Quantitative analysis of CL-20 explosive by smartphone-based chemiluminescence method.

A new smartphone-based chemiluminescence method has been introduced for the quantitative analysis of CL-20 (Hexanitroazaisowuertzitan) explosive. The solvent mixture, oxidizer agent, and concentration of the reactants were optimized using statistical procedures. CL-20 explosive showed a quenching effect on the chemiluminescence intensity of the luminol-NaClO reaction in the solvent mixture of DMSO/H2O. A smartphone was used as a detector to record the light intensity of chemiluminescence reaction as a video file. The recorded video file was converted to an analytical signal as intensity luminescence-time curve by a written code in MATLAB software. Dynamic range and limit of detection of the proposed method were obtained 2.0-240.0 and 1.1 mg⋅L-1, respectively, in optimized concentrations 1.5 × 10-3 mol⋅L-1 luminol and 1.0 × 10-2 mol⋅L-1 NaClO. Precursors TADB, HBIW, and TADNIW in CL-20 explosive synthesis did not show interference in measurement the CL-20 purity. The analysis of CL-20 spiked samples of soil and water indicated the satisfactory ability of the method in the analysis of real samples. The interaction of CL-20 molecules and OCl- ions is due to quench of chemiluminescence reaction of the luminol-NaClO.

Hemin as a Molecular Probe for Nitric Oxide Detection in Physiological Solutions: Experimental and Theoretical Assessment.

Given its pivotal role in modulating various pathological processes, precise measurement of nitric oxide (●NO) levels in physiological solutions is imperative. The key techniques include the ozone-based chemiluminescence (CL) reactions, amperometric ●NO sensing, and Griess assay, each with its advantages and drawbacks. In this study, a hemin/H2O2/luminol CL reaction was employed for accurately detecting ●NO in diverse solutions. We investigated how the luminescence kinetics was influenced by ●NO from two donors, nitrite and peroxynitrite, while also assessing the impact of culture medium components and reactive species quenchers. Furthermore, we experimentally and theoretically explored the mechanism of hemin oxidation responsible for the initiation of light generation. Although both hemin and ●NO enhanced the H2O2/luminol-based luminescence reactions with distinct kinetics, hemin's interference with ●NO/peroxynitrite- modulated their individual effects. Leveraging the propagated signal due to hemin, the ●NO levels in solution were estimated, observing parallel changes to those detected via amperometric detection in response to varying concentrations of the ●NO-donor. The examined reactions aid in comprehending the mechanism of ●NO/hemin/H2O2/luminol interactions and how these can be used for detecting ●NO in solution with minimal sample size demands. Moreover, the selectivity across different solutions can be improved by incorporating certain quenchers for reactive species into the reaction.

Wireless rotating bipolar electrochemiluminescence for enzymatic detection.

New dynamic, wireless and cost-effective analytical devices are developing rapidly in biochemical analysis. Here, we report on a remotely-controlled rotating electrochemiluminescence (ECL) sensing system for enzymatic detection of a model analyte, glucose, on both polarized sides of an iron wire acting as a bipolar electrode. The iron wire is controlled by double contactless mode, involving remote electric field polarization, and magnetic field-induced rotational motion. The former triggers the interfacial polarization of both extremities of the wire by bipolar electrochemistry, which generates ECL emission of the luminol derivative (L-012) with the enzymatically produced hydrogen peroxide in presence of glucose, at both anodic and cathodic poles, simultaneously. The latter generates a convective flow, leading to an increase in mass transfer and amplifying the corresponding ECL signals. Quantitative glucose detection in human serum samples is achieved. The ECL signals were found to be a linear function of the glucose concentration within the range of 10-1000 µM and with a limit of detection of 10 µM. The dynamic bipolar ECL system simultaneously generates light emissions at both anodic and cathodic poles for glucose detection, which can be further applied to biosensing and imaging in autonomous devices.

FeS2 nanosheets-luminol-O2 chemiluminescence method for determination of venlafaxine hydrochloride, imipramine hydrochloride, and cefazolin sodium.

