored the application of the peroxidase-like activity of clusterzymes in identification of multiple analytes. Herein, for the first time, we developed a clusterzyme sensor array utilizing gold nanoclusters (AuNCs) as sensing elements for five heavy metal ions identification including Hg2+, Pb2+, Cu2+, Cd2+ and Co2+. The heavy metal ions can differentially regulate the peroxidase-like activity of AuNCs, and that can be converted into colorimetric signals with 3,3',5,5'-tetramethylbenzidine (TMB) as the chromogenic substrate. Subsequently, the generated composite responses can be interpreted by combining pattern recognition algorithms. The developed clusterzyme sensor array can identify five heavy metal ions at concentrations as low as 0.5 µM and their multi-component mixtures. Especially, we demonstrated the successful identification of multiple heavy metal ions in tap water and traditional Chinese medicine, with an accuracy of 100% in blind test. This study provided a simple and effective method for identification and quantification of heavy metal ions, rendering a promising technique for environmental monitoring and drug safety assurance.

Changes in the esophagogastric junction outflow obstruction manometric feature based on the Chicago Classification updates.

BACKGROUND: The critical diagnostic criteria for esophagogastric junction outflow obstruction (EGJOO) were published in the latest Chicago Classification version 4.0 (CCv4.0). In addition to the previous criterion [elevated integrated relaxation pressure (IRP) in supine position], manometric diagnosis of EGJOO requires meeting the criteria of elevated median-IRP during upright wet swallows and elevated intrabolus pressure. However, with the diagnostic criteria modification, the change in manometric features of EGJOO remained unclear. AIM: To evaluate the esophageal motility characteristics of patients with EGJOO and select valuable parameters for confirming the diagnosis of EGJOO. METHODS: We performed a retrospective analysis of 370 patients who underwent high-resolution manometry with 5 mL water swallows × 10 in supine, × 5 in upright position and the rapid drink challenge (RDC) with 200 mL water from November 2016 to November 2021 at Peking University First Hospital. Fifty-one patients with elevated integrated supine IRP and evidence of peristalsis were enrolled, with 24 patients meeting the updated manometric EGJOO diagnosis (CCv4.0) as the EGJOO group and 27 patients not meeting the updated EGJOO criteria as the isolated supine IRP elevated group (either normal median IRP in upright position or less than 20% of supine swallows with elevated IBP). Forty-six patients with normal manometric features were collected as the normal high-resolution manometry (HRM) group. Upper esophageal sphincter (UES), esophageal body, and lower esophageal sphincter (LES) parameters were compared between groups. RESULTS: Compared with the normal HRM group, patients with EGJOO (CCv4.0) had significantly lower proximal esophageal contractile integral (PECI) and proximal esophageal length (PEL), with elevated IRP on RDC (P < 0.05 for each comparison), while isolated supine IRP elevated patients had no such feature. Patients with EGJOO also had more significant abnormalities in the esophagogastric junction than isolated supine IRP elevated patients, including higher LES resting pressure (LESP), intrabolus pressure, median supine IRP, median upright IRP, and IRP on RDC (P < 0.05 for each comparison). Patients with dysphagia had significantly lower PECI and PEL than patients without dysphagia among the fifty-one with elevated supine IRP. Further multivariate analysis revealed that PEL, LESP, and IRP on RDC are factors associated with EGJOO. The receiver-operating characteristic analysis showed UES nadir pressure, PEL, PECI, LESP, and IRP on RDC are parameters supportive for confirming the diagnosis of EGJOO. CONCLUSION: Based on CCv4.0, patients with EGJOO have more severe esophagogastric junction dysfunction and are implicated in the proximal esophagus. Additionally, several parameters are supportive for confirming the diagnosis of EGJOO.

Mixed-Ligand-Regulated Self-Enhanced Luminous Eu-MOF as an ECL Signal Probe for an Oriented Antibody-Decorated Biosensing Platform.

