Electrochemiluminescence Immunosensor Research Articles

A dual-signal ECL-RET immunosensor based on VC-g-C3N4 and Ru-Zr-MOF for the detection of β2-MG

This work proposes a novel dual-signal electrochemiluminescence (ECL) immunosensor based on energy resonance transfer (RET) for the detection of β2-Microglobulin (β2-MG). Introducing carbon vacancy into g-C3N4 (VC-g-C3N4) can lead to the narrowing of the band gap and the reduction of LUMO, thereby significantly enhancing the ECL efficiency of the material. Meanwhile, Zr-MOF can effectively load Ru(bpy)32+ (Ru-Zr-MOF), enabling its stable existence on the electrode. The ECL emission spectrum of VC-g-C3N4 overlaps well with the fluorescence excitation spectrum of Ru-Zr-MOF, indicating an effective ECL-RET effect between them. As the concentration of β2-MG increases, the intensity of anodic ECL signal gradually increases, while the intensity of cathodic ECL signal gradually decreases. The difference between the cathodic and anodic ECL signals has a good linear relationship within the concentration range from 0.2 pg/mL to 200 ng/mL, with a detection limit of 27.73 fg/mL. The constructed immunosensor can be used for practical analysis in human serum. The proposed sensor has great potential in clinical detection of β2-MG, providing new insights for biomolecular detection and disease diagnosis.

Electrochemiluminescence quenching effect of Cu2O towards flower-like ferric ion-doped g-C3N4 and its application for Cyfra21-1 immunosensing

In this article, ferric ion-doped floral graphite carbon nitride (Fe–CN-3, energy donor) was used to construct the substrate of the immunosensor and copper oxide nanocubes (Cu2O, energy acceptor) were taken as an efficient ECL quenching probe. A sandwich quench electrochemiluminescence (ECL) immunosensor for soluble cytokeratin 19 fragment (Cyfra21-1) detection was preliminarily developed based on a novel resonant energy transfer donor-acceptor pair. Fe–CN-3, a carbon nitride that combines the advantages of metal ion doping as well as morphology modulation, is used in ECL luminophores to provide more excellent ECL performance, which makes a significant contribution to the application and development of carbon nitride in the field of ECL biosensors. The regular shape, high specific surface area and excellent biocompatibility of the quencher Cu2O nanocubes facilitate the labeling of secondary antibodies and the construction of sensors. Meanwhile, as an energy acceptor, the UV absorption spectrum of Cu2O can overlap efficiently with the energy donor's ECL emission spectrum, making it prone to the occurrence of ECL-RET and thus obtaining an excellent quenching effect. These merits of the donor-acceptor pair enable the sensor to have a wide detection range of 0.00005–100 ng/mL and a low detection limit of 17.4 fg/mL (S/N = 3), which provides a new approach and theoretical basis for the clinical detection of lung cancer.

A novel electrochemiluminescence immunosensor: BiOBr/Bi2WO6 heterojunction for ultrasensitive detection of CA19-9

Bi2WO6, an environmentally friendly material with certain electrochemiluminescence (ECL) properties, has been used as a novel ECL luminescent material. In the present work, bismuth tungstate (Bi2WO6) was composited with bismuth bromide (BiOBr) to form a S-type heterojunction with a flower like morphology where the Bi2WO6 core was wrapped with BiOBr outer shell. The interface of the heterojunction is closely contacted, which can promote electron transfer, improve conduction and enhance ECL emission to a certain extent. The BiOBr/Bi2WO6 (BBW) heterojunction with K2S2O8 as a co-reactant demonstrates cathodic ECL emission at 550–800 nm in the potential range of −1.8–0 V. Cu2O@Ag with a special sea urchins morphology was introduced into the system to catalyze the reduction of S2O82− to generate more SO4•−, which further enhances the ECL emission. The ECL immunosensor constructed with the heterojunction for CA19–9 detection exhibits a robust linear relationship in the concentration range from 0.1 mU·mL−1 to 100 U·mL−1 and detection limit as low as 87.6 μU·mL−1. The immunosensor successfully detected CA19–9 in serum, showing great application potential in the clinical practice.

