Electrochemiluminescence Intensity Research Articles

Cu superparticle-based aggregation induced enhancement strategy with PVDF-HFP/CeVO4 NP sensing interface for miR-103a detection

Aggregation-induced emission (AIE) has been widely used in research on electrochemiluminescence (ECL) due to its excellent luminescence intensity. In this work, copper superparticles (Cu SPs) were used to construct ECL biosensor to detect the microRNA-103a (miRNA-103a) in triple-negative breast cancer (TNBC) tumor tissues. Firstly, GSH-capped copper clusters were used as precursors to prepare Cu SPs by the AIE effect. Compared with clusters, Cu SPs possessed higher luminescence performance and energy stability, making them an ideal choice for ECL nanoprobe. The film of PVDF-HFP/CeVO4 NPs was constructed and modified with CPBA and GSH as the sensing interface (PCCG). The PCCG film displayed good conductivity and hydrophilicity, and desirable mechanical stability. Moreover, the PCCG film can induce high carrier mobility rates and dissociate large amounts of the co-reactant K2S2O8 to enhance the ECL intensity of Cu SPs. As a result, the prepared ECL sensor with the catalyzed hairpin assembly (CHA) strategy was employed to quantify miRNA-103a in the range of 100 fM to 100 nM. The biosensor provided a novel analytical approach for the clinical diagnosis of TNBC.

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.

Bright luminescent Zn2GeO4:Mn NP/MXene hydrogel-based ECL biosensor for glioblastoma diagnosis

In this work, miRNA-10b in the glioblastoma (GBM) tumor tissues has been detected by a novel electrochemiluminescence (ECL) biosensor. Firstly, a new kind of bright luminescent Zn2GeO4:Mn NPs were prepared as ECL nanoprobe, which possessed high fluorescence quantum yield and ECL quantum efficiency. Secondly, Ti3C2 MXene hydrogel (MXG) have been developed as the sensing interface. The MXG retained the inherent biocompatibility and mechanical features of hydrogel. Furthermore, the uniform distribution of metallic Ti3C2 MXene in the hydrogel microstructure provided the good conductivity and multiple binding sites for biomolecules. MXene also can promote the separation of the electrons and holes to accelerate the electron-transfer rate and improve ECL efficiency. Due to these synergistic effects, the screen printed electrode was successfully modified with MXG as sensing platform to enhance the ECL intensity of Zn2GeO4:Mn NP, which greatly improved the detection efficiency and facilitated the high-throughput analysis. Finally, the toehold mediated strand displacement (TMSD) strategy was employed with then biosensor to detect miRNA-10b with the range of 10 fM to 1 nM. The limit of detection was 5 fM. This ECL biosensor has been used to analyze miRNA-10b expression in GBM tumor tissues, which possessed the great potential value for clinical diagnosis.

A magnetically fixed bifunctional monomer molecularly imprinted electrochemiluminescence sensor for specifically identifying thiabendazole in food

A magnetically fixed bifunctional monomer molecularly imprinted electrochemiluminescence (ECL) sensor (MIP/MMOF@g-C3N4/L-Aas/MGCE) was constructed to selective detection thiabendazole (TBZ). Fe3O4 modified by sulfonic acid group (–SO3H) acted as magnetic core to attract Co2+ to initiate the growth of ZIF-67 (MMOF). Graphitic carbon nitride nanosheets (g-C3N4) were doped into MMOF by inherent amino groups to prepare integrated magnetic ECL luminophore (MMOF@g-C3N4). MMOF@g-C3N4 was immobilized on the surface of magnetic glassy carbon electrode (MGCE) by using the superparamagnetism of Fe3O4, which enhanced the stability and reusability of ECL system. Sodium ascorbate (L-Aas) acted as co-reactant accelerators to further enhance ECL intensity. MIP prepared with TBZ as template molecule and o-phenylenediamine (oPD)/resorcinol (RS) as bifunctional monomers contained more imprinting sites, which can enhance the adsorption performance. The luminescence mechanism of magnetic ECL system was investigated, and the specific recognition mechanism of MIP recognition system was deeply explored. The linear range of the method was 1 × 10−9–5 × 10−5 mol L−1, and the detection limit was 3.77 × 10−10 mol L−1. A good recovery rate (80.08%–96.82%) was obtained in the actual sample detection, which was basically consistent with the detection results of High Performance Liquid Chromatography.