This study introduces a novel chemiluminescence (CL) approach utilizing FeS2 nanosheets (NSs) catalyzed luminol-O2 CL reaction for the measurement of three pharmaceuticals, namely venlafaxine hydrochloride (VFX), imipramine hydrochloride (IPM), and cefazolin sodium (CEF). The CL method involved the phenomenon of quenching induced by the pharmaceuticals in the CL reaction. To achieve the most quenching efficacy of the pharmaceuticals in the CL reaction, the concentrations of reactants comprising luminol, NaOH, and FeS2 NSs were optimized accordingly. The calibration curves demonstrated exceptional linearity within the concentration range spanning from 4.00 × 10-7 to 1.00 × 10-3 mol L-1, 1.00 × 10-7 to 1.00 × 10-4 mol L-1, and 4.00 × 10-6 to 2.00 × 10-4 mol L-1 with detection limits (3σ) of 3.54 × 10-7, 1.08 × 10-8, and 2.63 × 10-6 mol L-1 for VFX, IPM, and CEF, respectively. This study synthesized FeS2 NSs using a facile hydrothermal approach, and then the synthesized FeS2 NSs were subjected to a comprehensive characterization using a range of spectroscopic methods. The proposed CL method was effective in measuring the aforementioned pharmaceuticals in pharmaceutical formulations as well as different water samples. The mechanism of the CL system has been elucidated.

A dual amplified gold nanoparticle-based biosensor for ultrasensitive and selective detection of fibrin.

Ultrasensitive, selective, and non-invasive detection of fibrin in human serum is critical for disease diagnosis. So far, the development of high-performance and ultrasensitive biosensors maintains core challenges for biosensing. Herein, we designed a novel ribbon nanoprobe for ultrasensitive detection of fibrin. The probe contains gold nanoparticles (AuNPs) that can not only link with homing peptide Cys-Arg-Glu-Lys-Ala (CREKA) to recognize fibrin but also carry long DNA belts to form G-quadruplex-based DNAzyme, catalyzing the chemiluminescence of luminol-hydrogen peroxide (H2O2) reaction. Combined with the second amplification procedure of rolling circle amplification (RCA), the assay exhibits excellent sensitivity with a detection limit of 0.04 fmol L-1 fibrin based on the 3-sigma. Furthermore, the biosensor shows high specificity on fibrin in samples because the structure of antibody-fibrin-homing peptide was employed to double recognize fibrin. Altogether, the simple and inexpensive approach may present a great potential for reliable detection of biomarkers.

Dual-potential ratiometric electrochemiluminescence based on single emitter and single coreactant for the sensitive detection of carcinoembryonic antigen.

Dual-potential ratiometric electrochemiluminescence (ECL) is in favor of resistance to environmental interference. However, two kinds of emitters or coreactants, and a wide scan potential range (>2 V) are mandatory. This work developed a new dual-potential ratiometric ECL sensor for detection of carcinoembryonic antigen (CEA) using single emitter (luminol) and single coreactant (H2O2) with a mild potential range from -0.1 to 0.6 V. Luminol could produce a strong cathodic ECL (Ec) induced by hydroxyl radicals (HO‧) from the reduction of H2O2, and a relatively weak anodic ECL (Ea). After the ferrocene modified CEA aptamer (Apt-Fc) was attached, Fc could promote Ea by catalyzing the oxidation of H2O2, and reduce Ec by consuming HO‧. With the cycling amplification of the exonuclease I, CEA could substantially reduce the amount of Apt-Fc, resulting in the decrease of Ea and the rise of Ec. So, the ratio of Ec to Ea (Ec/Ea) was used as the detection signal, realizing the sensitive determination of CEA from 0.1 pg mL-1 to 10 ng mL-1 with a LOD of 41.85 fg mL-1 (S/N = 3). The developed sensor demonstrated excellent specificity, stability and reproducibility, with satisfactory results in practical detection.

Controlled-Release Electrochemiluminescence Biosensor with Strong Self-On Effect by a Multiple Signal Amplification Strategy for Trace Detection of Prostate-Specific Antigen.

The enhancement of sensitivity in biological analysis detection can reduce the probability of false positives of the biosensor. In this work, a novel self-on controlled-release electrochemiluminescence (CRE) biosensor was designed by multiple signal amplification and framework-enhanced stability strategies. As a result, the changes of the ECL signal were enhanced before and after the controlled-release process, achieving sensitive detection of prostate-specific antigen (PSA). Specifically, for one thing, Fe3O4@CeO2-NH2 with two paths for enhancing the generation of coreactant radicals was used as the coreaction accelerator to boost ECL performance. For another, due to the framework stability, zeolitic imidazolate framework-8-NH2 (ZIF-8-NH2) was combined with luminol to make the ECL signal more stable. Based on these strategies, the constructed CRE biosensor showed a strong self-on effect in the presence of PSA and high sensitivity in a series of tests. The detection range and limit of detection (LOD) were 5 fg/mL to 10 ng/mL and 2.8 fg/mL (S/N = 3), respectively, providing a feasible approach for clinical detection of PSA.