An AuNPs/Co3O4 nanocubic cage–based electrochemiluminescent immunosensor for Corin: A biomarker of stroke

Stroke, or cerebral apoplexy, is a paroxysmal disease that seriously threatens the neurological functions of middle-aged and older men, resulting in high rates of disability and mortality. The blood level of Corin can accurately predict the risk and subtype of stroke. Herein, an immunosensor was developed utilizing a nanocomposite of Au nanoparticles and Co3O4 nanocubic cages (AuNPs/Co3O4NcC) as the sensing substrate, with luminol serving as the sensing probe for Corin detection. Through the application of 3-aminopropyltrimethoxysilane, AuNPs/Co3O4NcC was affixed to the surface of indium tin oxide (ITO)-coated glass, considerably enhancing the electrochemiluminescence (ECL) performance of luminol due to its peroxidase-like activity. To confer biological specificity by immobilizing the Corin antibody on this substrate and to block residual active sites with bovine serum albumin, an immunosensor was developed. The capture of Corin protein by the antibody through an immune reaction, leading to its binding on the sensor, resulted in a decreased ECL signal. Under optimized conditions, the proposed ECL immunosensor demonstrated a broad linear response range from 1 pg/mL to 4800 pg/mL and a low detection limit of 0.26 pg/mL. This ECL immunosensor is characterized by its specificity, stability, and reproducibility and can detect Corin in real blood samples.

Dual signal amplification strategy for enhancing Eu2Sn2O7 electrochemiluminescence immunosensor for the sensitive detection of N-terminal pro-brain natriuretic peptide

Pyrochlore oxide Eu2Sn2O7, an electrochemiluminescence (ECL) emitter, exhibits favorable characteristics such as low toxicity, good stability, and abundant electron vacancies. In this work, the interfacial electron transfer efficiency of Eu2Sn2O7 was significantly enhanced through the in situ surface modification with silver nanoparticles (AgNP). Moreover, we introduced a dual signal-amplification strategy involving AgNP and H2O2. The AgNP as a co-reaction catalyst facilitated the reduction of the co-reactant K2S2O8. The OH• generated through H2O2 reduction on the electrode surface induced the decomposition of K2S2O8 to SO4•−. The MoS2-PEI-AuNP (PEI: polyethylenimine) composite was selected as an ideal substrate. A highly sensitive ECL immunosensor based on Eu2Sn2O7-Ag and MoS2-PEI-AuNP was constructed to detect N-terminal pro-brain natriuretic peptide (NT-proBNP). Under the optimized experimental conditions, the ECL immunosensor demonstrated a linear range of 10 fg·mL−1–50 ng·mL−1, with a detection limit of 2.9 fg·mL−1, and showed excellent stability and specificity. The results demonstrate the potential of the ECL immunosensor for clinical diagnosis applications.

An electrochemiluminescent dual-signal immunosensor based on a Ru(bpy)32+-doped silica nanoparticle/copper nanocluster composite for okadaic acid detection

In this study, a sensitive dual-signal electrochemiluminescence (ECL) immunosensor was developed for okadaic acid (OA) detection utilizing copper nanoclusters (CuNCs) and Ru(bpy)32+-doped silica nanoparticles (RuSiNPs). Interestingly, the CuNCs could simultaneously enhance both cathodic (−0.95 V) and anodic (+1.15 V) ECL signals of RuSiNPs, forming a dual-signal ECL sensing platform. Further, RuSiNPs@CuNCs were used as immunomarkers by covalently conjugating them with an anti-OA monoclonal antibody (mAb) to form probes. Finally, dual ECL signals of the immunosensor were fabricated and showed good linear relationships with OA concentrations in the range of 0.05–70 ng mL−1, having a median inhibitory concentration (IC50) of 1.972 ng mL−1 and a limit of detection of 0.039 ng mL−1. Moreover, the constant ratio of the cathodic and anodic ECL peaks achieved self-calibration of the detection signal and improved the reliability of the results. Finally, we successfully applied the ECL sensor to detect OA in spiked oyster samples.

A Co-Reactive Immunosensor Based on Ti3C2Tx MXene@TiO2-MoS2 Hybrids Promoting luminol@Au@Ni-Co NCs Electrochemiluminescence for CYFRA 21-1 Detection.

