Cathodic Electrochemiluminescence Emission Research Articles

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

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

Self-Assembly-Induced Enhancement of Cathodic Electrochemiluminescence of Copper Nanoclusters for a Split-Type Matrix Metalloproteinase 14 Sensing Platform.

The unique optoelectronic and tunable luminescent characteristics of copper nanoclusters (Cu NCs) make them extremely promising as luminophores. However, the limited luminescence intensity and stability of Cu NCs have restricted their application in the field of electrochemiluminescence (ECL). Herein, a self-assembly-induced enhancement strategy was successfully employed to enhance the cathodic ECL performance of flexible ligand-stabilized Cu NCs. Specifically, Cu NCs form ordered sheetlike structures through intermolecular force. The restriction of ligand torsion in this self-assembled structure leads to a significant improvement in the ECL properties of the Cu NCs. Experimental results demonstrate that the assembled nanoscale Cu NC sheets exhibit an approximately three-fold increase in cathodic ECL emission compared to the dispersed state of Cu NCs. Furthermore, assembled nanoscale Cu NCs sheets were utilized as signal probes in conjunction with a specific short peptide derived from the catalytic structural domain of matrix metalloproteinase 14 (MMP 14) as the identification probe, thereby establishing a split-type ECL sensing platform for the quantification of NMP 14. The investigation has revealed the exceptional performance of assembled nanoscale Cu NCs sheets in ECL analysis, thus positioning them as novel and promising signal probes with significant potential in the field of sensing.

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.

Development of reusable electrochemiluminescence sensing microchip for detection of vomitoxin

In this work, a reusable DNA sensing microchip was developed for detection of vomitoxin (deoxynivalenol, DON) in sorghum using Cd-based core-shell CdSe@CdS quantum dots (QDs) as promising electrochemiluminescence (ECL) emitter. The size-adjustable aqueous phase CdSe@CdS QDs were prepared through homogeneous method, exhibiting strong cathodic ECL emission with a central wavelength of 520 nm in S2O82− coreactant. And gold nanoparticles-modified iron cobalt cyanide hydrate (Fe–Co–Au) was introduced as an accelerator to amplify the ECL signal. ECL signal was quenched after the formation of a double-stranded (dsDNA) S1–S2 by generating an electron transfer system between the emitter and ferrocene (Fc), which are modified on the aptamer (ssDNA S1) and its complement sequence (ssDNA S2), respectively. When the target DON is presence, the aptamer ssDNA S1 will bind to the DON and trigger the unbinding of double strands DNA and the release of the ssDNA S2, thus the signal can be generated. This approach offers a feasible method for the detection of DON within the range of 1 ng/mL to 200 ng/mL.

A simplified molecularly imprinted ECL sensor based on Mn2SnO4 nanocubes for sensitive detection of ribavirin.

Conventional single-signal or emerging sandwich-type double-signal electrochemiluminescence (ECL) immunosensors/aptasensors have offered accurate detection of small molecules, yet suffer from complicated setup, long processing time, and non-reusability. Here, we demonstrate a simplified molecularly imprinted ECL sensor based on Mn2SnO4 nanocubes. As an n-type semiconductor, Mn2SnO4 has numerous active sites that can capture electrons to accelerate chemical reactions, resulting in enhanced ECL activity and stability. For the first time, we verify a robust cathodic ECL emission of Mn2SnO4 luminophores in the presence of K2S2O8 coreactants. The proposed ECL sensor applies to the sensitive detection of ribavirin (RBV), endowing a wide linear range (1-2000 ng mL-1), low detection limit (0.85 ng mL-1, S/N = 3), high stability, specificity, and reproducibility, and the detection capability in real milk and chicken samples. This work highlights single semiconductor luminophore-driven molecularly imprinted ECL sensors, meeting the original aspiration of uncomplicated but high-performance sensing in food safety inspection.

Nickel Single-Atom Catalyst Boosts Electrochemiluminescence of Graphitic Carbon Nitride for Sensitive Detection of HBV DNA.

