Luminol Electrochemiluminescence Research Articles

Sensitive detection of bisphenol A based on resonance energy transfer between zinc oxide nanoparticles enhanced luminol ECL and silver nanoparticles decorated TiVC MXene

This present work developed a highly sensitive electrochemiluminescence (ECL) sensor based on resonance energy transfer between ZnO nanoparticles (ZnONPs) enhanced luminol ECL as the energy donor and silver nanoparticle-modified TiVC MXene (AgNPs@TiVC) as the energy acceptor. ZnONPs were employed as catalysts to facilitate the reaction between luminol and dissolved oxygen, which could amplify the ECL signal of luminol without the need of additional co-reactants. The AgNPs@TiVC composite functioned as the energy acceptor, participating in ECL resonance energy transfer to quench the ECL emission. In the presence of bisphenol A (BPA), the specific recognition by the aptamer could detach the energy acceptor from the electrode surface, resulting in the recovery of ECL signal. The variation of ECL intensity exhibited a good linear relationship with the logarithm of BPA concentration in the range of 0.06 nM–0.08 μM, with a detection limit of 8.9 pM (3σ). This sensor owned satisfactory sensitivity and selectivity, which could further expand the utility of various MXenes in ECL sensing applications.

Multimodal generation of luminol electrochemiluminescence through TEMPO functionalized carbon nanotubes

The utilization of an elaborate nanomaterial is still a prevalent method to generate luminol electrochemiluminescence (ECL). Herein, we report on the multimodal generation of anodic and cathodic luminol ECL through a metal-free nanomaterial. This nanomaterial was prepared by covalently grafting 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) on the surface of multi-walled carbon nanotube (MWCNT). TEMPO-MWCNTs modified electrode exhibit high electrocatalytic activities toward H2O, luminol, H2O2 and O2 during the oxidation/reduction processes. Such electrocatalysis has not only resulted in significant enhancement of luminol ECL, but also enabled the generation of three ECL peaks in luminol/O2 system and two ECL peaks in luminol/H2O2 system on the electrode via different pathways. The natures of these ECL peaks are also revealed through the spooling ECL spectra. Furthermore, an ECL sensor has been designed for sensitive detection of an organophosphorus pesticide (OP) based on the enhanced ECL of luminol/H2O2 system. Therefore, this work suggests that nitroxyl radical functionalized carbon nanomaterial can be used as a new electrocatalyst for studying luminol ECL in the presence of either an endogenous or exogenous co-reactant.

Qualitative and quantitative electrochemiluminescence evaluation of trace Pt single-atom in MXenes

The analysis of trace Pt single-atom (SA) represents a significant challenge, given the crucial role of single-atom platinum (Pt) in energy storage and electrocatalysis. Here, we present an electrochemiluminescence (ECL) platform that enables the qualitative and quantitative analysis of trace Pt SA using luminol as the ECL luminophore. It is observed that different Pt species in Ti3-xC2Ty MXenes resulted in distinct reactive oxygen species (ROS) potentials for luminol cathodic electrochemiluminescence (ECL), achieved through distinctive oxygen reduction reaction (ORR) pathways, in which oxygen acts as the co-reactant. Furthermore, the cathodic luminol ECL intensity increases in proportion to the Pt atom content, thereby enabling quantitative analysis of trace Pt single atoms. The detection limit is 0.014 wt%, which is comparable to the current mainstream Pt SA quantification techniques. By utilizing this ECL method, it is possible to successfully evaluate both qualitatively and quantitatively the changes in Pt SA during the ORR processes. This ECL platform provides a valuable toolbox for the analysis of Pt SA catalysts and for the evaluation of the mechanisms involved in electrocatalysis applications.

Bright luminol electrochemiluminescence mediated by a simple TEMPO radical for visualized multiplex detection

In this work, a series of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) radicals bearing different functional groups were exploited as a simple catalyst to promote electrochemiluminescence (ECL) generation in luminol/H2O2 system. These TEMPO radicals were found to facilitate the electrochemical oxidation of H2O2 and luminol through different catalytic mechanisms, as well as the subsequent ECL generation of luminol/H2O2 system. The electrochemical oxidation and luminol ECL generation could be tuned by the functional group on the para-position of TEMPO, for which the structure/activity relationship was revealed. Finally, with the combination of enzymatic system, luminol ECL enhancement up to 9.6-fold was obtained through the catalysis of 4-hydroxyl-TEMPO. The enhanced luminol ECL allows acquiring brighter ECL images in a single-electrochemical system (SEES) for multiplex detection of cholesterol, H2O2 and glucose.

Sensitive detection of uric acid based on low-triggering-potential cathodic luminol electrochemiluminescence achieved by ReS2 nanosheets.