The construction of assays is capable of accurately detecting cytokeratin-19 (CYFRA 21-1), which is critical for the rapid diagnosis of nonsmall cell lung cancer. In this work, a novel electrochemiluminescence (ECL) immunosensor based on the co-reaction promotion of luminol@Au@Ni-Co nanocages (NCs) as ECL probe by Ti3C2Tx MXene@TiO2-MoS2 hybrids as co-reaction accelerator was proposed to detect CYFRA 21-1. Ni-Co NCs, as a derivative of Prussian blue analogs, can be loaded with large quantities of Au NPs, luminol, and CYFRA 21-1 secondary antibodies due to their high specific surface area. To further improve the sensitivity of the developed ECL immunosensor, Ti3C2Tx MXene@TiO2-MoS2 hybrids were prepared by in situ growth of TiO2 nanosheets on highly conductive Ti3C2Tx MXene, and MoS2 was homogeneously grown on Ti3C2Tx MXene@TiO2 surfaces by the hydrothermal method. Ti3C2Tx MXene@TiO2-MoS2 hybrids possess excellent catalytic performance on the electro-redox of H2O2 generating more O2·- and obtaining optimal ECL intensity of the luminol/H2O2 system. Under the appropriate experimental conditions, the quantitative detection range of CYFRA 21-1 was from 0.1 pg mL-1 to 100 ng mL-1, and the limit of detection (LOD) was 0.046 pg mL-1. The present sensor has a lower LOD with a wider linear range, which provides a new analytical assay for the early diagnosis of small-cell-type lung cancer labels.

L-Cysteine-Tuned the Hierarchical Structure Based on Benzimidazole: Synthesis, Characterization, and Application in Ratiometric Electrochemiluminescence Immunoassay.

Efficient and robust electrochemiluminescence (ECL) emitters are crucial for enhancing the ECL immunosensor sensitivity. This study introduces a novel ECL emitter, CoBIM/Cys, featuring a hierarchical core-shell structure. The core of the structure is created through the swift coordination between the sulfhydryl and carboxyl groups of l-cysteine (l-Cys) and cobalt ions (Co2+), while the shell is constructed by sequentially coordinating benzimidazole (BIM) with Co2+. This design yields a greater specific surface area and a more intricate porous structure compared to CoBIM, markedly enhancing mass transfer and luminophore accessibility. Moreover, the l-Cys and Co2+ core introduces Co-S and Co-O catalytic sites, which improve the catalytic decomposition of H2O2, leading to an increased production of hydroperoxyl radicals (OOH•). This mechanism substantially amplifies the ECL performance. Leveraging the competitive interaction between isoluminol and BIM for OOH• during ECL emission, we developed a ratiometric immunosensor for cardiac troponin I (cTnI) detection. This immunosensor demonstrates a remarkably broad detection range (1 pg mL-1 to 10 ng mL-1), a low detection limit (0.4 pg mL-1), and exceptional reproducibility and specificity.

Hollow graphitic carbon nitride with tunable shell thickness for electrochemiluminescence and photoelectrochemistry dual-mode detection of cardiac troponin I

An electrochemiluminescence (ECL) and photoelectrochemistry (PEC) dual-mode immunosensor based on hollow graphitic carbon nitride (H-C3N4) as dual-signal indicator was constructed for sensitive and accurate detection of cardiac troponin I (cTnI). Studied have been demonstrated that hollow structures rather than bulk nanomaterials can be able to decrease the inner filter effect and reduce the migration of photogenerated charges. Herein, we precisely control the shell thickness of H-C3N4 from 15.3 to 34.7 nm and clearly explore their correlating ECL-PEC performances. Notably, ECL and PEC performances of the optimal shell thickness of H-C3N4 (25.1 nm) is 2.7 and 4.4 times higher than that of solid C3N4, which leaves enormous room for optimization the performances of H-C3N4. Furthermore, TiO2 not only is a coreaction accelerator, but also possesses well-matched band structure with H-C3N4. By integrating TiO2 with the optimal H-C3N4, the obtained H-C3N4@TiO2 shows the highest ECL and PEC response. As a result, the established immunosensor shows the sensitive detection of cTnI with a desirable detection limit of 0.65 fg mL−1 (ECL) and 0.63 fg mL−1 (PEC), respectively. This work shows an effective strategy to develop a dual-mode immunosensor which allows signal cross-checking and presents a reliability detection in bioanalysis.