The self-luminescence behavior of lanthanide MOFs (Ln-MOFs) due to the unique antenna effect is considered to be a promising electrochemiluminescence (ECL) emission for biosensors. It is more challenging for Ln-MOFs on account of the difficulty to stimulate Ln ions with the desired energy-transfer efficiency to produce stronger ECL emissions at a low potential. Here, guided by a second ligand-assisted energy-transfer strategy, we present an efficient self-enhanced luminescence mixed-ligand Eu-MOF as an ECL signal probe for an oriented antibody-decorated biosensing platform with a low detection limit and a broad detection range. Diamino terephthalic acid (NH2-H2BDC) and 1,10-phenanthroline (Phen) were selected as the first and second ligands, respectively, to form highly conjugated structures, as well as suppress the nonradiative energy transfer. Impressively, Phen precisely adjusts the energy gap between the triplet ligand and the excited state of Eu3+, realizing the self-enhancement of ECL efficiency of the Eu-MOF. The mixed ligand adjusted the molar ratio to obtain the stable and strong ECL signal at a lowered triggering potential (0.83 V). In addition, FeCo@CNT features densely active FeCo sites along with a rich hierarchy conductive carbon nanotube (CNT) network, which is efficiently a co-reaction accelerator to produce more TPA•+ radicals to accelerate the reduction process of the Eu-MOF for achieving the ECL emission amplification. FeCo@CNT with heptapeptide HWRGWVC (HWR) constructed a matrix biosensing interface that allowed the fragment antigen-binding (Fab) regions to target specific antigens and enhance the incubation efficiency. The present study has gone some way toward designing a self-enhanced luminous Eu-MOF, thus giving new fresh impetus to develop high-performance ECL emitters for biological analysis.

Sandwich-type electrochemical immunosensor based on nitrogen-doped porous carbon and nanoporous trimetallic nanozyme (PdAgCu) for determination of prostate specific antigen.

A sandwich-type electrochemical immunosensor was designed for the ultrasensitive detection of prostate-specific antigen (PSA), using Au nanoparticles (Au NPs) modified nitrogen-doped porous carbon (NPC) as sensor platform and trimetallic PdAgCu mesoporous nanospheres (PdAgCu MNSs) as enzyme-mimicking labels. NPC was prepared by a facile one-step pyrolysis strategy of biomimetic phylloid zeolite imidazole framework (ZIF-L) nanosheets. Through this strategy, the graphitization of the microcrystalline structure enhanced the electrical conductivity, while its enlarged specific surface area and abundant pore volume can enrich H2O2 to improve the catalytic efficiency. Moreover, Au NPs were used to modify NPC without cross-linking agents to further optimize electron transport while capturing primary antibodies, improving stability and sensitivity of the immunosensor. PdAgCu MNSs with uniform size, cylindrical open mesoporous channels, and continuous crystal frame structure were self-assembling synthesized by electrostatic adsorption and ascorbic acid (AA) co-reduction with amphiphilic dioctadecyldimethylammonium chloride (DODAC) as surfactant-cum-micelle, whose unique structure maximizes the use of polyatoms to expose catalytic sites, exhibiting good biocompatibility and electrocatalytic ability. Under the optimal conditions, the immunosensor showed superior sensitivity, a wide dynamic detection range (10 fg mL-1 ~ 100 ng mL-1) and a low limit of detection (LOD, 3.29 fg mL-1). This work provides a convenient strategy for the clinical detection of PSA.

Ultrasensitive photoelectrochemical immunosensor based on Dual-Photosensitive electrodes.

In the study, a photoelectrochemical (PEC) immunosensor based on dual-photosensitive electrodes was developed for cardiac troponin I (cTnI) detection. The sensing photocathode with biometric functions was prepared by CuInS2 and narrow band gap semiconductor In2S3 as the counter electrode. In this way, the separation of photoanode and biometric events was realized, and the ability of stability of the immunosensor could be effectively improved. Moreover, the attraction to the photogenerated electrons (e-) from photoanode would be increased by the abundant holes (h+) of photocathode, under the radiation of light. This tremendously improves the photoelectric response, which further improves the sensitivity of the immunosensor. The controllable-synthesis uncomplicated photoelectric material not only accords with the principle of simplicity of electrode modification but also makes the immunosensor more conducive to the practical application. Additionally, even in the case of zero bias voltage, the constructed PEC immunosensor can operate with high efficiency, namely, self-powered. The immunosensor could provide the quantitative readout photocurrent to a concentration of cTnI in the range of 0.10 pg/mL to 1.00 µg/mL and the detection limit was 0.0113 pg/mL under the optimal experimental conditions. With favorable performance in terms of anti-interference, stability, specificity and reproducibility, this immunosensor will provide new prospects for general PEC bioanalysis development.

A "signal-off" electrochemiluminescence biosensing platform based on high efficiency quenching effect of functionalized copper oxide toward glutathione-gold nanoclusters.

A "signal-off" Electrochemiluminescence (ECL) biosensing platform based on Glutathione-Au nanoclusters covered reduced graphene oxide (GSH-Au NCs@rGO) and Au nanoparticles functionalized copper oxide (Au@CuO) was fabricated. The GSH ligand protected Au NCs were spontaneously adsorbed on the rGO surface via Van der Waals force. As ECL emitters, GSH-Au NCs@rGO not only support more luminophores and immobilization of bioreceptor units also facilitates mass transfer, accelerating ECL excitation to obtain a higher ECL signal intensity. Remarkably, Au@CuO with good biocompatibility was first applied as a quenching probe. Au@CuO (acceptor)-dependent resonance energy transfers (RET) with GSH-Au NCs@rGO (donor) could effectively quenched the ECL intensity to a reasonable range for requirements of trace analysis. The proposed ECL biosensing platform was evaluated with cardiac troponin I (cTnI) as a model analyte, achieving a low detection limit of 54.95 fg/mL. This strategy may provide as new approaches for the sensitive detection of biomarkers in the early clinical diagnosis of diseases.

