Anodic Electrochemiluminescence Research Articles

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

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

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

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

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.

N vacancy and self-enhancement induced high anodic electrochemiluminescence of 3D g-C3N4 for sensitive staphylococcus aureus analysis

Here, 3D g-C3N4 with dense N vacancy in its 3D porous interconnected open-framework was synthesized, and the co-reactive 3-(dibutylamino)propylamine (DBAPA) was further covalently coupled onto the surface, resulting in a strong self-enhanced anodic electrochemiluminescence (ECL). Through introduction of high-density N vacancy, for the obtained 3D g–C3N4–NV, the band gap was broadened and the electrical conductivity was enhanced, realizing an obvious ECL improvement. Moreover, after the covalent binding of co-reactive DBAPA, the obtained 3D g–C3N4–NV-DBAPA exhibited a more intensive self-enhanced ECL signal due to the higher co-reaction efficiency originated from shorter electron transfer distance and lower energy loss. Based on the high initial signal of the proposed 3D g–C3N4–NV-DBAPA, a sensitive ECL biosensor with signal “on-off” was fabricated in assistance with multiple horizontal ordered hybridization chain reaction (HO-HCR). Through orderly fixing the reacted DNA chains on the Y-shape DNA structure on the electrode could effectively decrease diffusion process and improve the reaction efficiency of HCR process, resulting in the formation of numerous long horizontal double-strand DNA that could immobilize abundant ferrocene-doxorubicin (Fc-Dox) with ECL quenching effect. Meanwhile, compared to the traditional vertical HCR, the HO-HCR could make the quench reagent closer to the ECL emitter on the electrode surface and obtain a more effective quenching effect to enhance the sensing sensitivity. As a result, the proposed ECL biosensor archived the sensitive measurement of staphylococcus aureus with a detection limit of 10.3 aM.

Regulating Reactive Oxygen Species over M-N-C Single-Atom Catalysts for Potential-Resolved Electrochemiluminescence.

The development of potential-resolved electrochemiluminescence (ECL) systems with dual emitting signals holds great promise for accurate and reliable determination in complex samples. However, the practical application of such systems is hindered by the inevitable mutual interaction and mismatch between different luminophores or coreactants. In this work, for the first time, by precisely tuning the oxygen reduction performance of M-N-C single-atom catalysts (SACs), we present a dual potential-resolved luminol ECL system employing endogenous dissolved O2 as a coreactant. Using advanced in situ monitoring and theoretical calculations, we elucidate the intricate mechanism involving the selective and efficient activation of dissolved O2 through central metal species modulation. This modulation leads to the controlled generation of hydroxyl radical (·OH) and superoxide radical (O2·-), which subsequently trigger cathodic and anodic luminol ECL emission, respectively. The well-designed Cu-N-C SACs, with their moderate oxophilicity, enable the simultaneous generation of ·OH and O2·-, thereby facilitating dual potential-resolved ECL. As a proof of concept, we employed the principal component analysis statistical method to differentiate antibiotics based on the output of the dual-potential ECL signals. This work establishes a new avenue for constructing a potential-resolved ECL platform based on a single luminophore and coreactant through precise regulation of active intermediates.

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.

Potential-Resolved Ratiometric Aptasensor for Sensitive Acetamiprid Analysis Based on Coreactant-free Electrochemiluminescence Luminophores of Gd-MOF and "Light Switch" Molecule of [Ru(bpy)2dppz]2.