FeNi-MIL-88B-based electrochemiluminescence immunosensor for ultra-sensitive detection of CD44 protein via dual-quenching strategy

BackgroundCluster of Differentiation 44 (CD44) is considered an important biomarker for various cancers, and achieving highly sensitive detection of CD44 is crucial, which plays a significant role in tumor invasion and metastasis, providing essential information for clinical tumor diagnosis. Commonly used methods for analysis include fluorescence spectroscopy (FL), photoelectrochemical analysis (PEC), electrochemical analysis (EC), and commercial ELISA kits. Although these methods offer high sensitivity, they can be relatively complex to perform experimentally. Electrochemiluminescence (ECL) has gained widespread research attention due to its high sensitivity, ease of operation, effective spatiotemporal control, and close to zero background signal. ResultsIn this work, a sandwich-type ECL immunosensor for detecting CD44 was constructed using luminol as a luminophore. In this sensing platform, bimetallic MOFs (Pd@FeNi-MIL-88B) loaded with palladium nanoparticles (Pd NPs) were used as a novel enzyme mimic, exhibiting excellent catalytic performance towards the electroreduction of H2O2. The hybrids provided a strong support platform for luminol and antibodies, significantly enhancing the initial ECL signal of luminol. Subsequently, core-shell Au@MnO2 nanocomposites were synthesised by gold nanoparticles (Au NPs) encapsulated in manganese dioxide (MnO2) thin layers, as labels. In the luminol/H2O2 system, Au@MnO2 exhibited strong light absorption in the broad UV–vis spectrum, similar to the black body effect, and the scavenging effect of Mn2+ on O2•−, which achieved the dual-quenching of ECL signal. Under the optimal experimental conditions, the immunosensor demonstrated a detection range of 0.1 pg mL−1 − 100 ng mL−1, with a detection limit of 0.069 pg mL−1. SignificanceBased on Pd@FeNi-MIL-88B nanoenzymes and Au@MnO2 nanocomposites, a dual-quenching sandwich-type ECL immunosensor for the detection of CD44 was constructed. The proposed immunosensor exhibited excellent reproducibility, stability, selectivity, and sensitivity, and provided a valuable analytical strategy and technical platform for the accurate detection of disease biomarkers, and opened up potential application prospects for early clinical treatment.

Novel immunosensor based on electrochemiluminescence inner filter effect and static quenching between fibrillary Ag-MOGs and SiO2@PANI@AuNPs for enabling the sensitive detection of neuron-specific enolase.

Metal-organic gels (MOGs) are unique supramolecular gels that are convenient to synthesize. In this work, a cathodic electrochemiluminescence (ECL) system based on Ag-MOGs as a luminophore and K2S2O8 as a co-reactor was developed. The ECL spectrum of the Ag-MOGs overlapped significantly with the strong UV-Vis spectrum of the SiO2@PANI@AuNPs, which effectively quenched the ECL luminescence of the Ag-MOGs. Relying on theinner filter effect between Ag-MOGs and SiO2@PANI@AuNPs, a novel ECL-IFE immunosensor was developed for the detection of neuron-specific enolase (NSE). Under optimal conditions, the ECL signal of the immunosensor displayed excellent linearity over the NSE concentration range of 10 fg/mL-100 ng/mL. The limit of detection (LOD) was 2.6 fg/mL (S/N = 3) with a correlation coefficient R2 of 0.9975. The ECL immunosensor also exhibited excellent stability and reproducibility for the detection of NSE. The results reported provide afeasible concept for the development analytical methods for the detection of other clinically relevant biomarkers.

Ultrasensitive Detection of SARS-CoV-2 Nucleocapsid Protein Based on Porphyrin-Based Metal-Organic Gels with Highly Efficient Electrochemiluminescence at Low Potential.

