Stable Electrochemiluminescence Research Articles

Improvement on electrochemiluminescence properties of graphite carbon nitride by metal oxidation state regulation

AbstractReasonable design is of great significance for improving the performance of electrochemiluminescence (ECL) co‐reactant accelerators. The different d‐band structure of metal single atoms will produce different oxidation states, which may change the adsorption of reaction intermediates to the catalyst and affect its catalytic activity. In this study, we have demonstrated that the ECL performances of graphite carbon nitride (CN) can be promoted by modulating the metal oxidation states of co‐reaction accelerator for the first time. The oxidation states of Au were modulated by the different electronic metal–support interaction (EMSI) between the co‐reaction accelerator (Au single atoms, Au nanoparticles [Au NPs]) and CN, and the effects of Au oxidation states on the ECL performances of CN were investigated. Comparison to pristine CN and CN nanosheets supported Au nanoparticles (Au NPs/CN), stronger and more stable ECL intensity of CN nanosheets supported Au single‐atoms (AuS/CN) was obtained. The ECL signal of AuS/CN was about 32.2 times that of the original CN, and 2.8 times that of Au NPs/CN in the same Au loading content (0.8%). Detailed mechanism revealed that AuS/CN with higher Au oxidation state has better conductivity and stronger catalytic activity, which promotes the electric reduction of CN and S2O82−, increases the lifetime of the excited state CN*, and significantly improves the ECL performance of CN. In addition, this work provides a detailed understanding of the essence of EMSI for the ECL intensity amplification and established a feasible method for the improvement of ECL capacities of co‐reactant accelerators.

Microfluidic Immunosensor Platform for Sensitive Detection of Human Epidermal Growth Factor Receptor-2 Based on Enhanced Cathode Electrochemiluminescence of Bimetallic Nanoclusters.

In this work, a microfluidic immunosensor chip was developed by incorporating microfluidic technology with electrochemiluminescence (ECL) for sensitive detection of human epidermal growth factor receptor-2 (HER2). The immunosensor chip can achieve robust reproducibility in mass production by integrating multiple detection units in a series. Notably, nanoscale materials can be better adapted to microfluidic systems, greatly enhancing the accuracy of the immunosensor chip. Ag@Au NCs closed by glutathione (GSH) were introduced in the ECL microfluidic immunosensor system with excellent and stable ECL performance. The synthesized CeO2-Au was applied as a coreaction promoter in the ECL signal amplification system, which made the result of HER2 detection more reliable. In addition, the designed microfluidic immunosensor chip integrated the biosensing system into a microchip, realizing rapid and accurate detection of HER2 by its high throughput and low usage. The developed short peptide ligand NARKFKG (NRK) achieved an effective connection between the antibody and nanocarrier for improving the detection efficiency of the sensor. The immunosensor chip had better storage stability and sensitivity than traditional detection methods, with a wide detection range from 10 fg·mL-1 to 100 ng·mL-1 and a low detection limit (LOD) of 3.29 fg·mL-1. In general, a microfluidic immunosensor platform was successfully constructed, providing a new idea for breast cancer (BC) clinical detection.

Multiple signal-enhanced electrochemiluminescence aptamer sensors based on carboxylated ruthenium (II) complexes for acetamiprid detection