For conventional potential-resolved ratiometric electrochemiluminescence (ECL) systems, the introduction of multiplex coreactants is imperative. However, the undesirable interactions between different coreactants inevitably affect analytical accuracy and sensitivity. Herein, through the coordination of aggregation-induced emission ligands with gadolinium cations, the self-luminescent metal-organic framework (Gd-MOF) is prepared and serves as a novel coreactant-free anodic ECL emitter. By the intercalation of [Ru(bpy)2dppz]2+ with light switch effect into DNA duplex, one high-efficiency cathodic ECL probe is obtained using K2S2O8 as a coreactant. In the presence of acetamiprid, the strong affinity between the target and its aptamer induces the release of [Ru(bpy)2dppz]2+, resulting in a decreasing cathode signal and an increasing anode signal owing to the ECL resonance energy transfer from Gd-MOF to [Ru(bpy)2dppz]2+. In this way, an efficient dual-signal ECL aptasensor is constructed for the ratiometric analysis of acetamiprid, exhibiting a remarkably low detection limit of 0.033 pM. Strikingly, by using only one exogenous coreactant, the cross interference from multiple coreactants can be eliminated, thus improving the detection accuracy. The developed high-performance ECL sensing platform is successfully applied to monitor the residual level of acetamiprid in real samples, demonstrating its potential application in the field of food security.

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.

Electroless Deposition of Palladium Nanoparticles on Graphdiyne Boosts Electrochemiluminescence.

Modulating the electronic structure of metal nanoparticles via metal-support interaction has attracted intense interest in the field of catalytic science. However, the roles of supporting substrates in regulating the catalytic properties of electrochemiluminescence (ECL) remain elusive. Here, we find that the use of graphdiyne (GDY) as the substrate for electroless deposition of Pd nanoparticles (Pd/GDY) produces the most pronounced anodic signal enhancement in luminol-dissolved oxygen (O2) ECL system as co-reactant accelerator over other carbon-based Pd composite nanomaterials. Pd/GDY exhibits electrocatalytic activity for the reduction of O2 through a four-electron pathway at approximately -0.059 V (vs Ag/AgCl) in neutral solution forming reactive oxygen species (ROS) as intermediates. The study shows that the interaction of Pd and GDY increases the amount and stability of ROS on the Pd/GDY electrode surface and promotes the reaction of ROS and luminol anion radical to generate excited luminol, which significantly boosts the luminol anodic ECL emission. Based on quenching of luminol ECL through the consumption of ROS by antioxidants, we develop a platform for the detection of intracellular antioxidants. This study provides an avenue for the development of efficient luminol ECL systems in neutral media and expands the biological application of ECL systems.

Co3O4/NiCo2O4 heterojunction as oxygen evolution reaction catalyst for efficient luminol anode electrochemiluminescence

Luminol has garnered significant attention from analysts as one of the most effective and commonly used electrochemiluminescence (ECL) reagents. However, the efficient luminescence of luminol anode is limited by the excitation of various reactive oxygen species (ROS). Typically, ROS are generated through co-reactive reagents and dissolved oxygen. Unfortunately, the former suffers from two drawbacks, namely biotoxicity and instability, while the latter cannot offer sufficient oxygen due to its limited solubility in aqueous solutions. Consequently, a low decomposition rate is usually obtained, leading to insufficient ROS. Therefore, there is an urgent need to develop efficient luminol anode systems. This study focuses on the use of zeolitic imidazolate framework-67 (ZIF-67) as a template, employing a controlled chemical etching method to create a ZIF-67/Ni-Co-layered double hydroxide (LDH). The intermediate composite is then annealed in air, resulting in the formation of a Co3O4/NiCo2O4 double-shelled nanobox (DSNB) heterostructure. Due to its structural advantages, the DSNB exhibits excellent electrocatalytic performance in the oxygen evolution reaction (OER). Furthermore, it was found that both the intermediates and products of OER can directly participate in the luminol chemiluminescence process, ultimately resulting in a 700-fold increase in the electrochemiluminescence (ECL) signal compared to an equal molar concentration of luminol solution. This work not only establishes the OER-mediated ECL system but also deepens the understanding of the relationship between ROS and luminol, providing a new pathway to study the luminol anodic ECL luminescence system.

Chiral electrochemiluminescence for simultaneous enantiomeric detection of aspartic acid and phenylalanine.