Sensitive detection of kanamycin based on ECL resonance energy transfer between iridium complex doped SiO2 nanospheres and Au nanoparticles decorated TiVC MXene

Herein, a novel sandwich electrochemiluminescence (ECL) aptasensor was developed based on the resonance energy transfer (RET) with iridium complex doped silicate nanoparticles (SiO2@Ir) as energy donor and gold nanoparticles modified TiVC MXene (AuNPs@TiVC) as energy acceptor. Strong anodic ECL signal of SiO2@Ir was obtained through both co-reactant pathway and annihilation pathway. Electrochemical results showed that SiO2@Ir has good electron transfer rate and large specific surface area to immobilize more aptamers. AuNPs@TiVC apparently quenched the ECL signal of SiO2@Ir due to the ECL resonance energy transfer between them. In the presence of kanamycin (KAN), a sandwich type sensor was formed with the aptamer probes as connecters between the donor and the acceptor, resulting in the decrease of ECL intensity. Under the optimal condition, KAN could be sensitively detected in the range of 0.1 pg/mL to 10 ng/mL with a low detection limit of 24.5 fg/mL. The proposed ECL system exhibited satisfactory analytical performance, which can realize the detection of various biological molecules by adopting suitable aptamer.

Local electrochemiluminescence imaging using scanning electrochemical cell microscopy

In this communication, local electrochemiluminescence (ECL) imaging is achieved using scanning electrochemical cell microscopy (SECCM) to create a localized region for the occurrence of ECL reaction. The system is demonstrated using a droplet at the micropipette that is contact with the prepared Ru-Silica@Au particles at indium tin oxide (ITO) slide. Tri-n-propylamine (TPrA) in the droplet reacts with ruthenium complex in a 10 μm-diameter-region to produce ECL emission, which is recorded by photo multiplier tube (PMT) underneath the ITO slide. By contacting each local region consecutively, the distribution of steady-state current and the related ECL emission at the ITO surface is imaged. The local ECL intensity show an approximately linear dependence with the current, but obvious deviation from the linear curve is observed at some regions. This result suggests that the ECL emission is not only determined by the transferred electron number in the electrochemical reaction, and also affected by local environments at ITO surface. As compared with the traditionally used ECL imaging in the bulk solution, this strategy avoids the cross-talking of ECL emission from nearby regions, and could offer a new way to unveil more molecular mechanism in the ECL reaction.

Etching of Ag nanoparticles triggered bidirectional regulation for electrochemiluminescence ratiometric immunoassay.

A highly efficient ratiometric electrochemiluminescence (ECL) immunoassay was explored by bidirectionally regulating the ECL intensity of two luminophors. The immunoassay was conducted in a split-type mode consisting of an ECL detection procedure and a sandwich immunoreaction. The ECL detection was executed using a dual-disk glassy carbon electrode modified with two potential-resolved luminophors (g-C3N4-Ag and Ru-MOF-Ag nanocomposites), and the sandwich immunoreaction using glucose oxidase (GOx)-modified SiO2 nanospheres as labels was carried out in a 96-well plate. The Ag nanoparticles (NPs) acted as bifunctional units both for triggering the resonance energy transfer (RET) with g-C3N4 and for accelerating the electron transfer rate of the Ru-MOF-Ag ECL reaction. When the H2O2 catalyzed by GOx in the 96-well plate was transferred to the dual-disk glass carbon electrode, the doped Ag NPs in the two luminophors could be etched, thus destroying the RET between C3N4 and the accelerated reaction to Ru-MOF, resulting in an opposite trend in the ECL signal outputted from the dual disks. Using the ratio of the two signals for quantification, the constructed immunosensor for a model target, i.e. myoglobin, exhibited a low detection limit of 4.7 × 10-14g/mL. The ingenious combination of ECL ratiometry, bifunctional Ag NPs, and a split-type strategy effectively reduces environmental and human errors, offering a more precise and sensitive analysis for complex samples.