Owing to excellent catalytic activity, single-atom catalysts (SACs) have recently attracted considerable research interest in the electrochemiluminescence (ECL) field. However, the applications of SACs are mostly limited to conventional luminol ECL system. Hence, it is necessary to explore the application of SACs in more ECL systems. In this work, nickel single-atom catalysts (Ni SACs) were successfully applied in the graphitic carbon nitride (g-C3N4)-H2O2 ECL system to significantly enhance its cathodic emission. Notably, g-C3N4 acted not only as an ECL luminophore but also as a support to anchor Ni SACs. Ni SACs can significantly activate H2O2 to produce abundant OH• radicals for enhancing the cathodic ECL emission of g-C3N4. Ni SACs-anchored g-C3N4 (Ni SACs@g-C3N4) had a 10-fold enhanced ECL intensity as compared to g-C3N4. Finally, the Ni SACs@g-C3N4-H2O2 ECL system was developed to detect hepatitis B virus (HBV) DNA by incorporating an entropy-driven DNA walking machine-assisted CRISPR-Cas12a amplification strategy. The constructed biosensor exhibited excellent detection performance for HBV DNA with a limit of detection as low as 17 aM. This work puts forward a new idea for enhancing the cathodic ECL of g-C3N4-H2O2 and expands the application of SACs in the ECL system.

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.

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.

Pyronin Derivatives as Efficient Electrochemiluminescence Emitters in Aqueous Solution

The electrochemiluminescence (ECL) behavior of pyronin derivatives was reported. We found that these derivatives, as novel ECL emitters, generated an efficient emission phenomenon; that is, they showed anodic emission using tri-propylamine (TPA) as the coreactant and cathodic ECL emission using K2S2O8 as the coreactant. Because of its remarkable luminescent performance, the ECL mechanism (reductive-oxidative and oxidative-reductive) of benzylthiol-substituted pyronin (BTP) was specifically studied. Surprisingly, the cathodic ECL emission of BTP had a lower ECL peak potential at −0.54 V (vs. SCE) in aqueous solution. The potential range of −0.7 V to 0.0 V is lower than that of previously reported K2S2O8 cathodic ECL systems. Its good water solubility, easy modification, and excellent emission properties facilitate appealing (bio)analytical applications in ECL biosensors and cell imaging.

Electrochemistry and electrochemiluminescence of resorufin dye: Synergetic reductive-oxidation boosted by hydrogen peroxide

To develop robust field diagnostic systems capable of responding to medical needs, miniaturization of devices and high target sensitivity remain significant challenges. Electrochemiluminescence (ECL) is an ideal analysis tool to meet these challenges, and developing novel ECL materials is essential. Here we report the reversible electrochemical properties of resorufin, a commercial fluorescent dye, and its highly stable cathodic ECL. We find the cathodic ECL emission from the resorufin quantitatively changes upon the H2O2 content and propose the selective ECL molecular sensor against it. Resorufin undergoes reversible two-electron-transfer electrochemical reduction, and it generates cathodic ECL via a reductive-oxidation pathway with the S2O82− co-reactant. Interestingly, highly enhanced, synergetic ECL is produced in the dual K2S2O8–H2O2 co-reactant system, and especially, it can be used for selective molecular recognition of H2O2. Via the chronoamperometric application, the resorufin ECL signal reveals the linear correlation with the H2O2 concentration range of 0–150 µM with a detection limit of 6.8 µM. Resorufin exhibits strong potential as a new ECL luminophore. Also, selective enhancement of ECL suggests potential applicability to various immunoassays using H2O2.

Molecular engineered graphitic carbon nitride with strong and stable electrochemiluminescence for immunosensing

Graphitic carbon nitride (g-CN) is a semiconductor polymer with strong electrochemiluminescence (ECL) emission. However, the sensing application of g-CN ECL suffers from poor ECL stability due to its low electrical conductivity. In this work, g-CN is molecularly engineered with phenyl groups to improve its electrical conductivity. The prepared Ph-CN nanosheets (Ph-CNNS) show stable and strong cathodic ECL emission benefiting from the synergetic effect of improved conductivity preventing electron over-injection and higher luminescent efficiency of Ph-CNNS as compared to CNNS. Based on the strong and stable ECL emission of Ph-CNNS, a ECL immunosensor with biocatalytic precipitation reaction-mediated signal amplification is developed for the detection of cardiac Troponin I (cTnI), a biomarker of acute myocardium infarction. The ECL immunosensor shows a linear response to cTnI in the concentration range of 1 pg mL−1 ∼ 10 ng mL−1 with a detection limit of 0.5 pg mL−1, and exhibits good specificity, reproducibility and long-term stability. The ECL immunosensor is further used for the detection of cTnI in human serum sample. The good recovery suggests its feasibility in clinical application. This work provides a facile molecular engineering strategy to modulate g-CN ECL property, and would promote g-CN ECL in sensing application.