BackgroundRapid and sensitive detection for acetamiprid, a kind of widely used neonicotinoid insecticide, is very meaningful for the development of modern agriculture and the protection of human health. Highly stable electrochemiluminescence (ECL) materials are one of the key factors in ECL sensing technology. ECL materials prepared by porous materials (e.g., MOFs) coated with chromophores have been used for ECL sensing detection, but these materials have poor stability because the chromophores escape when they are in aqueous solution. Therefore, the development of highly stable ECL materials is of great significance to improve the sensitivity of ECL sensing technology. ResultsIn this work, by combining etched metal-organic frameworks (E-UIO-66-NH2) as carrier with Tris(4,4′-dicarboxylic acid-2,2′-bipyridine)Ru(II) chloride (Ru(dcbpy)32+) as signal probe via amide bonds, highly stable nanocomposites (E-UIO-66-NH2-Ru) with excellent ECL performance were firstly prepared. Then, using MoS2 loaded with AuNPs as substrate material and co-reactant promoter, a signal off-on-off ECL aptamer sensor was prepared for sensitive detection of acetamiprid. Due to the excellent catalytic activity of E-UIO-66-NH2-Ru and MoS2@Au towards K2S2O8, the ECL signals can be enhanced by multiple signal enhancement pathways, the prepared ECL aptamer sensor could achieve sensitive detection of acetamiprid in the linear range of 10−13 to10−7 mol L−1, with the limit of detection (LOD) of 2.78ⅹ10−15 mol L−1 (S/N = 3). After the evaluation of actual sample testing, this sensing platform was proven to be an effective method for the detection of acetamiprid in food and agricultural products. Significance and noveltyThe E-UIO-66-NH2-Ru prepared by linking Ru(dcbpy)32+ to E-UIO-66-NH2 via amide bonding has very high stability. The synergistic catalytic effect of MoS2 and AuNPs enhanced the ECL signal. By exploring the sensing mechanism and evaluating the actual sample tests, the proposed signal "on-off" ECL sensing strategy was proved to be an effective and excellent ECL sensing method for sensitive and stable detection of acetamiprid.

Ultrasensitive Electrochemiluminescence Biosensor Based on Efficient Signal Amplification of Copper Nanoclusters Induced by CaMnO3 for CD44 Trace Detection.

Metal nanoclusters (Me NCs) have become a research hotspot in the field of electrochemiluminescence (ECL) sensing analysis. This is primarily attributed to their excellent luminescent properties and biocompatibility along with their easy synthesis and labeling characteristics. At present, the application of Me NCs in ECL mainly focuses on precious metals, whose high cost, to some extent, limits their widespread application. In this work, Cu NCs with cathode ECL emissions in persulfate (S2O82-) were prepared as signal probes using glutathione as ligands, which exhibited stable luminescence signals and high ECL efficiency. At the same time, CaMnO3 was introduced as a co-reaction promoter to increase the ECL responses of Cu NCs, thereby further expanding their application potential in biochemical analysis. Specifically, the reversible conversion of Mn3+/Mn4+ greatly promoted the generation of sulfate radicals (SO4•-), providing a guarantee for improving the luminescence signals of Cu NCs. Furthermore, a short peptide (NARKFYKGC) was introduced to enable the fixation of antibodies to specific targets, preventing the occupancy of antigen-binding sites (Fab fragments). Therefore, the sensitivity of the biosensor could be significantly enhanced by releasing additional Fab fragments. Considering the approaches discussed above, the constructed biosensor could achieve sensitive detection of CD44 over a broad range (10 fg/mL-100 ng/mL), with an ultralow detection limit of 3.55 fg/mL (S/N = 3), which had valuable implications for the application of nonprecious Me NCs in biosensing analysis.

Renewable Electrochemiluminescence Biosensor Based on Eu-MOGs as a Highly Efficient Emitter and a DNAzyme-Mediated Dual-drive DNA Walker as a Signal Amplifier for Ultrasensitive Detection of miRNA-222.

Herein, novel europium metal-organic gels (Eu-MOGs) with excellent cathode electrochemiluminescence (ECL) emission are first used to construct biosensors for the ultrasensitive detection of miRNA-222. Impressively, N and O elements of organic ligand 2,2':6,2″-terpyridine 4,4',4″-tricarboxylic acid (H3-tctpy) can perfectly coordinate with Eu3+ to form Eu-MOGs, which not only reduce nonradiative transition caused by the intramolecular free rotation of phenyl rings in other MOGs to enhance the ECL signal with extraordinary ECL efficiency as high as 37.2% (vs the [Ru(bpy)3]2+/S2O82- ECL system) but also reinforce ligand-to-metal charge transfer (LMCT) by the strong affinity between Eu3+ and N and O elements to greatly improve the stability of ECL signals. Besides, an improved nucleic acid cascade amplification reaction is developed to greatly raise the conversion efficiency from target miRNA-222 to a DNAzyme-mediated dual-drive DNA walker as output DNA, which can simultaneously shear the specific recognition sites from two directions. In that way, the proposed biosensor can further enhance the detection sensitivity of miRNA-222 with a linear range of 10 aM-1 nM and a detection limit (LOD) of 8.5 aM, which can also achieve an accurate response in cancer cell lysates of MHCC-97L and HeLa. Additionally, the biosensor can be self-regenerated by the folding/unfolding of related triplets with pH changes to simplify experimental operations and reduce the cost. Hence, this work proposed novel MOGs with stable and intense ECL signals for the construction of a renewable ECL biosensor, supplying a reliable detection method in biomarker analysis and disease diagnosis.