A double reaction system induced electrochemiluminescence enhancement based on SnS2 QDs@MIL-101 for ultrasensitive detection of CA242.

At present, the development of electrochemiluminescence (ECL) immunosensor with excellent performance is still the research focus of immunoassay and detection. Herein, SnS2 quantum dots (SnS2 QDs) and metal-organic framework (MIL-101 (Cr)) are effectively combined to achieve synergistic signal amplification based on K2S2O8 co-reactant, thereby constructing SnS2 QDs/SO4•- and SO4•-/O2 ECL double reaction luminous systems. SnS2 QDs and singlet oxygen (1(O2)2*) produced from the system as light-emitting devices jointly enhance the ECL response and significantly improve the sensitivity of the ECL immunosensor. Dissolved oxygen and SnS2 QDs respectively generate HOO• and SnS2 QDs•- under negative potential, and react with transient SO4•- to emit strong light respectively, so as to jointly enhance the ECL response. MIL-101 catalyzes the oxygen cathode reduction reaction to promote the conversion of dissolved oxygen into HOO•, which greatly improves the ECL response of 1(O2)2*. CuS with spherical nanoflower-like form as a co-reaction promoter of K2S2O8 generate more SO4•- active substances, which further enhance the ECL response of the immunosensor. The constructed ECL immunosensor has the advantages of low detection limit, high sensitivity and better stability. Under the optimal conditions, the detection range is 0.1 mU/mL∼100 U/mL, and the detection limit is 0.015 mU/mL. The results show that the constructed ECL immunosensor can detect human CA242 samples and have a broad application prospect in biological analysis and early diagnosis of diseases.

An efficient electrochemical immunosensor for Alpha-Fetoprotein detection based on the CoFe prussian blue analog combined PdAg hybrid nanodendrites.

A sandwich-type electrochemical immunosensor was developed using PdAg nanodendrites modified CoFe prussian blue analog (PdAg NDs/CoFe PBA) as the signal label for the alpha-fetoprotein (AFP) detection. The novel hollow porous CoFe PBA with KCoFe phase was synthesized via self-template epitaxial growth strategy. Benefiting from the filling of K ions and the hollow porous structure, the electron transfer rate and the mass transfer rate of CoFe PBA were improved, further enhancing the catalytic capacity. In addition, the special dendritic morphology of PdAg NDs can maximize the proportion of catalytic active sites, and stable Pd-N and Ag-N bonds can further fix more immune molecules to increase the sensitivity of electrochemical immunosensors. Under optimized parameters, the fabricated immunosensor demonstrated a wide linear range detection from 100.0 fg mL-1 to 200.0 ng mL-1, and a low detection limit of 18.6 fg mL-1. Simultaneously, the immunosensor with acceptable reproducibility, specificity, stability and exhibited satisfactory performance in human serum analysis. This work provides a new line for the detection of other tumor markers, which means that it has great application potential in immune analysis.

A dual-signal output electrochemical immunosensor based on Au-MoS2/MOF catalytic cycle amplification strategy for neuron-specific enolase ultrasensitive detection.

In this work, a dual-signal output electrochemical immunosensor based on the Au-MoS2/MOF high-efficiency catalytic cycle amplification strategy for the sensitive detection of neuron-specific enolase (NSE). The mixed-valence structure MOF (Fe2+/Fe3+-MOF) exhibits high-speed charge mobility and excellent electrochemical performance. Notably, nanoflowers-like MoS2 (MoS2 NFs), as a co-catalyst, were introduced into Fe2+/Fe3+-MOF to successfully ensure the stable cycle of Fe2+/Fe3+ at the electrode interface. The constantly emerging of "fresh" active sites significantly amplified the current signal response. According to the electrochemical behavior, the catalytic cycle mechanism and electron transfer pathways between MoS2 and Fe2+/Fe3+-MOF were further discussed. The two output signals of a sample realized the self-calibration of the immunoassay results, which improved the reliability and sensitivity of the immunosensor. Under optimal conditions, the linear range was 1.00 pg/mL∼100 ng/mL, and the low detection limits were 0.37 pg/mL and 0.52 pg/mL. The results suggest that the as-proposed immunosensor will be promising in the biological analysis and early clinical diagnosis of cancer biomarkers.