Cathodic luminol electrochemiluminescence on TiO2 nanotube array

This study introduces a novel fabrication of screen-printed electrode of hierarchical thin layers of TiO2 nanotube arrays (TNA) and its preliminary investigation for cathodic electrochemiluminescence (ECL) of luminol. The TNA growth on titanium foil by anodization technique was studied under various anodization times and counter electrodes (Pt wire and stainless-steel plate). Characterization using FTIR, UV-VIS DRS, and XRD revealed the increase of TiO2 formation at longer anodization times. The TNA synthesized with a stainless-steel counter electrode (TNA-SS) for 2000 s exhibited better nanotube growth and a higher electrochemical active surface area compared to the one using Pt counter electrode (TNA-Pt). The SEM characterization verified the nanotube morphology of TNA-SS with an average pore diameter of 50.46 nm and a tube length of ∼1100 nm. Notably, when TNA applied as the working electrode for the ECL of luminol, a reduction peak at −0.8 V accompanied by a clear ECL signal were observed, reaching an optimum intensity at 15 μM luminol. A comparative analysis between TNA-SS and TNA-Pt revealed the same trend of ECL signals with a significantly higher ECL intensity of TNA-SS than that of TNA-Pt. The ECL intensity of TNA-SS 2000s was also higher than TNA-SS 300s, confirming the importance of TNA surface area to the ECL activity. Nevertheless, the synthesized SPE-TNA shows great prospect to be applied in electroanalytical and sensing fields, offering opportunities for the development of electrochemiluminescence technologies.

An electrochemiluminescence sensor based on Ag NPs amplifying PDDA-modified TbPO4:Ce NWs signal for sensitive detection of lincomycin

The residue of lincomycin in water will not only aggravate the drug resistance of bacteria but also cause damage to the human body through biological accumulation. In this work, an electrochemiluminescence (ECL) aptasensor for the detection of lincomycin was constructed based on polydimethyldiallylammonium chloride (PDDA) functionalized Ce-doped TbPO4 nanowires (PDDA-TbPO4:Ce NWs) and silver nanoparticles (Ag NPs). TbPO4:Ce NWs were used as the luminophore, and PDDA was used to functionalize the luminophore to make the surface of the luminophore positively charged. The negatively charged silver nanoparticles were combined with PDDA-TbPO4:Ce NWs by electrostatic interaction. Ag NPs accelerated the electron transfer rate and promoted the ECL efficiency, which finally increased the ECL intensity of TbPO4:Ce NWs by about 4 times. Under the optimal conditions, the detection limit of the ECL sensor was as low as 4.37 × 10−16 M, and the linear range was 1 × 10 − 15 M to 1 × 10 − 5 M, with good selectivity, stability, and repeatability. The sensor can be applied to the detection of lincomycin in water, and the recovery rate is 97.7–103.4 %, which has broad application prospects.

Electrochemiluminescent properties of carbon nitride nanoflowers and their application to the detection of melatonin in foods

Carbon nitride nanoflower materials (CNNFs) modified electrodes were prepared and used as electrochemiluminescence (ECL) sensors for the sensitive detection of melatonin (MT) in food. The luminescence intensity of CNNFs is increased by 4.6 times compared with bulk g-C3N4. In addition, the effect of dissolved oxygen on the material was eliminated, and the stability of ECL intensity of CNNFs was improved. Under the optimal experimental conditions, there is a good linear relationship between the ECL intensity ratio and logCMT in a concentration range of 2.0 × 10−11–1.0 × 10−6 mol/L, and the detection limit is 6.2 × 10−13 mol/L. This experiment has been successfully used for the detection of MT in rice, black rice, oats, apples, bananas, grapes, carrots, tomatoes, cucumbers, bread, and beers. The results are consistent with those obtained by high-performance liquid chromatography (HPLC). Therefore, this sensor is a sensitive and effective method for detecting MT content in food.