A perovskite-based electrochemiluminescence aptasensor for tetracycline screening.

Tetracyclines are currently the most commonly used class of antibiotics, and their residue issue significantly impacts public health safety. In this study, a surface modification of perovskite with cetyltrimethylammonium bromide led to the generation of stable electrochemiluminescence (ECL) emitters in aqueous systems and improved the biocompatibility of perovskite. A perovskite quantum dot-based ECL sensing strategy was developed. Utilizing the corresponding aptamer of the antibiotics, strain displacement reactions were triggered, disrupting the ECL quenching system composed of perovskite and Ag nanoclusters (Ag NCs) on the electrode surface, generating a signal to achieve quantitative detection of several common tetracycline antibiotics. The perovskite quantum dot provided a strong and stable initial signal, while the efficient catalytic activity of the silver cluster enhanced the recognition sensitivity. Tetracycline, chlortetracycline, and oxytetracycline were used as examples to demonstrate the differentiation and quantitative detection through this method. In addition, the aptasensor exhibited analytical performance with the linear range (0.1-10μM OTC) and good recovery rates of 94.7% to 101.6% in real samples. This approach has the potential to become a sensitive and practical approach for assessing antibiotic residues.

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.

Hydrogen-Bonded Organic Cocrystal-Encapsulated Perovskite Nanocrystals as Coreactant-Free Electrochemiluminescent Luminophore for the Detection of Uranium.

Lead halide perovskite nanocrystals with excellent photophysical properties are promising electrochemiluminescence (ECL) candidates, but their poor stability greatly restricts ECL applications. Herein, hydrogen-bonded cocrystal-encapsulated CsPbBr3 perovskite nanocrystals (PeNCs@NHS-M) were synthesized by using PeNCs as nuclei for inducing the crystallization of melamine (M) and N-hydroxysuccinimide (NHS). The as-synthesized composite exhibits multiplicative ECL efficiencies (up to 24-fold that of PeNCs) without exogenous coreactants and with excellent stability in the aqueous phase. The enhanced stability can be attributed to the well-designed heterostructure of the PeNCs@NHS-M composite, which benefits from both moiety passivation and protection of the peripheral cocrystal matrix. Moreover, the heterostructure with covalent linkage facilitates charge transfer between PeNCs and NHS-M cocrystals, realizing effective ECL emission. Meanwhile, the NHS and M components act as coreactants for PeNCs, shortening the electron-transport distance and resulting in a significant increase in the ECL signal. Furthermore, by taking advantage of the specific binding effect between NHS-M and uranyl (UO22+), an ECL system with both a low detection limit (1 nM) and high selectivity for monitoring UO22+ in mining wastewater is established. The presence of UO22+ disrupted the charge-transfer effect within PeNCs@NHS-M, weakening the ECL signals. This work provides an efficient design strategy for obtaining stable and efficient ECLs from perovskite nanocrystals, offering a new perspective for the discovery and application of perovskite-based ECL systems.

Exogenous Co-Reactant-Free Electrochemiluminescent Biosensor for Ratiometric Measurement of α-Glucosidase Based on a ZIF-67-Regulated Hydrogen-Bonded Organic Framework.