The majority of previously reported cathodic electrochemiluminescence (ECL) systems often required very negative potential to be carried out, which hasgreatly limited their applications in the sensing field. Screening high-performance cathodic ECL systems with low triggering potential is a promising way to broaden their applications. In this work, rhenium disulfide nanosheets (ReS2 NS) have been revealed as an efficient co-promoter to realize low-triggering-potential cathodic luminol ECL. One strong cathodic ECL signal appeared at a potential of -0.3V and one anodic ECL peak was obtained at -0.15V under the reverse potential scan, which were caused by electrogenerated reactive oxygen species (ROS) from hydrogen peroxide. The generation of strong luminol ECL at low potential was the result of the electrocatalytic effect of ReS2 NS on the reduction of H2O2. The scavenging effect of uric acid (UA) on the ROS could significantly inhibit the cathodic ECL. As a result, an ECL sensor was proposed, which showed outstanding performance for the detection of UA in the range of 10nM to 0.1mM with a low detection limit of 1.53nM. Moreover, the ECL sensor was successfully applied in the sensitive detection of UA in real samples. This work provides anew avenue to establish a low-potential cathodic ECL system, which will sufficiently expand the potential application of cathodic ECL in the sensing field.

Electrochemiluminescence Immunosensor for Alpha-Fetoprotein Based on Polypyrrole-Luminol Nanoparticles

The study of luminol electrochemiluminescence (ECL) is commonly conducted in alkaline solutions. However, many substances, especially biomolecules, are only stable in neutral or weakly acidic media. In this study, a sensitive ECL immunosensor was developed using polypyrrole-luminol (PPY-Lu) nanoparticles for the determination of alpha-fetoprotein (AFP) in a neutral buffer. Polypyrrole (PPY) nanoparticles were synthesized by chemical oxidation. Subsequently, luminol was attached to the PPY nanoparticles via electrostatic interaction, resulting in the formation of the desired nanoparticles which exhibited strong and stable electrochemiluminescence in neutral solution. Furthermore, the PPY-Lu nanoparticles have abundant amino groups suitable for immobilizing biomolecules. An ECL immunosensor for AFP was fabricated by immobilizing anti-AFP on the PPY-Lu-modified electrode surface. The electrochemiluminescence decreased when AFP was captured. The immunosensor exhibited a linear range from 1.0 × 10−11 to 1.0 × 10−6 mg/mL with a low detection limit of 8.5 × 10−12 mg/mL and excellent specificity, reproducibility, and long-term stability. This designed immunosensor provides a new method for the determination of biomarkers in clinical analysis.

Ultrastable Luminol-OH--(Ni-WOx-CNT) ECL System with High Strength and Its Applications in Sensing.

In traditional luminol electrochemiluminescence (ECL) systems, hydrogen peroxide (H2O2) and dissolved oxygen (DO) are the commonly used coreactants to generate reactive oxygen species (ROS) for ECL emission. However, the self-decomposition of hydrogen peroxide and the limited solubility and content of oxygen in solution undoubtedly restrict the luminescence efficiency and stability of the luminol ECL system. Inspired by the ROS-mediated ECL mechanism, we pioneered hydroxide ion as an advanced luminol ECL coreactant using nickel-doped and carbon nanotube-modified tungsten oxide (Ni-WOx-CNT) as the coreactant accelerator. Owing to the excellent catalytic activity of Ni-WOx-CNT, amounts of ROS were generated from OH- at a low excitation voltage, which subsequently reacted with luminol anion radicals and triggered intense ECL signals. Experiments confirmed an impressive ECL behavior in terms of high luminescent intensity (85,563 a.u.) and super stability over 1300 consecutive tests; both are superior to those recently reported luminol-H2O2 and luminol-DO systems with smaller ECL intensities and consecutive tests less than 25 times. To validate the feasibility and versatility of the developed system in sensor, traditional three-electrodes system and closed bipolar electrodes system with various sensing strategies of direct oxidation, "gate-effect" of molecularly imprinted polymer, immune reaction, and enzyme-catalyzed reaction were proposed to monitor uric acid (UA), C-reactive protein (CRP), immunoglobulin G (IgG), and glucose (Glu). The superior sensing performances confirmed the great application potential of the developed ROS-mediated ECL system.

Boosting Electrochemiluminescence Performance of a Dual-Active Site Iron Single-Atom Catalyst-Based Luminol-Dissolved Oxygen System via Plasmon-Induced Hot Holes.