Identifying Luminol Electrochemiluminescence at the Cathode via Single-Atom Catalysts Tuned Oxygen Reduction Reaction.

Luminol-based electrochemiluminescence (ECL) can be readily excited by various reactive oxygen species (ROS) electrogenerated with an oxygen reduction reaction (ORR). However, the multiple active intermediates involved in the ORR catalyzed with complex nanomaterials lead to recognizing the role of ROS still elusive. Moreover, suffering from the absence of the direct electrochemical oxidation of luminol at the cathode and poor transformation efficiency of O2 to ROS, the weak cathodic ECL emission of luminol is often neglected. Herein, owing to the tunable coordination environment and structure-dependent catalytic feature, single-atom catalysts (SACs) are employed to uncover the relationship between the intrinsic ORR activity and ECL behavior. Interestingly, the traditionally negligible cathodic ECL of luminol is first boosted (ca. 70-fold) owing to the combination of electrochemical ORR catalyzed via SACs and chemical oxidation of luminol. The boosted cathodic ECL emission exhibits electron-transfer pathway-dependent response by adjusting the surrounding environment of the center metal atoms in a controlled way to selectively produce different active intermediates. This work bridges the relationship between ORR performance and ECL behavior, which will guide the development of an amplified sensing platform through rational tailoring of the ORR activity of SACs and potential-resolved ECL assays based on the high-efficiency cathodic ECL reported.

Enhanced Cathodic Electrochemiluminescence of Luminol on Iron Electrodes.

Electrochemiluminescence (ECL) behavior of luminol derivative was investigated in reduction on different electrode materials. We found that luminol and its widely used L-012 derivative, emitting at physiological pH values, exhibit strong cathodic ECL emission on iron and stainless steel electrodes with hydrogen peroxide, whereas no ECL signal was observed with other classic electrode materials (Au, Pt, and C). On a Ni electrode, a low cathodic ECL signal was observed. This points out to the essential role of iron-containing materials to enhance the cathodic ECL emission. Under the reported conditions, the cathodic ECL signal of L-012 is comparable to the classically used anodic ECL emission. Thus, dual bright ECL emissions with L-012 were obtained simultaneously in oxidation and in reduction on iron materials as imaged in a wireless bipolar electrochemistry configuration. Such an ECL system generating light emission concomitantly in oxidation and in reduction is extremely rare and it opens appealing (bio)analytical and imaging applications, in biosensing, remote detection, bipolar ECL analysis, and ECL-based cell microscopy.

B, N co-doped graphene synergistic catalyzed ZnO quantum dots with amplified cathodic electrochemiluminescence for fabricating microcystin-LR aptasensor

Exploring efficient methods for microcystin-LR (MC-LR) detection is of great significance for protecting ecological environment safety and human health. Herein, an MC-LR aptasensor was fabricated based on the synergistic amplified cathodic electrochemiluminescence (ECL) of the functional nanocomposite of ZnO quantum dots decorated B, N co-doped graphene (BNG/ZnO). With K2S2O8 as co-reactant, a robust cathodic ECL emission of BNG/ZnO was observed based on the synergistic catalytic effect of B, N in graphene. Interestingly, the ECL intensity of BNG/ZnO nanocomposite was 1.8, 2.9, and 5.4 times enhanced than N-doped graphene/ZnO, B-doped graphene/ZnO, and graphene/ZnO, which was because of the difference in the electronegativity of B, C, and N could generate a unique synergistic effect to make graphene-based materials realizing signal amplification. Subsequently, a novel cathodic ECL aptasensor was constructed for sensitive and selective detection of MC-LR with aptamer as the recognition element and BNG/ZnO as the luminous reagent. Under optimized conditions, the linear range of the prepared cathodic ECL aptasensor for MC-LR detection was 0.1–5000 pM, the detection limit was 0.03 pM (S/N = 3). At the same time, the proposed aptasensor had good selectivity and stability and showed satisfactory results in actual water sample analysis.

Electrochemistry and Electrochemiluminescence of Coumarin Derivative Microrods: Mechanism Insights.