The development of highly sensitive and selective analytical approaches for monitoring enzymatic activity is critical for disease diagnosis and biomedical research. Herein, we develop an exogenous co-reactant-free electrochemiluminescence (ECL) biosensor for the ratiometric measurement of α-glucosidase (α-Glu) based on a zeolitic imidazolate framework (ZIF-67)-regulated pyrene-based hydrogen-bonded organic framework (HOF-101). Target α-Glu can hydrolyze maltose to α-d-glucose, which can subsequently react with GOx to produce gluconic acid. The resultant gluconic acid can dissolve ZIF-67, leading to the recovery of the HOF-101 cathodic ECL signal and the decrease of the luminol anodic ECL signal. The long-range ordered structure of HOF-101 can speed up charge transfer, resulting in a stable and strong cathodic ECL signal. Moreover, ZIF-67 can not only efficiently quench the ECL signal of HOF-101 due to ECL resonance energy transfer between HOF-101 and ZIF-67 as well as the steric hindrance effect of ZIF-67 but also enhance the anodic ECL emission of luminol in dissolved O2 system because of its ordered and porous crystalline structure and the atomically dispersed Co2+. Notably, HOF-101 possesses a higher ECL efficiency (32.22%) compared with the Ru(bpy)32+ standard. Importantly, this ratiometric ECL biosensor shows high sensitivity (a detection limit of 0.19 U L-1) and a broad linear range (0.2-50 U L-1). This biosensor can efficiently eliminate systematic errors and enhance detection reliability without the involvement of exogenous co-reactants, and it displays good assay performance in human serum samples, holding great promise in biomedical research studies.

Co-Reactive Ligand In Situ Engineered Gold Nanoclusters with Ultra-Bright Near-Infrared Electrochemiluminescence for Ultrasensitive and Label-Free Detection of Carboxylesterase Activity.

Ultrasensitive and accurate monitoring of carboxylesterase (CE) activity is extremely crucial for the early diagnosis of hepatocellular carcinoma (HCC), which is still a considerable challenge. Herein, using a co-reactive ligand engineering strategy, ultra-bright near-infrared (λmax = 830 nm) and self-enhanced electrochemiluminescence (ECL) Au nanoclusters (NCs) were in situ prepared with 2-(diethylamino) ethanethiol (DEAET) as a co-reactive ligand. Remarkably, the co-reactive ligand not only acts as a stabilizer like traditional ligands but also plays a crucial role as a co-reactant to ensure a confinement effect to shorten the charge transfer distance and increase the local concentration, significantly improving the collision efficiency between the electrogenerated free radicals. Consequently, the DEAET Au NCs exhibited a record and stable anodal ECL without the addition of an exogenous co-reactant, dramatically superior to classical Au NCs and Ru(bpy)32+ with a certain amount of the co-reactant. As a proof of concept, a convenient and label-free CE biosensor was innovatively constructed using 1-naphthyl acetate as a selective substrate, achieving ultrasensitive detection for CE activity with a low limit of detection of 9.1 × 10-7 U/L. Therefore, this work not only paves a co-reactive ligand engineering strategy for in situ preparation of high-efficiency metal NCs but also provides an ultrasensitive and convenient platform for the early diagnosis of HCC.

Electrochemiluminescence Sensor Based on CeO2 Nanocrystalline for Hg2+ Detection in Environmental Samples.

The excessive concentration of heavy-metal mercury ions (Hg2+) in the environment seriously affects the ecological environment and even threatens human health. Therefore, it is necessary to develop rapid and low-cost determination methods to achieve trace detection of Hg2+. In this paper, an Electrochemiluminescence (ECL) sensing platform using a functionalized rare-earth material (cerium oxide, CeO2) as the luminescent unit and an aptamer as a capture unit was designed and constructed. Using the specific asymmetric matching between Hg2+ and thymine (T) base pairs in the deoxyribonucleic acid (DNA) single strand, the "T-Hg-T" structure was formed to change the ECL signal, leading to a direct and sensitive response to Hg2+. The results show a good linear relationship between the concentration and the response signal within the range of 10 pM-100 µM for Hg2+, with a detection limit as low as 0.35 pM. In addition, the ECL probe exhibits a stable ECL performance and excellent specificity for identifying target Hg2+. It was then successfully used for spiked recovery tests of actual samples in the environment. The analytical method solves the problem of poor Hg2+ recognition specificity, provides a new idea for the efficient and low-cost detection of heavy-metal pollutant Hg2+ in the environment, and broadens the prospects for the development and application of rare-earth materials.

Target-Driven Annular DNA Walker Coupled with Electrochemiluminescent Silicon Quantum Dots for APE1 Bioanalysis.