A novel self-enhanced ECL-RET aptasensor based on the bimetallic MOFs with homogeneous catalytic sites for kanamycin detection

The inappropriate use of antibiotics undoubtedly poses a potential threat to public health, creating an increasing need to develop highly sensitive tests. In this study, we designed a new type of porphyrin metal-organic frameworks (Fe TCPP(Zn) MOFs) with homogeneous catalytic sites. The ferric-based metal ligands of Fe TCPP(Zn) MOFs acted as co-reaction accelerators, which effectively improved the conversion efficiency of H2O2 on the surface of MOFs, then increased the concentration of •OH surrounding porphyrin molecules to achieve self-enhanced electrochemiluminescence (ECL). Based on this, an aptasensor for the specific detection of kanamycin (KAN) in food and environmental water samples was constructed in combination with resonance energy transform (RET), in which Fe TCPP(Zn) MOFs were used as luminescence donor and AuNPs were used as acceptor. Under the best conditions, there was a good linear relationship between the ECL intensity and the logarithm of KAN concentration with a detection limit of 0.28 fM in the range of 1.0 × 10−7–1.0 × 10−13 M, demonstrating satisfactory selectivity and stability. At the same time, the complexity of the detection environment was reduced, which further realized the reliable analysis of KAN in milk, honey and pond water. Overall, this innovative self-enhanced ECL strategy provides a novel approach for constructing efficient ECL systems in MOFs, and also extends the application of MOFs to the analysis and detection of trace antibiotics in food and the environment.

Ultrastable Anion Radicals in Ligand-Dimerized Frameworks for Self-Accumulated Electrochemiluminescence.

Electrochemiluminescence (ECL) is a light-emitting process that occurs via an annihilation reaction among energetic radical intermediates, whose stabilities determine the ECL efficiency. In this study, a ligand-dimerized metal-organic framework (MOF) with ultrastable anion radical is designed as an efficient nanoemitter for self-accumulated ECL. Due to the nonplanar structure of perylene diimide (PDI) derivate, two PDI ligands in the framework form a J-dimer unit with a vertical distance of ∼5.74 Å. In cathodic scanning, the ligand-dimerized MOF demonstrates three-step ECL emissions with a gradual increase in ECL intensity. Unlike the decrease in the PDI ligand, the self-accumulated ECL of the MOF was observed with 16.8-fold enhancement due to the excellent stability of radical intermediates in frameworks. Electron paramagnetic resonance demonstrated the ultrastability of free radicals in the designed frameworks, with 82.2% remaining even after one month of storage. Density functional theory calculations supported that PDI dimerization was energetically favorable upon successive electron injection. Moreover, the ECL wavelength is 610 nm, corresponding to the emission of excited dimers. The radical-stabilized reticular nanoemitters open up a new platform for decoding the fundamentals of self-accumulated ECL systems.

Electron Transfer Efficiency-Regulated Electrochemiluminescence for Rapid Crystallinity Analysis in Layered Materials.

The electrochemiluminescence (ECL) signal is largely determined by the electron transfer efficiency. Therefore, in the nanomaterial-involved ECL system, the structure-related electron distribution could affect the electron transfer efficiency and further alter the ECL intensity. These features make the design of versatile ECL-based analytical techniques for probing the correlated structure possible. And it is generally accepted that the increased crystallinity of nanomaterials usually leads to a uniform electron distribution, which provides higher conductivity. Therefore, the crystallinity-improved conductivity could facilitate electron transfer, promote the electrochemical activity of support materials, and boost the efficiency of the ECL reaction. In this study, we have demonstrated that the ECL signal of the graphitic carbon nitride reporter was proportional to the crystallinity of layered double hydroxides (LDHs), which meets the supposition well. On the basis of this phenomenon, an ECL-based crystallinity analysis approach has been established using CdAl-LDHs as the model materials. The universality of this proposed technique was further validated by the rapid and accurate crystallinity determination of ZnAl-LDH samples with diverse crystallinities. This work not only contributes an alternative to the X-ray diffraction technique for the rapid screening of crystallinity in layered materials but also opens a new avenue for the design of ECL-based structure analysis techniques toward nanomaterials and even organic materials by involving electron transfer regulation correlation.