Metal-organic gels (MOGs) are a new type of intelligent soft material, which are bridged by metal ions and organic ligands through noncovalent interactions. In this paper, we prepared highly stable P-MOGs, using the classical organic electrochemiluminescence (ECL) luminescence meso-tetra(4-carboxyphenyl)porphine as the organic ligand and Fe3+ as the metal ion. Surprisingly, P-MOGs can stably output ECL signals at a low potential. We introduced P-MOGs into the ECL resonance energy transfer strategy (ECL-RET) and constructed a quenched ECL immunosensor for the detection of the SARS-CoV-2 nucleocapsid protein (SARS-CoV-2-N). In the ECL-RET system, P-MOGs were used as energy donors, and Au@Cu2O@Fe3O4 were selected as energy acceptors. The ultraviolet-visible spectrum of Au@Cu2O@Fe3O4 partially overlaps with the ECL spectrum of P-MOGs, which can effectively touch off the ECL-RET behavior between the donors and receptors. Under the ideal experimental situation, the linear detection range of the SARS-CoV-2-N concentration was 10 fg/mL to 100 ng/mL, and the limit of detection was 1.5 fg/mL. This work has broad application prospects for porphyrin-MOGs in ECL sensing.

Ultrasensitive ECL immunosensor for trenbolone detection based on double-assisted signal amplification strategy of Nb2O5-decorated TiO2 nanorods and Co3O4-Co3(PO4)2 nanosheets

Trenbolone (TB) is used for treating malnutrition in livestock and increasing their muscle mass. However, its excessive intake can lead to metabolic and reproductive disorders in animals. In addition, it causes adverse effects in humans even at very low concentrations. Herein, an innovative electrochemiluminescence (ECL) immunosensor based on a double-assisted signal amplification strategy has been proposed for the sensitive detection of TB. Nb2O5-decorated TiO2 nanorods, with a large surface area, good biocompatibility, and excellent catalytic properties, were used as the substrates for the effective loading of TB antibodies. In addition, Co3O4-Co3(PO4)2 nanosheets, used as labels, improved the ECL signals and were used to incorporate TB antigens for designing competitive ECL immunosensors. Various experimental factors, such as the pH of the phosphate buffer solution, concentration of the co-reactant, and time of incubation, were examined. The proposed ECL immunosensor exhibited high sensitivity, good repeatability, and high stability for TB concentration and was successfully implemented for the analysis of real water samples. Under optimal conditions, the proposed immunosensor responded linearly to relevant concentrations of TB from 1.0 × 10−3 to 1.0 × 103 ng/mL, with a detection limit of 0.39 × 10−3 ng/mL (S/N = 3). Notably, this study fabricated a simple and ultrasensitive TB detection system with novelty of practical application in environmental monitoring.

Multimetal-Based Metal-Organic Framework System for the Sensitive Detection of Heart-Type Fatty Acid Binding Protein in Electrochemiluminescence Immunoassay.

In this work, an electrochemiluminescence (ECL) quenching system using multimetal-organic frameworks (MMOFs) was proposed for the sensitive and specific detection of heart-type fatty acid-binding protein (H-FABP), a marker of acute myocardial infarction (AMI). Bimetallic MOFs containing Ru and Mn as metal centers were synthesized via a one-step hydrothermal method, yielding RuMn MOFs as the ECL emitter. The RuMn MOFs not only possessed the strong ECL performance of Ru(bpy)32+ but also maintained high porosity and original metal active sites characteristic of MOFs. Moreover, under the synergistic effect of MOFs and Ru(bpy)32+, RuMn MOFs have more efficient and stable ECL emission. The trimetal-based MOF (FePtRh MOF) was used as the ECL quencher because of the electron transfer between FePtRh MOFs and RuMn MOFs. In addition, active intramolecular electron transfer from Pt to Fe or Rh atoms also occurred in FePtRh MOFs, which could promote intermolecular electron transfer and improve electron transfer efficiency to enhance the quenching efficiency. The proposed ECL immunosensor demonstrated a wide dynamic range and a low detection limit of 0.01-100 ng mL-1 and 6.8 pg mL-1, respectively, under optimal conditions. The ECL quenching system also presented good specificity, stability, and reproducibility. Therefore, an alternative method for H-FABP detection in clinical diagnosis was provided by this study, highlighting the potential of MMOFs in advancing ECL technology.

Europium Metal-Organic Framework with a Tetraphenylethylene-Based Ligand: A Dual-Mechanism Quenching Immunosensor for Enhanced Electrochemiluminescence via the Coordination Trigger.