Functional DNA walkers with substantial nanostructures have been extensively investigated; however, their stability still faces challenges when exposed to diverse nuclease in clinical biological samples, resulting in the unreliability of actual assessment. This work proposed a target-driven annular DNA walker with enhanced stability enabling the sensitive and reliable response to different concentrations of apurinic/apyrimidinic endonuclease 1 (APE1), by preparing silicon quantum dots (SiQDs) as electrochemiluminescence (ECL) emitters. Specifically, the SiQDs showed significant strong and stable ECL signals by purifying the microenvironment of SiQDs through the dialysis removal of the gel-like layers surrounding the SiQDs. The relative standard deviation (RSD) of their ECL signal had been improved 16.59 times under consecutive scanning compared to that of SiQDs without dialysis, demonstrating a significant improvement in ECL stability. Subsequently, in the presence of APE1, the designed annular DNA walker was activated to move along the numerous quenching probes within the continuous cross-based DNA orbits, which were immobilized to the SiQD-modified electrode, providing ECL readout signals. The linear range of this ECL biosensor was 1.0 × 10-13 U·μL-1 to 1.0 × 10-7 U·μL-1, and the limit of detection (LOD) was as low as 1.766 × 10-14 U·μL-1. This work provides a novel structure of a DNA walker with nuclease resistance for clinical sample detection and designs a new strategy for synthesizing SiQDs with favorable ECL performance, tremendously expanding the ECL application of SiQDs.

Facile synthesis of dual-ligand europium-metal organic gels for ratiometric electrochemiluminescence detecting I27L gene

Metal organic gels (MOGs) are a new kind of intelligent soft materials with excellent luminescence properties. However, MOGs with dual electrochemiluminescence (ECL) properties have not been reported. In this study, using Eu3+ as metal node, 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine (Hcptpy) and Luminol as organic ligands, a novel dual-ligand Europium-organic gels (Eu-L-H MOGs) were prepared by simple mixing at room temperature. On the one hand, Eu-L-H MOGs could exhibit strong and stable anodic ECL signals in the phosphate buffered saline (PBS) without the addition of co-reactants, which came from the blue emission of Luminol. On the other hand, using K2S2O8 as a cathodic co-reactant, Eu-L-H MOGs produced cathodic signals, which were derived from the red emission of Eu sensitized by Hcptpy through the antenna effect. Based on the independent dual ECL signals of Eu-L-H MOGs, we selected Alexa Flour 430 as the receptor and anodic ECL emission of Eu-L-H MOGs as the donor to construct the ECL resonance energy transfer (ECL-RET) ratio biosensor, which utilized exonuclease III assisted DNA cycle amplification to achieve ultrasensitive detection of the I27L gene. The detection linearity of I27L ranged from 1 fM to 10 nM, with a detection limit as low as 284 aM. This study developed a straightforward technique for obtaining a single luminescent material with dual signals, and further broadened the analytical application of MOGs in the realm of ECL.

Unraveling Mechanisms of Highly Efficient Yet Stable Electrochemiluminescence from Quantum Dots.

With CdSe/CdS/ZnS core/shell/shell quantum dots (QDs) as the model system, time- and potential-resolved spectroelectrochemical measurements are successfully applied for studying the general mechanisms and kinetics of electrochemiluminescence (ECL) generation. The rate constant of electron injection from the cathode into a QD to form a negatively charged QD (QD-) increases monotonically from -0.88 V to -1.2 V (vs Ag/AgCl). Mainly due to the deep LUMO of the QDs, the resulting QD- as the key intermediate for ECL generation is structurally stable and possesses very slow spontaneous deionization channels. The latter (the main non-ECL channels) are usually 3-4 orders of magnitude slower than the rate constant of the successive hole injection from an active co-reactant into a QD-. The kinetic studies quantify the internal ECL quantum yield of ideal QD ECL emitters to be nearly identical to that of photoluminescence, which is near unity for the current system. Identification of the key intermediate, discovery of the related elementary steps, and determination of all rate constants not only establish a general framework for understanding ECL generation but also offer basic design rules for ECL emitters.