The burgeoning interest in rapid, simultaneous multi-target detection has propelled advancements in chiral electrochemiluminescence (ECL) assays. This study presents the design and implementation of a potential-resolved dual-color ECL sensor, engineered for the concurrent detection of aspartic acid (Asp) and phenylalanine (Phe) enantiomers. The sensor array was meticulously constructed by amalgamating anodic chiral ECL probe Ru(phen)2(L-Cys) nanocrystals with cathodic ECL probe ZnO nanoflowers (ZnO NFs). This research explored the potential of executing multianalyte assays via a potential-resolved ECL strategy, contributing to the advancements in the field of chiral ECL assays.

Ratiometric Electrochemiluminescence of Zirconium Metal-Organic Framework as a Single Luminophore for Sensitive Detection of HPV-16 DNA.

This study developed a new zirconium metal-organic framework (MOF) luminophore named Zr-DPA@TCPP with dual-emission electrochemiluminescence (ECL) characteristics at a resolved potential. First, Zr-DPA@TCPP with a core-shell structure was effectively synthesized through the self-assembly of 9,10-di(p-carboxyphenyl)anthracene (DPA) and 5,10,15,20-tetra(4-carboxyphenyl)porphyrin (TCPP) as the respective organic ligands and the Zr cluster as the metal node. The reasonable integration of the two organic ligands DPA and TCPP with ECL properties into a single monomer, Zr-DPA@TCPP, successfully exhibited synchronous anodic and cathodic ECL signals. Besides, due to the impressively unique property of ferrocene (Fc), which can quench the anodic ECL but cannot affect the cathodic ECL signal, the ratiometric ECL biosensor was cleverly designed by using the cathode signal as an internal reference. Thus, combined with DNA recycle amplification reactions, the ECL biosensor realized sensitive ratiometric detection of HPV-16 DNA with the linear range of 1 fM-100 pM and the limit of detection (LOD) of 596 aM. The distinctive dual-emission properties of Zr-DPA@TCPP provided a new idea for the development of ECL luminophores and opened up an innovative avenue of fabricating the ratiometric ECL platform.

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.

Free PCR virus detection via few-layer bismuthene and tetrahedral DNA nanostructured assemblies

In this work we describe a highly sensitive method based on a biocatalyzed electrochemiluminescence approach. The system combines, for the first time, the use of few-layer bismuthene (FLB) as a platform for the oriented immobilization of tetrahedral DNA nanostructures (TDNs) specifically designed and synthetized to detect a specific SARS-CoV-2 gene sequence. In one of its vertices, these TDNs contain a DNA capture probe of the open reading frame 1 ab (ORF1ab) of the virus, available for the biorecognition of the target DNA/RNA. At the other three vertices, there are thiol groups that enable the stable anchoring/binding to the FLB surface. This novel geometry/approach enables not only the binding of the TDNs to surfaces, but also the orientation of the capture probe in a direction normal to the bismuthine surface so that it is readily accessible for binding/recognition of the specific SARS-CoV-2 sequence. The analytical signal is based on the anodic electrochemiluminescence (ECL) intensity of luminol which, in turn, arises as a result of the reaction with H2O2, generated by the enzymatic reaction of glucose oxidation, catalyzed by the biocatalytic label avidin-glucose oxidase conjugate (Av-GOx), which acts as co-reactant in the electrochemiluminescent reaction. The method exhibits a limit of detection (LOD) of 4.31 aM and a wide linear range from 14.4 aM to 1.00 μM, and its applicability was confirmed by detecting SARS-CoV-2 in nasopharyngeal samples from COVID-19 patients without the need of any amplification process.

Nanoconfined Cathodic Electrochemiluminescence for Self-Sensitized Bioimaging of Membrane Protein.