The effective applications of electrochemiluminescence (ECL) across various fields necessitate ongoing research into novel luminophores and ECL strategies. In this study, self-luminous flower-like nanocomposites (Eu-tcbpe-MOF) were prepared by coordination self-assembly using the aggregation-induced emission material 1,1,2,2-tetrakis(4-carboxyphenyl)ethylene (H4TCBPE) and Eu(III) ions as the precursors. Compared with the monomers and aggregates of H4TCBPE, Eu-tcbpe-MOF exhibits stronger ECL emission. Such enhanced electrochemiluminescence is due to coordination as the coordination-triggered electrochemiluminescence (CT-ECL) enhancement effect. In this study, a cubic-structured nanocomposite (Co9S8@Au@MoS2) was used as an efficient quencher, and a more sensitive ECL detection platform was achieved by two quenching mechanisms: resonance energy transfer and competitive consumption of coreactants. N,N-Diethylethanolamine (DBAE) was used as a coreactant, and DBAE has a faster electron transfer rate and stronger energy supply efficiency than the traditional anodoluminescent coreactant tripropylamine, which effectively improves the ECL signal intensity of Eu-tcbpe-MOF. Hence, a sandwich-type ECL immunosensor was prepared by employing a dual-quenching mechanism, utilizing Eu-tcbpe-MOF as the detection probe and Co9S8@Au@MoS2 as the quencher, achieving precise detection of carcinoembryonic antigen from 0.1 pg·mL-1 to 100 ng·mL-1 with a detection limit of 35.1 fg·mL-1.

Electrochemiluminescence immunosensor based on tin dioxide quantum dots and palladium-modified graphene oxide for the detection of zearalenone

Developing low-cost and efficient methods to enhance the electrochemiluminescence (ECL) intensity of luminophores is highly desirable and challenging. Herein, we developed an efficient ECL system based on palladium-modified graphene oxide as a substrate and tin dioxide quantum dot-modified spike-like gold-silver alloy as an immunoprobe. Specifically, palladium-modified graphene oxide was rationally selected as the sensor substrate for the attachment of zearalenone antigens while facilitating the amplification of the ECL signal through enhanced electron transfer efficiency. A spike-like gold-silver alloy modified with tin dioxide quantum dots was attached to the zearalenone antibody as an immunoprobe, and the sensor exhibited remarkable sensitivity due to the exceptional ECL performance of the quantum dots. To demonstrate the practical feasibility of the principle, zearalenone levels were detected in actual samples of maize and pig urine, and the sensor showed a broad linear range (0.0005–500 ng mL−1) and low detection limit (0.16 pg mL−1) in the high-sensitivity detection of Zearalenone. Overall, this work first reports the construction of a highly sensitive ECL immunosensor for the detection of zearalenone using a protruding gold-silver alloy modified with tin dioxide as an immunoprobe and a palladium modified graphene oxide as a substrate. It provides a novel approach for the detection of small molecule toxin-like substances.

Electrochemiluminescent biosensor based on ECL-RET between Ru@TiO2-MXene and Pd@UiO-66-NH2 for the detection of carcinoembryonic antigens

Carcinoembryonic antigen (CEA) is often employed as a crucial tumor marker for both colon and rectal cancer. The assessment of CEA levels holds significant therapeutic importance in the diagnosis of these malignancies. In this study, an electrochemiluminescence immunosensor with a signal off was ingeniously designed with Ru@TiO2-MXene as the base material of the energy donor, and Pd@UiO-66-NH2 as the marker of the energy acceptor. This immunosensor was constructed based on the strong interaction between the two components of ECL-RET. Remarkably, TiO2-MXene exhibits favorable film-forming properties and electrical conductivity while effectively immobilizing Ru(bpy)32+. On the other hand, Pd@UiO-66-NH2 has excellent biocompatibility and light absorption, making it an ideal choice for use as a secondary antibody marker. The electrochemiluminescence immunosensor constructed exhibits an extensive detection range of 1 × 10−5 ng·ml−1 to 80 ng·ml−1 and a narrow detection limit of 2.65 fg·ml−1. The novel electrochemiluminescence immunosensor, as presented in this investigation, introduces a distinct methodology for CEA detection, carrying immense clinical significance in the field of colon and rectal cancer diagnosis.