Ultrasensitive electrochemiluminescence sensor for the detection of synthetic cannabinoids based on perovskite as coreaction accelerator and light-scattering effects of photonic crystals

As is common knowledge, a strong electrochemiluminescence (ECL) signal is required to ensure the high sensitivity of trace target detection. Here, a dual signal amplification strategy by integrating of perovskite and photonic crystal was fabricated for quantitative synthetic cannabinoids (AB-PINACA) detection based on Zr-connected PTCA and TCPP (PTCA-TCPP) with excellent ECL performance as luminophores. On the one hand, the co-reaction accelerator perovskite (LaCoO3) improved the effective electroactive area of the electrode and promoted the decomposition of K2S2O8, resulting in a stronger ECL signal value. On the other hand, polystyrene inverse opal (PIOPCs) formed after the swelling of PS microspheres not only taken advantage of the light scattering effect and excellent catalytic property of photonic crystals to amplify the ECL signal, but also could be used as a binder to fix LaCoO3 and PTCA-TCPP on the electrode surface to generate unprecedented ECL response and stable ECL signals. Subsequently, the detection substance AB-PINACA was loaded on the electrode surface via the amide bond with the luminophores PTCA-TCPP, thus quenching the ECL signal, so as to realize the sensitive detection of synthetic cannabinoids. Under the optimal conditions, the proposed sensor achieved highly sensitive AB-PINACA detection with a dynamic range from 1.0 × 10−12 to 1.0 × 10−3 g/L and the detection limit was 1.1 × 10−13 g/L, which had great application potential in the detection of synthetic cannabinoids.

Intramolecular D-A structure achieved excellent electrochemiluminescence of g-C3N4 originated from doping thiophene ring

The low electrochemiluminescence (ECL) efficiency and poor ECL stability of graphitic carbon nitride (g-C3N4) under high excitation potential due to obvious electrode passivation seriously restrict its further wider application. Here, construction of intramolecular donor–acceptor (D-A) structure had proposed to well resolve above problems, which had been rarely reported. As a research model, thiophene ring (electron donor, D) with strong electron donating property was doped into the heptazine (electron acceptor, A) of 3D g-C3N4. An intramolecular D-A structure of 3D Thing-g-C3N4 was obtained, which had extended π-conjugated system and high-speed intramolecular electron transfer. As a result, 3D Thing-g-C3N4 with intramolecular D-A structure exhibiting excellent cathodic ECL performance with endogenous dissolved O2 as coreactant under lower potential. Based on the above ECL system, an ultrasensitive biosensor was assembled for microRNA-221 detection with multiple HCR based cascade amplification strategy. The target-like DNA obtained through the initial HCR process induced by target could trigger multiple HCR processes again to realize the effective amplification of the target. The constructed biosensor had excellent detection performance for microRNA-221 and the detection limit was calculated as 5.25 aM. In conclusion, construction of intramolecular D-A structure was a novel and effective way to improve the ECL performance of g-C3N4, and the newly proposed multiple HCR based cascade amplification strategy paved provided new opportunities for the detection of cancer marker in early cancer diagnosis.

Cobaltous sulfide/S-doped Ti3C2 MXene nanocomposites with coreaction acceleration effect for high-performance luminol electrochemiluminescence sensing by coupling micro-nano bubbles-mediated amplification strategy

Exploration of a feasible method to enhance dissolved oxygen (DO) content and design a supplementary accelerator to accelerate the reduction efficiency of DO in the luminol-DO system was significantly meaningful for developing a high-performance electrochemiluminescence (ECL) sensing platform. Herein, a novel luminol-DO ECL system was designed by coupling the micro-nano bubbles (MNBs) and CoS2/S-Ti3C2 heterostructure for sensitive detection of chloramphenicol (CAP). Specifically, the introduction of MNBs could increase the DO content in PBS solution and the special conditions caused by MNBs rupture generated abundant reactive oxygen species (ROS). Meanwhile, CoS2/S-Ti3C2 could be used as advanced co-reaction accelerator to accelerate the reduction efficiency of DO, which could produce more ROS. Remarkably, the ECL intensity of the as-fabricated system not only revealed an 8.7-fold enhanced signal, but also displayed a more stable ECL signal compared to individual luminol-DO system. With the assistance of CAP aptamer, the as-fabricated luminol − DO system exhibited a wide linear range from 0.1 fM to 10 pM with an ultra-low detection limit of 105 fM (S/N = 3), and it performed excellent stability, reproducibility and sensitivity, so as to be applied to real sample monitoring. This strategy not only provided a new avenue to design more efficient MXene-based co-reaction accelerator, but also paved the way for the development of high-performance luminol − DO ECL system.