Self-enhanced electrochemiluminescence (ECL) can be achieved via the confinement of coreactants and ECL emitters in a single nanostructure. This strategy has been used for the design of anodic ECL systems with amine compounds as coreactants. In this work, a novel confinement system was proposed by codoping positively charged ECL emitter tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)32+) and negatively charged coreactant peroxydisulfate (S2O82-) in silica nanoparticles. The codoping process could be performed by introducing S2O82- in cationic poly(diallyldimethylammonium chloride) (PDDA) to form PDDA@S2O82- and then encapsulating it and Ru(bpy)32+ in the Triton X-100 vesicle followed by the hydrolysis of tetraethyl ortosilicate, surface modification, and demulsification. The obtained RuSSNs exhibited good homogeneity, excellent monodispersity, acceptable biocompatibility, and 2.9-fold stronger ECL emission than Ru(bpy)32+-doped silica nanoparticles at an equal amount of nanoparticles in the presence of 0.1 M K2S2O8. Thus, an in situ self-sensitized cathodic ECL imaging method was designed for the monitoring of glycoprotein on living cell membranes. This work provides a new way for the modification, enhancement, and application of nano-ECL emitters in biological analysis.

Carboxyl groups on carbon nanodots as co-reactant sites for anodic electrochemiluminescence of tris(2,2-bipyridine)ruthenium(II)

Carbon nanodots (C-dots) with good biocompatibility have been extensively utilized as co-reactants for electrochemiluminescence (ECL) of the tris(2,2′-bipyridine)ruthenium(II) (Ru(bpy)32+) system. However, the ECL intensity of this system is still relatively low and the mechanism of C-dots as co-reactants remains unclear, which greatly limits its further application in bio-analysis. In this work, we revealed that the carboxyl groups on C-dots are co-reactant sites for Ru(bpy)32+ ECL by systematically investigating the contribution of carboxyl, hydroxyl and carbonyl groups on the surface of C-dots to the ECL intensity. Further treatment with hydrogen peroxide to increase the carboxyl-group content on C-dots resulted in a 10-fold increase in ECL intensity over the original Ru(bpy)32+/C-dots system. This work provides new insights for the rational design of ECL systems with C-dots as co-reactants and offers new chances for further applications of C-dots in the field of ECL.

Signal-Enhanced Immunosensor-Based MOF-Derived ZrO2 Nanomaterials as Electrochemiluminescence Emitter for D-Dimer Detection.

Metal oxide nanomaterials have garnered significant attention in the field of electrochemiluminescence (ECL) sensing due to their efficient, stable, and nontoxic properties. However, the current research on metal oxide nanomaterials has primarily focused on their cathodic luminescence properties, with limited reports on their anodic ECL properties. In this study, we utilized MOF-derived ZrO2 nanomaterials as luminophores to generate stable anodic ECL signals in the presence of the coreactant tripropylamine (TPrA). Additionally, a signal-enhancing immunosensor was developed to analyze D-dimer by incorporating the coreaction accelerator Cu-doped TiO2 (TiO2-Cu). The ZrO2 synthesized by calcining UiO-67 demonstrated nontoxicity and biocompatibility, exhibiting efficient and stable ECL emission in a TPrA solution. The inclusion of TiO2-Cu as a coreaction accelerator in the immunosensor resulted in the formation of a ternary system of ZrO2/TiO2-Cu/TPrA. The Cu doping effectively narrowed the bandgap of TiO2 and enhanced its conductivity. As a substrate, TiO2-Cu reacted with more TPrA, generating sufficient free radicals to effectively enhance the ECL signal of ZrO2. In this article, a short peptide ligand, NFC (NARKFYKGC), was designed to immobilize antibodies and maintain the activity of antigen-binding sites during the construction of the immunosensor. The developed immunosensor was used for the accurate detection of D-dimers, with a wide linear range of 0.05-600 ng/mL and a low detection limit of 21 pg/mL..