Single-atom iron boosts electrochemiluminescence for ultrasensitive carcinoembryonic antigen detection.

Asimple and ultrasensitive sandwich-type electrochemiluminescence (ECL) immunosensor has been developedusing porous three-dimensional gold nanoparticles (Au NPs) iron(Fe)-zinc(Zn) metal-organic frameworks (Au NPs-FeZn-MOFs@luminol) as high-efficiency ECL signal probes with Fe single-atom catalysts (SACs) (Fe-N-C SACs) as potentially advanced coreaction accelerators and dissolved oxygen as a coreaction agent to realize an H2O2-free amplification method for detecting carcinoembryonic antigen (CEA). The cathodic ECL of luminol, which was usually negligible, increased first. Because the Fe-N-C SACs exhibited an outstanding catalytic performance and a unique electronic structure, different reactive oxygen species (ROS) were generated via the oxygen reduction reaction. ROS oxidized the luminol anions to luminol anion radicals, preventing the time-consuming luminol electrochemical oxidation. Furthermore, the luminol anion radicals generated in situ reacted with ROS to produce potent cathodic ECL emissions. The immunosensor exhibited favorable analytical accuracy (detection range: 0.1 pg mL-1-80 ng mL-1), and its detection limit for serum samples was 0.031 pg mL-1 (S/N = 3). Consequently, the proposed strategy offers a new approach for early screening of CEA.

Double-Amplified Electrochemiluminescence Immunoassay Sensor for Highly Sensitive Detection of CA19-9 Using a Ternary Semiconductor CdSSe.

In this paper, an electrochemiluminescence (ECL) immunosensor for ultrasensitive detection of CA19-9 was constructed using ternary compound CdSSe nanoparticles as ECL emitter. The immunosensor employs Cu2S and gold-doped diindium trioxide (Au-In2O3) nanocubes as coreaction accelerators to achieve a double-amplification strategy. In general, a hexagonal maple leaf-shaped Cu2S with a large surface area was selected as the template, and the in situ growth of CdSSe on its surface was achieved using a hydrothermal method. The presence of Cu2S not only inhibited the aggregation of CdSSe nanoparticles to reduce their surface energy but also acted as an ECL cathode coreaction promoter, facilitating the generation of SO4•-. Consequently, the ECL intensity of CdSSe was significantly enhanced, and the reduction potential was significantly lower. In addition, the template method was employed to synthesize Au-In2O3 nanocubes, which offers the advantage of directly connecting materials with antibodies, resulting in a more stable construction of the immunosensor. Furthermore, In2O3 serves as a coreaction promoter, enabling the amplification strategy for ECL intensity of CdSSe, thus contributing to the enhanced sensitivity and performance of the immunosensor. The constructed immunosensor exhibited a wide linear range (100 μU mL-1 to 100 U mL-1) and a low detection limit of 80 μU mL-1, demonstrating its high potential and practical value for sensitive detection of CA19-9.

Sensitive electrochemiluminescence immunosensor based on a novel luminescent europium metal–organic framework and antenna effect for detecting pro-gastrin-releasing peptide

Sensitive detection of pro-gastrin-releasing peptide (Pro-GRP) is crucial because it is a highly sensitive and specific tumor marker for small cell lung cancer. Herein, we synthesized an efficient luminescent europium metal–organic framework and developed a sandwich ECL immunosensor for the sensitive detection of Pro-GRP, which used Eu3+ as the central ion and 2,4,6-tri (4-carboxyphenyl)-1,3,5-triazine (H3TATB) as the organic ligand. H3TATB acted as a strong absorbing reagent and transferred its energy to Eu3+ via the antenna effect to enhance the ECL response signal of Eu3+. As per calculations, the ECL efficiency of Eu-TATB, which was a promising ECL luminophore, was up to 130 %. The Cu2O cube worked as a substrate to assist the electron transfer and was used as a co-reaction accelerator to catalyze S2O82− to produce more SO4•− and then enhance the ECL intensity of Eu-TATB. Under optimal experimental conditions, the ECL immunosensor had a linear range of 5 fg mL−1–50 ng mL−1 for detecting Pro-GRP with a detection limit of 1.6 fg mL−1; moreover, it demonstrated excellent stability and specificity and has been successfully applied for detecting Pro-GRP in the human serum.