Due to the commonly low content of biomarkers in diseases, increasing the sensitivity of electrochemiluminescence (ECL) systems is of great significance for in vitro ECL diagnosis and biodetection. Although dissolved O2 (DO) has recently been considered superior to H2O2 as a coreactant in the most widely used luminol ECL systems owing to its improved stability and less biotoxicity, it still has unsatisfactory ECL performance because of its ultralow reactivity. In this study, an effective plasmonic luminol-DO ECL system has been developed by complexing luminol-capped Ag nanoparticles (AgNPs) with plasma-treated Fe single-atom catalysts (Fe-SACs) embedded in graphitic carbon nitride (g-CN) (pFe-g-CN). Under optimal conditions, the performance of the resulting ECL system could be markedly increased up to 1300-fold compared to the traditional luminol-DO system. Further investigations revealed that duple binding sites of pFe-g-CN and plasmonically induced hot holes that disseminated from AgNPs to g-CN surfaces lead to facilitate significantly the luminous reaction process of the system. The proposed luminol-DO ECL system was further employed for the stable and ultrasensitive detection of prostate-specific antigen in a wide linear range of 1.0 fg/mL to 1 μg/mL, with a pretty low limit of detection of 0.183 fg/mL.

Fe-single-atom catalysts boosting electrochemiluminescence via bipolar electrode integrated with its peroxidase-like activity for bioanalysis

Multifunctional single-atom catalysts (SACs) have been extensively investigated as outstanding signal amplifiers in bioanalysis field. Herein, a type of Fe single-atom catalysts with Fe-nitrogen coordination sites in nitrogen-doped carbon (Fe–N/C SACs) was synthesized and demonstrated to possess both catalase and peroxidase-like activity. Utilizing Fe–N/C SACs as dual signal amplifier, an efficient bipolar electrode (BPE)-based electrochemiluminescence (ECL) immunoassay was presented for determination of prostate-specific antigen (PSA). The cathode pole of the BPE-ECL platform modified with Fe–N/C SACs is served as the sensing side and luminol at the anode as signal output side. Fe–N/C SACs could catalyze decomposition of H2O2 via their high catalase-like activity and then increase the Faraday current, which can boost the ECL of luminol due to the electroneutrality in a closed BPE system. Meanwhile, in the presence of the target, glucose oxidase (GOx)-Au NPs-Ab2 was introduced through specific immunoreaction, which catalyzes the formation of H2O2. Subsequently, Fe–N/C SACs with peroxidase-like activity catalyze the reaction of H2O2 and 4-chloro-1-naphthol (4-CN) to generate insoluble precipitates, which hinders electron transfer and then inhibits the ECL at the anode. Thus, dual signal amplification of Fe–N/C SACs was achieved by increasing the initial ECL and inhibiting the ECL in the presence of target. The assay exhibits sensitive detection of PSA linearly from 1.0 pg/mL to 100 ng/mL with a detection limit of 0.62 pg/mL. The work demonstrated a new ECL enhancement strategy of SACs via BPE system and expands the application of SACs in bioanalysis field.

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.

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.

Triggering Anodic Luminol Electrochemiluminescence through Electrostatic Interactions: An Innovative Approach Utilizing Conductive Metal–Organic Framework Co-HHTP

Triggering Anodic Luminol Electrochemiluminescence through Electrostatic Interactions: An Innovative Approach Utilizing Conductive Metal–Organic Framework Co-HHTP

Double-enhanced sandwich electrochemiluminescence aptasensor based on g-C3N4–Au-luminol nanocomposites and ZnCuS nanosheets for highly sensitive detection of mucin 1

The traditional luminol electrochemiluminescence (ECL) sensing suffers from low signal response and instability issues. Here, an Au/ZnCuS double-enhanced g-C3N4-supported luminol ECL aptasensor is constructed for the sensitive detection of human mucin 1 (MUC1). In this platform, g-C3N4 of a large specific surface area is beneficial to load more luminol illuminants. Au nanoparticles promote the decomposition of H2O2 coreactants to generate more reactive oxygen (•OH and O2•−) intermediates, while ZnCuS can immobilize the aptamer and simultaneously catalyze H2O2 decomposition, realizing the double-wing signal amplification. Under optimal conditions, this sensor shows a good detection capability within 1.0 × 10−4–1.0 × 103 ng mL−1 and a low detection limit of 5.0 × 10−5 ng mL−1, as well as ideal stability, selectivity, and reproducibility. This double-enhanced aptasensor highlights a new signal-enhancement approach for early biomarker detection.

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.

Single-atom iron boosts electrochemiluminescence for ultrasensitive carcinoembryonic antigen detection.