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.

Cathodic electrochemiluminescence of L012 and its application in antioxidant detection.

Cathodic electrochemiluminescence (ECL) of a luminol (or its analogues)-dissolved oxygen (O2) system is an ideal alternative to ECL of the traditional luminol-hydrogen peroxide (H2O2) system, which can efficiently avoid the self-decomposition of H2O2 at room temperature. However, the mechanism for the generation of cathodic ECL by the luminol (or its analogues)-O2 system is still ambiguous. Herein, we report the study of cathodic ECL generation by the L012-O2 system at a glassy carbon electrode (GCE). The types of reactive oxygen species (ROS) involved generated during ECL reactions were verified. A possible reaction mechanism for the system was proposed and the rate constants of related reactions were estimated. Furthermore, several intermediates of L012 involved in the proposed pathways were validated by electrochemistry-coupled mass spectrometry. Finally, the cathodic ECL system was successfully used for measuring the antioxidant capacity of commercial juice with Trolox as a standard.

Photocatalytic Aptamer Chemiluminescent System for a Homogeneous, Reliable, Label-Free, Generic Assay of Small Molecules.

Chemiluminescence is a powerful analytical technique with many advantages, while aptamers are well-known as good molecular recognition units. However, many aptamer-based chemiluminescence assays employed interface sensing, which often needed several immobilization, separation, and washing steps. To minimize the risks of contamination and false-positive, we for the first time proposed a photocatalytic aptamer chemiluminescent system for a homogeneous, label-free, generic assay of small molecules. After binding to a DNA aptamer, thioflavin T has a unique photocatalytic oxidase activity to activate the system's luminol chemiluminescence. Then, the specific binding between the aptamer and target molecules will compete with the above process. Therefore, we can realize the efficient assay of different analytes including estradiol and adenosine. Such a homogeneous chemiluminescent system allowed a direct assay of small molecules with limits of detection in a nM level. Several control tests were carried out to avoid possible false-positive results, which were originated from the interactions between analytes and sensing interfaces previously. This homogeneous chemiluminescent system provides a useful strategy to reliably assay various analytes in the pharmacy or biology field.

Shared hairpin structure electrochemiluminescence biosensor based on Au@Ni-Co metal organic frameworks for simultaneous detection of Pb(II) and S.aureus.

The excessive content of lead (Pb(II)) and Staphylococcus aureus (S.aureus) seriously harms the quality of aquatic products. In this paper, a highly sensitive electrochemiluminescence (ECL) biosensor was constructed using the synergistic effect of Au NPs@Nickel-Cobalt-Metal-organic frameworks (Au@Ni-Co-MOFs) and double potential resolution function of urchin-like Au@luminol and Cadmium sulfide quantum dots (CdS QDs) for synchronous detection of Pb(II) and S.aureus in aquatic products. Au@Ni-Co-MOFs as the base material, its cube structure can improve the surface active area and sensitivity of the sensor, providing more catalytic active sites for the two functional probes. Urchin-like Au@luminol binding aptamer DNA2 specifically recognizes Pb(II), CdS QDs binding aptamer DNA3 specifically recognizes S.aureus, which collaboratively catalyzed hydrogen peroxide reduction to produce two electrochemiluminescence signals. The shared hairpin structure DNA1 binds stably to Au@Ni-Co-MOFs via the Au-S bond, and the two functional probes are complementary paired with the DNA1 respectively to ensure the specificity of the aptamer. According to the ECL intensity changes of different potentials signal sources, the synchronous detection of Pb(II) and S.aureus with different concentrations is realized. The sensor realizes the detection of two targets in aquatic products and provides a new strategy for the simultaneous detection of multiple targets.

Ti3C2 MXene-based nanozyme as coreaction accelerator for enhancing electrochemiluminescence of glucose biosensing.