Organic molecules and related nanomaterials have attracted extensive attention in the realm of electrochemiluminescence (ECL). Herein, a well-known electroluminescence (EL) dopant 2,3,6,7-tetrahydro-1,1,7,7,-tetramethyl-1H,5H,11H-10-(2-benzothiazolyl)quinolizino-[9,9a,1gh] coumarin (C545T) is selected as a new ECL illuminant, which shows a high photoluminescence quantum yield of nearly 100% and excellent ECL performance in the organic phase. For utilizing C545T to achieve ECL detection in aqueous solution, organic microrods of C545T (C545T MRs) were synthesized by a precipitation method. Cyclic voltammetry and differential pulse voltammetry of C545T and C545T MRs in acetonitrile or phosphate buffer showed one reduction and multiple oxidation peaks, suggesting that the multiple charge states of C545T could be produced by continuous electron- or hole-injection processes. The annihilated ECL emission of C545T and C545T MRs was observed using ECL transient technology. In the presence of triethanolamine (TEOA) or potassium persulfate (K2S2O8), C545T MRs can also give bright anodic and cathodic ECL emission at the GCE/water interface. The proposed ECL system not only has multichannel ECL emission but also shows intense yellow emission (569 nm) with a relative ECL efficiency of 0.81 when TEOA was used as a coreactant. Benefiting from the strong ECL emission of the C545T MRs/TEOA system and the quenching effect of dopamine (DA) on ECL, a convenient sensor for DA was developed with high selectivity and sensitivity.

DNA-targeted formation and catalytic reactions of DNAzymes for label-free ratiometric electrochemiluminescence biosensing

A label-free ratiometric electrochemiluminescence (ECL) sensing strategy for the sensitive detection of target DNA (T-DNA) was proposed on the basis of G-quadruplex/hemin-regulated ECL emissions of CdS quantum dots (QDs) and luminol with their common coreactant of H2O2. The ECL biosensor was constructed through stepwise assemblies of CdS QDs and hairpin DNA (H-DNA) on a glassy carbon electrode, and subsequent introduction of T-DNA resulted in the development of G-quadruplex/hemin DNAzymes via the specific recognition of T-DNA and H-DNA in the presence of hemin and K+ ions. The formed DNAzymes not only prompted the catalytic oxidation of hydroquinone followed by deposition of insoluble oxidation oligomers on the electrode surface to attenuate the cathodic ECL emission of CdS QDs but also triggered the catalytic oxidation of luminol to enhance the anodic ECL emission. The label-free ratiometric ECL biosensor for the detection of T-DNA showed a wide response range from 1 to 10,000 fM (10−15 M) with a low detection limit of 0.2 fM and exhibited excellent selectivity against mismatched base sequences. This work provides a reliable and sensitive sensing platform for the detection of targets in analytical community by means of rational design of DNA sequences.

Gold nanostar-enhanced electrochemiluminescence immunosensor for highly sensitive detection of cancer stem cells using CD133 membrane biomarker

Gold nanostars (AuNSs) demonstrate an intense electromagnetic field around tip of branches. In this research, we employed AuNSs-enhanced electrochemiluminescence (ECL) emission from graphitic carbon nitride nanosheets (g-CN nanosheets) to detect CD133 peptide as a cancer stem cell membrane biomarker. In this biosensor, the g-CN nanosheets were decorated with AuNSs (AuNSs@g-CN nanosheets). AuNSs@g-CN nanosheets exhibited strong and stable cathodic ECL emission compared to that of pure g-CN nanosheets. The ECL intensity from the AuNSs@g-CN nanosheets was over 30% higher than that of spherical gold nanoparticles (spherical AuNPs) decorated g-CN nanosheets. The additional ECL enhancement of AuNSs was due to the localized surface plasmon resonance (LSPR) effect located around multiple branch tips of AuNSs. The RSD of ECL curves intensities, obtained from successive potential scans for 10 cycles, were less than 4%, indicating the superior stability of the AuNSs@g-CN nanosheets. Under optimum conditions, the ECL intensity of GCE/AuNSs@g-CN nanosheets/anti-CD133 decreased linearly with CD133 peptide concentration in the range of 0.05–100 ng mL−1. The LOD achieved was 0.257 ng mL−1 (S/N = 3). The applicability of the designed biosensor in real samples was examined through the determination of CD133 peptide in spiked serum samples, from which satisfactory results were obtained.