Coreactant-free dual-emitting conjugated polymer for ratiometric electrochemiluminescence detection of SARS-CoV-2 RdRp gene

Constructing mono-luminophor-based electrochemiluminescence (ECL) ratio system is a great challenge due to the limitations of the luminescent species with dual-signal-output, luminescence efficiency and coreactant. This work developed carboxyl-functionalized poly[9,9-bis(3'-(N,N-dimethylamino) propyl)-2,7-fluorene]-alt-2,7-(9,9 dioctylfluorene)] nanoparticles(PFN NPs) as dual-emitting luminophors, which can synchronously output strong cathodic and anodic ECL signals without any exogenous coreactants. The inherent molecular structure enabled efficient intramolecular electron transfer between tertiary amine groups and backbone of PFN to generate strong cathodic and anodic ECL emission. Particularly, H+ in aqueous solution played an irreplaceable role for cathodic ECL emission. The silver nanoparticles (AgNPs) were developed as signal regulator because of their excellent hydrogen evolution reaction (HER) activity, which significantly quenched the cathodic signal while kept the anodic signal unchanged. The dual-emitting PFN NPs cleverly integrated signal regulator AgNPs and bicyclic strand displacement amplification (SDA) to construct a coreactant-free mono-luminophor-based ratiometric ECL sensing for SARS-CoV-2 RdRp gene assay. The strong dual-emitting of PFN NPs and excellent quenching effect of AgNPs on cathodic emission endowed the biosensor with a high detection sensitivity, and the detection limit was as low as 39 aM for RdRp gene. The unique dual-emitting properties of PFN NPs open up a new path to construct coreactant-free mono-luminophor-based ECL ratio platform, and excellent HER activity of AgNPs offers some new thoughts for realizing ECL signal changes.

Donor-acceptor based enhanced electrochemiluminescence of coumarin microcrystals: Mechanism study and sensing application

Simple and efficient strategy to obtain ideal organic electrochemiluminescence (ECL) luminophores still is a central challenge. Here a series of coumarin microcrystals (C545 MCs) as new generation of ECL luminophores were facilely synthesized by a solvent exchange process. Among them, leaf-like C545 MCs with donor-acceptor system display a stable and robust anodic ECL response with triethanolamine (TEOA) as coreactant, which is 9.28 times higher than that of C545 monomer. Combined with its predecessors (coumarin and coumarin 6 H), the effects of donor and acceptor on the ECL properties of C545 were investigated with the help of experiments and theoretical calculation. On the basis of the quenching effect of dopamine (DA) toward the C545 MCs-TEOA ECL system, it was employed to construct a sensitive sensing platform for DA detection. A low limit of detection (0.38 nmol·L−1, S/N = 3) is obtained in a wide linear range (1 nmol·L−1 – 1 mmol·L−1). This work forcefully enriches the design and application of donor-acceptor based coumarin materials in ECL sensing.

Iron Single-Atom Catalyst-Enabled Peroxydisulfate Activation Enhances Cathodic Electrochemiluminescence of Tris(bipyridine)ruthenium(II).

The tris(bipyridine)ruthenium(II) (Ru(bpy)32+)-tripropylamine anodic electrochemiluminescence (ECL) system has been widely applied in commercial bioanalysis. However, the presence of amine compounds in the biological environment results in unavoidable anodic interference signals, which hinder further extensive use of the system. In contrast, the cathodic Ru(bpy)32+ ECL system can overcome these limitations. The Ru(bpy)32+/peroxydisulfate (S2O82-, PDS) ECL system has been extensively employed due to its ability to produce a sulfate radical anion (SO4•-) with strong oxidation ability, which enhances the ECL signal. However, the symmetrical molecular structure of PDS makes it challenging to be activated and causes low luminescence efficiency. To address this issue, we propose an efficient Ru(bpy)32+-based ternary ECL system that uses the iron-nitrogen-carbon single-atom catalyst (Fe-N-C SAC) as an advanced accelerator. Fe-N-C SAC can efficiently activate PDS into reactive oxygen species at a lower voltage, which significantly boosts the cathodic ECL emission of Ru(bpy)32+. Benefiting from the outstanding catalytic activity of Fe-N-C SAC, we successfully established an ECL biosensor that detects alkaline phosphatase activity with high sensitivity, demonstrating the feasibility of practical application.