Delamination of the exfoliated multilayer MXenes with electro-catalysts, not only leads to increasing surface area for high electrochemiluminescent (ECL) signal tracer loading but also provides highly sensitive achievements in a coreaction accelerator manner. To this end, herein, we used bromophenol blue (BPB)-delaminated multilayer Ti3C2 MXene as both a coreaction accelerator to promote the electrochemiluminescent (ECL) reaction rate of luminol (LUM) and the co-reactant H2O2 and a substrate for retaining high loading of glucose oxidase (GOx)-conjugated polyethylene imine (PEI) along with luminophore species into more open structure of Ti3C2 MXene for sensitive detection of glucose. In the presence of glucose, in situ generating H2O2 product through a GOx-catalyzed process could produce abundant •OH radicals via the peroxidase-like activity of the BPB@Ti3C2 in the LUM ECL reaction. Moreover, decreasing the distance between the high-content LUM into the BPB@Ti3C2 and the generated •OH, minimizes the decomposition of highly active •OH, providing a superb ECL signal. Last, the proximity of incorporated GOx into the delaminated Ti3C2 MXene near the electrode allows efficient electron transfer between the electrode and enzyme. The integration of such amplifying effects endowed high sensitivity and excellent selectivity for glucose with a low limit of detection of 0.02 µM in the wide range of 0.01 µM-40,000 µM, enabling the feasibility of the glucose analysis in human serum samples. Overall, the enhanced ECL based on the BPB@Ti3C2 opens a new horizon to develop highly sensitive MXene-based ECL toward the field of biosensors.

Novel electrochemiluminescence aptasensor based on AuNPs-ABEI encapsulated TiO2 nanorod for the detection of acetamiprid residues in vegetables.

Gold nanoparticles (AuNPs)@N-(4-aminobutyl)-N-ethylisoluminol (ABEI)@Titanium dioxide nanorods (TiO2NRs) were used as sensing materials to produce a unique encapsulated nanostructure aptasensor for the detection of acetamiprid residues in this work. ABEI, an analog of luminol, was extensively used as an electrochemiluminescence (ECL) reagent. The ECL mechanism of ABEI- hydrogen peroxide (H2O2) system had connections to a number of oxygen-centered free radicals. TiO2NRs improved ECL response with high electron transfer and a specific surface area. AuNPs were easy to biolabel and could catalyze H2O2 to enhance ECL signal. AuNPs were wrapped around TiO2NRs by utilizing the reduction property of ABEI to form wrapped modified nanomaterials. The sulfhydryl-modified aptamer bound to the nanomaterial by forming gold-sulfur (Au-S) bonds. The aptamer selectively bound to its target with the addition of acetamiprid, which caused a considerable decrease in ECL intensity and enabled quantitative detection of acetamiprid. The aptasensor showed good stability, repeatability and specificity with a broad detection range (1×10-2-1×103 nM) and a lower limit of detection (3 pM) for acetamiprid residues in vegetables. Overall, this aptasensor presents a simple and highly sensitive method for ECL detecting acetamiprid, with potential applications in vegetable safety monitoring.

Boosting Photon Emission from the Chemiluminescence of Luminol Based on Host-Guest Recognition for the Determination of Dopamine.

Modulating the photon emission of the luminophore for boosting chemiluminescence (CL) response is very crucial for the construction of highly sensitive sensors via the introduction of functionalized materials. Herein, the integration of the emitter and coreactant accelerator into one entity is realized by simply assembling cucurbit[7]uril (CB[7]) on the surface of gold nanoparticles (AuNPs) through simple assembly via a Au-O bond. The loaded CB[7] on the AuNPs improves their catalytic capacity for the generation of hydroxyl radicals(•OH). Moreover, the host-guest recognition interaction between luminol and CB[7] enables the capture of luminol on AuNPs efficiently. Also, the intramolecular electron-transfer reaction between the luminol and •OH enables the CL response more effectively in the entity, which greatly boosts photon emission ca 100 folds compared with the individual luminol/H2O2. The host-guest recognition between luminol and CB[7] is revealed by Fourier transform infrared spectroscopy, electrochemical, and thermogravimetric characterization. Moreover, the proposed CL system is successfully used for the sensitive and selective determination of dopamine (DA) based on a synergistic quenching mechanism including the competition quenching and radical-scavenging effect from DA. The present amplified strategy by integrating recognized and amplified elements within one entity simplifies the sensing process and holds great potential for sensitive analysis based on the self-enhanced strategies.

Surface Oxygen Vacancy-Rich Co3O4 Nanowires as an Effective Catalyst of Luminol-H2O2 Chemiluminescence for Sensitive Immunoassay.