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.

Electrochemiluminescence detection of catechol and tryptophol using nitrogen, sulfur co-doped graphene quantum dots based on a paper-based sensor

In this study, Nitrogen and Sulfur co-doped Graphene Quantum Dots (N, S-GQDs) were synthesized via a pyrolysis approach, utilizing citric acid as the carbon source and L-cysteine as the nitrogen and sulfur sources. These N, S-GQDs were used to develop a novel paper-based electrochemiluminescence (ECL) sensor for the detection of catechol (CC) and tryptophol, two potentially hazardous substances in the environment. Screen printing technology was utilized to construct the ECL sensor on filter paper, incorporating a hydrophobic layer, working and counter electrodes, and a reference electrode. The presence of CC and tryptophol was found to result in a decrease in the ECL intensity of the quantum dots (QDs), this quenching phenomenon is attributed to the oxidation of these substances within the electrochemical system and the subsequent electron transfer from the excited state of the QDs to the oxidation products. The sensor demonstrated a linear detection range for CC and tryptophol from 0.01 to 1000 μM, with detection limits of 0.0082 μM and 0.0066 μM, respectively, and exhibited excellent selectivity, stability, and repeatability. This cost-effective and efficient monitoring technique holds significant promise for environmental and health safety by facilitating the detection of CC and tryptophol, thereby mitigating their potential adverse impacts.

Enhancing electrochemiluminescence for chloramphenicol detection based on the synergistic effect of doped Ti3C2 with ultrasound

Chloramphenicol (CAP) is known to be harmful to the environment and food, posing a threat to human health. Developing an effective and convenient method for detecting CAP is crucial. An electrochemiluminescence (ECL) biosensor has been designed for sensitive detection of CAP. The improved ECL behavior was attributed to the synergistic effect of N and P co-doped Ti3C2-Apt1 (N, P-Ti3C2-Apt1) nanoprobes and high intensity focused ultrasound (HIFU) pretreatment. The doping of N and P could improve the electrochemical performance of Ti3C2. HIFU pretreatment generated more reactive oxygen species (ROS) in the luminol-O2 system. N, P-Ti3C2 could aggregate and catalyze ROS, causing an increase in ECL intensity. Furthermore, N, P-Ti3C2 as a carrier loaded more aptamer, which could recognize CAP with high specificity. The detection limit was 0.01 ng/mL. This biosensor has been successfully applied in milk and environmental water samples, highlighting its potential in the field of food and environmental analysis.

Chemiluminescence and electrochemiluminescence of water-soluble iridium(III) complexes containing a tetraethylene-glycol functionalised triazolylpyridine ligand

BackgroundIridium(III) complexes, exhibiting high luminescence quantum yields and a wide range of emission colours, are promising alternatives to tris(2,2ʹ-bipyridine)ruthenium(II) for chemiluminescence (CL) and electrochemiluminescence (ECL) detection. This emerging class of reagent, however, is limited by the poor solubility of many iridium(III) complexes in aqueous solution, and lack of understanding of their remarkably variable selectivities towards different analytes. ResultsSeven [Ir(C^N)2(pt-TEG)]+ complexes, exhibiting a wide range of reduction potentials and emission energies, were examined with six model analytes. For CL, cerium(IV) was used as the oxidant. The alkylamine analytes generally produced greater CL and ECL with the more readily oxidised Ir(III) complexes (C^N = piq, bt, ppy), predominantly through the ‘direct’ pathway requiring oxidation of both metal complex and analyte. Aniline derivatives that did not also contain secondary or tertiary alkylamines elicited CL from the less readily oxidised complexes (C^N = df-ppy-CF3, df-ppy) via energy transfer. The most difficult to oxidise complexes (C^N = df(CF3)-ppy-Me, df(CN)-ppy) gave poor responses due to the limited potential window of the solvent and inefficiency of energy transfer to their high energy excited states. Greater CL and/or ECL intensities were generally obtained for each analyte with at least one Ir(III) complex than with [Ru(bpy)3]2+; superior limits of detection for two analytes were demonstrated. SignificanceThis exploration of CL/ECL in which the properties of luminophore, analyte and oxidant are all varied provides a new understanding of the influence of the metal-complex potentials and excited state energy on the light-producing and quenching pathways, and consequently, their distinct selectivity towards different analytes. These findings will guide the development of water-soluble Ir(III) complexes as CL and ECL reagents.