Asimple and ultrasensitive sandwich-type electrochemiluminescence (ECL) immunosensor has been developedusing porous three-dimensional gold nanoparticles (Au NPs) iron(Fe)-zinc(Zn) metal-organic frameworks (Au NPs-FeZn-MOFs@luminol) as high-efficiency ECL signal probes with Fe single-atom catalysts (SACs) (Fe-N-C SACs) as potentially advanced coreaction accelerators and dissolved oxygen as a coreaction agent to realize an H2O2-free amplification method for detecting carcinoembryonic antigen (CEA). The cathodic ECL of luminol, which was usually negligible, increased first. Because the Fe-N-C SACs exhibited an outstanding catalytic performance and a unique electronic structure, different reactive oxygen species (ROS) were generated via the oxygen reduction reaction. ROS oxidized the luminol anions to luminol anion radicals, preventing the time-consuming luminol electrochemical oxidation. Furthermore, the luminol anion radicals generated in situ reacted with ROS to produce potent cathodic ECL emissions. The immunosensor exhibited favorable analytical accuracy (detection range: 0.1 pg mL-1-80 ng mL-1), and its detection limit for serum samples was 0.031 pg mL-1 (S/N = 3). Consequently, the proposed strategy offers a new approach for early screening of CEA.

Cathodic electrochemiluminescence of L012 and its application in antioxidant detection.

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

Spotting d-band centers of single-atom catalysts by oxygen intermediate-boosted electrochemiluminescence.

Catalytic activities of single-atom catalysts are strongly dependent on their d-band centers. However, it is a long-standing challenge to provide a cost-effective and accurate evaluation for the positions of d-band centers of these catalysts due to the fact that the widely applicable photoelectron spectroscopy methodologies require complicated sampling and spectral unfolding processes. In this contribution, we have proposed oxygen intermediate-boosted electrochemiluminescence (ECL) for rapid spotting of the d-band centers of single-atom catalysts, involving single atomic Au, Ag, Cu and Fe. It was disclosed that the d-band centers of single-atom catalysts closer to the Fermi level could facilitate the interaction between catalysts and oxygen intermediates, leading to higher luminol ECL intensities as a result of the promoted adsorption and reduction ability towards oxygen intermediates. Moreover, this correlation was also adapted for other metal catalysts such as Au and Ag nanoparticles. This correspondence could be utilized for an accurate identification of d-band centers of single-atom catalysts. It is anticipated that the proposed strategy could be beneficial for a deep understanding of microstructure studies of single-atom catalysts to achieve advanced catalytic performances.

PdPtB Electrochemiluminescence Nanoenhancer and SiC@Au-PEDOT Nanowires-Based Detection of β-Amyloid Oligomers in Alzheimer's Disease.

β-Amyloid oligomers (AβOs) are promising biomarkers for the diagnosis of Alzheimer's disease (AD). The present research introduces a novel electrochemiluminescence (ECL) immunosensor based on PdPtB nanoenhancer and SiC@Au-PEDOT nanowires (NWs) for the specific and ultrasensitive detection of AβOs. The PdPtB nanoenhancer exhibited excellent oxidase-like catalytic activity with in situ generation of reactive oxygen species (ROS) to enhance luminol ECL in neutral media. In addition, SiC@Au-PEDOT NWs were utilized as a biocompatible and conductive substrate for the modification of the glassy carbon electrode (GCE). With this design, the ECL immunosensor showed outstanding AβOs analytical performance without exogenous coreactant. The ECL immunosensor demonstrated a favorable linear range of 20 pM to 20 nM and a detection limit of 10 pM under optimized conditions with potential straightforward clinical application. In general, the developed ECL immunosensor provides a promising strategy for the early diagnosis of AD.

N-doped TiO2/Ti3C2-driven self-photocatalytic molecularly imprinted ECL sensor for sensitive and steady detection of dexamethasone

The conventional luminol-based electrochemiluminescence (ECL) biosensor suffers from hampered signal stability due to the self-decomposition of the H2O2 co-reactant. Here, we propose an N-doped TiO2/Ti3C2 heterojunction driven self-photocatalytic platform for ECL signal amplification and then combine it with molecular imprinting technology for sensitive and steady detection of dexamethasone (DXM). Unlike traditional cases involving specific catalysts or external electron injection, the initial luminescence of luminol in this new system is utilized as the excitation light of N-doped TiO2/Ti3C2 photocatalyst to promote the conversation of dissolved oxygen to H2O2, supplying more co-reactants to improve ECL of luminol in turn. Thanks to the heterojunction and self-photocatalytic cyclic amplification, this molecularly imprinted ECL sensor exhibits a wide linear range (1.0 × 10−6–1.0 × 101 μg mL−1) and a low detection limit, as well as excellent anti-interference capability, sensitivity, and stability. This work contributes to more reliable and steady detection of DXM and brings new insights into developing exogenous co-reactant-free self-enhancement ECL models for biosensor applications.

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.