Oxygen vacancy is one intrinsic defect in metal oxide materials. Interestingly, we herein found that the surface oxygen vacancy can significantly enhance the catalytic activity of Co3O4 nanowires in the luminol-H2O2 chemiluminescence (CL) reaction. 0.1 ng/mL Co3O4 nanowires containing 51.3% surface oxygen vacancies possessed ca. 2.5-fold catalytic activity of free Co2+ (the best metal ionic catalyst for the luminol-H2O2 CL reaction). The superior catalytic efficiency is attributed to the enhanced adsorption of H2O2 by surface oxygen vacancies, which in turn accelerates the cleavage of O-O bonds and generates •OH radicals. More importantly, the surface oxygen vacancy-rich Co3O4 nanowires retained about 90% catalytic activity after modification with antibodies. The surface oxygen vacancy-rich Co3O4 nanowires were used to label the secondary antibody, and one sandwich-type CL immunoassay of carcinoembryonic antigen was established. The detection limit was 0.3 ng/mL with a linear range of 1-10 ng/mL. This proof-of-concept work proves that surface oxygen vacancy-rich Co3O4 nanowires are suitable for labeling biomolecules in CL bioanalysis and biosensing.

Proximity-Enhanced Electrochemiluminescence Sensing Platform for Effective Capturing of Exosomes and Probing Internal MicroRNAs Involved in Cancer Cell Apoptosis.

Exosomal microRNAs (miRNAs) play critical regulatory roles in many cellular processes, and so how to probe them has attracted increasing interest. Here we propose an aptamer-functionalized dimeric framework nucleic acid (FNA) nanoplatform for effective capture of exosomes and directly probing internal miRNAs with electrochemiluminescence (ECL) detection, not requiring RNA extraction in conventional counterparts. A CD63 protein-binding aptamer is tethered to one of the FNA structures, allowing exosomes to be immobilized there and release internal miRNAs after lysis. The target miRNA induces the formation of a Y-shaped junction on another FNA structure in a close proximity state, which benefits the loading of covalently hemin-modified spherical nucleic acid enzymes for enhanced ECL readout in the luminol-H2O2 system. In this facile way, the ultrasensitive detection of exosomal miR-21 from cancer cells is accomplished and then used for cell apoptosis analysis, indicating that the oncogene miR-21 negatively participates in the regulation of the apoptotic process; namely, downregulating the miR-21 level is unbeneficial for cancer cell growth.

Preparation of Co dual atomic site catalysts loaded on defect-engineered MOFs material with superb chemiluminescent enhancement effect for sensitive detection of bacteria.

BACKGROUND: Dual atomic site catalysts (DASCs) have aroused extensive interest in analytical chemistry on account of the superb catalytic activity caused by the highly-exposed active centers and synergistic effect of adjacent active centers. The reported protocols for preparing DASCs usually involve harsh conditions such as acid/base etching and high-temperature calcination, leading to unfavorable water dispersity and restricted application. It is crucial to develop DASCs with satisfactory water dispersity, improved stability, and mild preparation procedures to facilitate their application as signal probes in analytical chemistry. RESULTS: Formic acid was adopted as a modulator for preparing MOF-808 with abundant defective sites, which was used as the carrier for implanting Co atoms. Co DASCs with a special coordination structure of Co2-O10 and a high loading efficiency of 11.1 wt% were prepared with a mild solvothermal protocol. The resultant Co DASCs can significantly accelerate decay of H2O2 for forming numerous reactive oxygen radicals and boost chemiluminescent (CL) signal. Co DASCs at 1.0 µg mL-1 can enhance the CL signal of luminol-H2O2 system by about 5800 times. Thanks to their satisfactory water dispersity and excellent CL enhancement performance, they were used as ultra-sensitive CL signal probes for monitoring methicillin-resistant Staphylococcus aureus. The method shows a detection range of 102-107 CFU mL-1 and a detection limit of 47 CFU mL-1. Antibiotic susceptibility test was performed with the established CL method to prove its practicality. SIGNIFICANCE: The water dispersible Co DASCs prepared with facile and mild solvothermal protocol exhibit prominent peroxidase-like activity and can promote the production of reactive oxygen radicals for boosting CL signal. Therefore, this study paves an avenue for implanting DASCs in defect-engineered carrier to prepare signal probes suitable for development of ultra-sensitive CL analytical methods.

Nanozyme-Based Biofuel Cell Ingeniously Coupled with Luminol Chemiluminescence System through In Situ Co-Reactant Generation for Dual-Signal Biosensing.