Charge Density-Regulated Microchannel-Based Electrochemiluminescence Sensor for Hydrogen Sulfide Detection with a Highly Efficient Accumulation Strategy.

The electrochemiluminescence (ECL) intensity can be regulated by ionic current passing through the microchannel, which broadened the regulation of the ECL sensors. But in the early reported sensors, the electrostatic repulsion and steric hindrance caused few targets to approach the interface of the microchannel driven by concentration difference, which reduced the detection efficiency and prolonged the detection period. In this study, different accumulation strategies, such as a positive electric field and different polarity electric fields, were designed to accumulate targets in the microchannel. The interaction of azide groups and hydrogen sulfide served as a research model. Hydrogen sulfide can react with the negatively charged azide groups in the microchannel surface to produce positively charged amino groups, decreasing the negative charge density of the microchannel and thus altering the ionic current and ECL intensity. The accumulation of hydrogen sulfide at the microchannel tip can increase the collision probability with azide groups to improve the detection efficiency, and the integration of accumulation and reaction can shorten the detection period to 28 min. The hydrogen sulfide concentration on the microchannel tip accumulated by applying different polarity electric fields was 22.3-fold higher than that accumulated by applying a positive electric field. The selected research model broadened the application range of a microchannel-based ECL sensor and confirmed the universality of the microchannel-based ECL sensor.

Bimodal Oxidation Electrochemiluminescence Mechanism of Coreactant-Embedded Covalent Organic Frameworks via Postsynthetic Modification.

Electrochemiluminescence (ECL) efficiency is determined by charge transfer between coreactants and emitters in coreactant systems, which are usually limited by their slow intermolecular charge transfer. In this study, a covalent organic framework (COF) with aldehyde residue was synthesized, and then coreactants were covalently integrated into the skeleton through the postsynthetic modification strategy, resulting in a crystalline coreactant-embedded COF nanoemitter (C-COF). Compared to the pristine COF with an equivalent external coreactant, C-COF exhibited an extraordinary 1008-fold enhancement of ECL intensity due to the rapid intrareticular charge transfer. Significantly, with the pH increase, C-COF shows protonation-induced ECL enhancement for the first ECL peaked at +1.1 V and an opposite trend for the second ECL at +1.4 V, which were attributed to the antedating oxidation of coreactant in framework and COF self-oxidation, respectively. The resulting bimodal oxidation ECL mechanism was rationalized by spectral characterization and density functional theory calculations. The postsynthetic coreactant-embedded nanoemitters present innovative and universal avenues for advancing ECL systems.

Bimodal Oxidation Electrochemiluminescence Mechanism of Coreactant‐Embedded Covalent Organic Frameworks via Postsynthetic Modification

AbstractElectrochemiluminescence (ECL) efficiency is determined by charge transfer between coreactants and emitters in coreactant systems, which are usually limited by their slow intermolecular charge transfer. In this study, a covalent organic framework (COF) with aldehyde residue was synthesized, and then coreactants were covalently integrated into the skeleton through the postsynthetic modification strategy, resulting in a crystalline coreactant‐embedded COF nanoemitter (C–COF). Compared to the pristine COF with an equivalent external coreactant, C–COF exhibited an extraordinary 1008‐fold enhancement of ECL intensity due to the rapid intrareticular charge transfer. Significantly, with the pH increase, C–COF shows protonation‐induced ECL enhancement for the first ECL peaked at +1.1 V and an opposite trend for the second ECL at +1.4 V, which were attributed to the antedating oxidation of coreactant in framework and COF self‐oxidation, respectively. The resulting bimodal oxidation ECL mechanism was rationalized by spectral characterization and density functional theory calculations. The postsynthetic coreactant‐embedded nanoemitters present innovative and universal avenues for advancing ECL systems.