Ru(bpy)3]2+ doped mesoporous carbon nanospheres as enhanced ECL luminophore for ultrasensitive detection of β-hydroxybutyric acid

Electrochemiluminescence (ECL) sensing by virtue of its low background interference and great controllability, has emerged as a significant method in analysis. However, how to gain well-performed ECL sensors in a facile effective way remains a challenge. Herein, we synthesized [Ru(bpy)3]2+ doped mesoporous carbon nanospheres (RMCNs) as an enhanced ECL luminophore via a one-step approach, which present great ECL emission and stability. The synergistic effects of [Ru(bpy)3]2+ doping level, Zeta potential, pore size and particle size of RMCNs on the ECL intensity were systematically studied, and the ECL efficiency of individual [Ru(bpy)3]2+ cation in RMCNs was clearly clarified through approximate calculation. Combined with molecularly imprinted polymer (MIP), an ECL sensor featuring good selectivity and wide detection range was developed for the detection of β-hydroxybutyric acid (0.1 nM∼10 mM). This work puts forward an effective solution for the design of nanoluminophores with excellent and stable ECL property.

A novel micron europium cluster coordination polymer as a strong electrochemiluminescent emitter for accurate and sensitive detection of tetracycline.

In this work, a self-luminescent micron europium cluster coordination polymer (Eu-CCP) cathode electrochemiluminescence (ECL) emitter is first reported. The mass percentage of Eu in Eu-CCP is 50.1%, indicating that Eu-CCP has a high-nucleation luminescence center. In addition, our Eu-CCP possesses a stable and efficient ECL red emission performance, and the intensity is approximately 6.5-fold higher than that of the traditional tris(2,2'-bipyridyl)ruthenium(II) dichloride. The enhancement of Eu-CCP luminescence in our system is due to the following reasons: (1) the mixed ligand and high nuclear europium luminescent center can cooperate to improve the quenching effect induced by water or hydroxyl groups; and (2) external coreaction accelerator and coreactant enhancement. We also investigate the application of Eu-CCP in ECL sensors by sensitive detection of tetracycline (TC). The low detection limit (73.5 fmol·L-1), high selectivity, good stability and satisfactory recoveries indicate that our ECL strategy can be used to detect TC accurately and sensitively.

A novel molecularly imprinting polypyrrole electrochemiluminescence sensor based on MIL-101-g-C3N4 for supersensitive determination of ciprofloxacin.

Ciprofloxacin (CIP), a quinolone antibiotic, was rapidly and sensitively detected by integrating the molecularly imprinted polymer (MIP) with an ultra-sensitive electrochemiluminescence (ECL) method. g-C3N4, a typical polymer semiconductor, exhibited outstandingECL efficiency and excellent ECL stability after combining with an iron-based metal-organic framework (MIL-101). Subsequently, the molecularly imprinted polypyrrole was electropolymerized on the composites of MIL-101-g-C3N4 modified glassy carbon electrode (GCE). The specific sites that could target rebinding the CIP molecules were formed on the surface of MIP after extracting the CIP templates. The determination of specific concentrations of CIP could be realized according to the difference in ECL intensity (△ECL) between the eluting and rebinding of the CIP. Under optimal conditions, a good linear response of △ECL and the logarithm of CIP concentrations wasobtained in the range 1.0 × 10-9 ~ 1.0 × 10-5 mol/L, with adetection limit of 4.5 × 10-10 mol/L (S/N = 3) (the working potentialwas-1.8 ~ 0 V). The RSD of all points in the calibration plot was less than 5.0% and the real samples recovery was between 98.0 and 104%. This paper displays satisfactory selectivity and sensitivity, providing a rapid, convenient, and cheap method for the determination of CIP in realsamples.