Classical luminol-based chemiluminescence (CL) is the process of emitting light enhanced by the addition of coreactant hydrogen peroxide (H2O2). To address the instability issue of H2O2 decomposition, herein, we proposed a nanozyme-based biofuel cell (BFC) ingeniously coupled with a luminol CL system via in situ generation of H2O2. Specifically, the gold nanoparticle (AuNP) nanozyme with glucose oxidase-like activity can act as the anodic enzyme of BFC to catalyze the oxidation of glucose to produce H2O2 and electrons. In this case, H2O2 as a coreactant enhanced the CL intensity and the cathode of the BFC obtained electrons to generate the open circuit voltage (EOCV) signals. As a result, a dual-signal biosensing platform was successfully constructed. Interestingly, the AuNPs-catalyzed system operates in an alkaline medium, which precisely meets the pH requirement for luminol luminescence. Such a BFC-CL system not only greatly lessens the effect of unstable exogenous H2O2 on the signal stability but also enhances the CL of luminol. Furthermore, both CL and EOCV signals present a positive correlation with the glucose concentration. Therefore, this novel BFC-CL system shows good performance for dual-signal biosensing, which would serve as a valuable guideline for the design and application of BFC-based self-powered or CL biosensors.

Remarkably Enhanced Luminol/H2O2 Chemiluminescence with Excellent Peroxidase-like Activity of FeCoNi-based Metal-Organic Xerogels for the Sensitive Detection of Dopamine.

Metal-organic gels (MOGs) are a category of metal-organic smart soft materials with large specific surface areas, loose porous structures, and open metal active sites. In this work, trimetallic Fe(III)Co(II)Ni(II)-based MOGs (FeCoNi-MOGs) were synthesized at room temperature via a simple and mild one-step procedure. Fe3+, Co2+, and Ni2+ were the three central metal ions in it, while 1,3,5-benzenetricarboxylic acid (H3BTC) served as the ligand. The solvent enclosed in it was then removed by freeze-drying to get the corresponding metal-organic xerogels (MOXs). The as-prepared FeCoNi-MOXs have excellent peroxidase-like activity and can significantly enhance luminol/H2O2 chemiluminescence (CL) by more than 3000 times, which is very effective compared with other reported MOXs. Based on the inhibitory effect of dopamine on the CL of the FeCoNi-MOXs/luminol/H2O2 system, a simple, rapid, sensitive, and selective CL method for dopamine detection was established with a linear range of 5-1000 nM and a limit of detection of 2.9 nM (LOD, S/N = 3). Furthermore, it has been effectively used for the quantitative measurement of dopamine in dopamine injections and human serum samples, with a recovery rate of 99.5-109.1%. This research brings up prospects for the application of MOXs with peroxidase-like activity in CL.

Co-amplification of luminol-based electrochemiluminescence immunosensors based on multiple enzyme catalysis of bimetallic oxides CoCeOx and NiMnO3 for the detection of CYFRA21-1.

The accelerated energy supply of co-reactants is an extremely effective strategy for achieving highly sensitive electrochemiluminescence analysis, and binary metal oxides would be an excellent tool for this purpose owing to the nano-enzyme acceleration of mixed metal valence states. Herein, an electrochemiluminescent (ECL) immunosensor for monitoring the concentration of cytokeratin 19 fragment antigen 21-1 (CYFRA21-1) was developed based on a co-amplification strategy triggered by two bimetallic oxides, CoCeOx and NiMnO3, with luminol as the luminophore. CoCeOx derived from an MOF exhibits a large specific surface area and excellent loading capacity as a sensing substrate, and the peroxidase properties enable the catalysis of hydrogen peroxide to provide energy supply to the underlying radicals. The dual enzymatic properties of flower-like NiMnO3 were employed as probe carriers for luminol enrichment. The peroxidase properties built on Ni2+/Ni3+ and Mn3+/Mn4+ binary redox pairs resulted in the integration of highly oxidative hydroxyl radicals, and the oxidase properties provided additional superoxide radicals via dissolved oxygen. The practically proven multi-enzyme-catalyzed sandwich-type ECL sensor easily accomplished an accurate immunoassay of CYFRA21-1, harvesting a detection limit of 0.3 pg mL-1 in the linear range of 0.001-150 ng mL-1. In conclusion, this work explores the cyclic catalytic amplification of mixed-valence binary metal oxides with nano-enzyme activity in the field of ECL and develops an effective pathway for ECL immunoassay.