Quaternary Ammonium Salt-Functionalized Tetraphenylethene Derivative Boosts Electrochemiluminescence for Highly Sensitive Aqueous-Phase Biosensing.

Aggregation induced emission active compounds (AIEgens) have appeared as a new kind of electrochemiluminescence (ECL) emitters due to their bright emission in the aggregated state but lack functional groups. Herein, we report a quaternary ammonium salt groups-functionalized AIEgen (QAU-1) and discover that coating QAU-1 on the indium tin oxide (ITO) surface (QAU/ITO) enabled QAU-1 to display significant cathodic ECL emission compared with that of QAU-1 in the dissolved state. Inspired by this, we applied QAU-1 as emitters to develop a novel ECL biosensor (Fc-DNA/QAU/ITO) through electrostatic attraction between QAU/ITO and a ferrocene-labeled ssDNA (Fc-DNA), and the developed biosensor was employed to detect bleomycin (BLM) with high sensitivity based on the target-initiated specific cleavage and subsequent removal of Fc molecules from the electrode. We envision this work will open up a new avenue to development of high-performance ECL biosensors, which will display a significant potential application in the field of analysis.

Highly Efficient Dual-Polar Electrochemiluminescence from Au25 Nanoclusters: The Next Generation of Multibiomarker Detection in a Single Step

For the first time, simultaneous cathodic and anodic electrochemiluminescence (ECL) emissions of bull serum albumin stabilized Au25 nanoclusters (Au25 NCs) as highly efficient bipolar ECL probes were constructed for the single-step and synchronous determination of carcinoembryonic antigen (CEA) and mucin 1 (MUC1) based on different coreactant and coreaction accelerators. Under the potential cathodic scanning, TiO2 nanosheets (TiO2 NSs) as cathodic coreaction accelerators could catalyze the reduction of coreactant dissolved O2 for promoting cathodic ECL emission of Au25 NCs, while, under the potential anodic scanning, Cu2O@Cu nanoparticles (Cu2O@Cu NPs) as anodic coreaction accelerators could stimulate the oxidation of coreactant N,N-diethylethylenediamine (DEDA) for enhancing anodic ECL emission of Au25 NCs. Thus, the proposed strategy easily solved one main technical challenge of cross reactions of dual-luminophors for dual-biomarker detection, resulting in great sensitivity and accuracy toward the detection of CEA down to 0.43 pg/mL and MUC1 down to 5.8 fg/mL. As a proof of concept, this work realized single-step and simultaneous detection of dual biomarkers, which initiates a new thought in realizing a new generation of dual-biomarker ECL detection beyond the traditional ones in sensing analysis and diagnostic sensing.

Ratiometric electrochemiluminescence sensing platform for sensitive glucose detection based on in situ generation and conversion of coreactants

A novel ratiometric electrochemiluminescence (ECL) biosensor was developed for sensitive detection of glucose in combination of graphitic-phase carbon nitride-supported Au nanocomposites (Au-g-C3N4) and luminol as cathodic and anodic ECL emitters, respectively, only with dissolved oxygen in aqueous solution. Glucose oxidase-immobilized Au-g-C3N4 nanocomposites (GOx/Au-g-C3N4) were modified on a glassy carbon electrode to construct a sensing platform in the presence of luminol. Before glucose was added, the g-C3N4 nanosheets could give a strong cathodic ECL emission with dissolved oxygen as a coreactant in aqueous solution. In the presence of glucose, hydrogen peroxide was in situ generated from dissolved oxygen, catalyzed by GOx and further by Au nanoparticles, and was then converted to reactive oxygen species, which led to an anodic ECL emission from luminol, concomitant with a decrease in the cathodic ECL emission from the g-C3N4 nanosheets. The ratiometric ECL responses were closely related to the competitive consumption of dissolved oxygen by the g-C3N4 nanosheets and luminol (by means of the GOx-immobilized Au nanoparticles). The constructed ratiometric ECL biosensor showed high sensitivity and selectivity for the detection of glucose, with a wide concentration range of 0.1–8000μM and a low detection limit of 0.05μM (S/N=3). Furthermore, this constructed ratiometric ECL sensing platform was successfully applied to detect glucose in real samples independent of interference from other biomolecules. This proposed strategy opens an alternative avenue for ECL signal transduction and shows a promising application in clinical diagnostics.