Electrochemiluminescence Detection Research Articles

Electrochemiluminescence in Graphitic Carbon Nitride Decorated with Silver Nanoparticles for Dopamine Determination Using Machine Learning.

Electrochemiluminescence (ECL) luminophores with wavelength-tunable multicolor emissions are essential for multicolor ECL imaging detection and multiplexed analysis. In this work, silver nanoparticle (Ag NP)-decorated graphitic carbon nitride (g-CN@Ag) nanocomposites were synthesized. The morphology, chemical composition, structure, and ECL property of g-CN@Ag were investigated. The prepared g-CN, g-CN@Ag1, g-CN@Ag5, and g-CN@Ag10 can produce blue, blue-green, chartreuse, and yellow colored ECL emissions, respectively, by using K2S2O8 as the coreagent. The ECL emission wavelength of g-CN@Ag can be regulated from 460 to 565 nm by modulating the content of the immobilized Ag NPs. Then, a multicolor ECL detection array was fabricated by using g-CN, g-CN@Ag1, g-CN@Ag5, and g-CN@Ag10 as four ECL luminophores. Dopamine was detected based on its inhibition effect on the multicolor ECL emissions. The linear range is from 0.1 nM to 1 mM with the lowest detection limit of 44 pM. Then, machine learning-assisted multiparameter concentration prediction of dopamine was further carried out by combining the deep neural network (DNN) algorithm. This work provides a new avenue to regulate the ECL emission wavelength of g-CN by using the metal nanoparticle modification strategy and presents an effective machine learning-assisted multicolor ECL detection strategy for accurate multiparameter quantitative detection.

Electrochemiluminescent evaluation of GLUT4 expression in rat adipocytes induced by Ganoderma lucidum polysaccharides

Glucose transporter 4 (GLUT4) directly facilitates cellular uptake of glucose and plays a crucial role in mammalian adipose tissue glucose metabolism. In this work, we constructed a cytosensor for sensitive electrochemiluminescence (ECL) detection of GLUT4 in rat adipocytes (RA cells). A carbon nanotube sponge (CNTSP) was selected to fabricate a permeable electrode to overcome the steric hindrance of cells on the electrode. The expression of GLUT4 after treatment with Ganoderma lucidum polysaccharide (GLP) was assessed by analyzing the luminescence emitted from cell-surface ECL probes. Our preliminary results suggest that GLP promote the expression of GLUT4, thereby enhancing the uptake of the fluorescent glucose 2-NBDG. Treatment with GLP affected GLUT4 expression in RA cells in a dose-dependent manner. Additionally, the ECL cytosensor contributes to the development of ECL imaging of receptors on the cell surface for clinical drug evaluation.

Visualized electrochemiluminescence detection of trace copper in practical food samples

Copper as a widely applied element in food supply chain can cause serious contamination issues that threats food safety. In this research, we present a quick and visible method for trace copper ion (Cu2+) quantification in practical food samples. Polymer dots (Pdots) were firstly conjugated with a copper-specific DNA aptamer and then tailored with rhodamine B (RhB) to extinguish the electrochemiluminescence (ECL) signal through a resonance energy transfer process. The selective release of RhB leads to signal restoration when exposed to trace Cu2+ levels, achieving remarkable linearity with the logarithm of Cu2+ concentration within the range of 1 ng/L to 10 μg/L with an impressively low limit of detection at 11.8 pg/L. Most notably, our device was also applicable on visualizing and quantifying trace Cu2+ (∼0.2 μg/g) in practical Glycyrrhiza uralensis Fisch. samples, underscoring its potential as a tool for the early prevention of potential copper contamination in food samples.

Logic Signal Amplification System for Sensitive Electrochemiluminescence Detection and Subtype Identification of Cancer Cells.

Achieving sensitive detection and accurate identification of cancer cells is vital for diagnosing and treating the disease. Here, we developed a logic signal amplification system using DNA tetrahedron-mediated three-dimensional (3D) DNA nanonetworks for sensitive electrochemiluminescence (ECL) detection and subtype identification of cancer cells. Specially designed hairpins were integrated into DNA tetrahedral nanostructures (DTNs) to perform a catalytic hairpin assembly (CHA) reaction in the presence of target microRNA, forming hyperbranched 3D nanonetworks. Benefiting from the "spatial confinement effect," the DNA tetrahedron-mediated catalytic hairpin assembly (DTCHA) reaction displayed significantly faster kinetics and greater cycle conversion efficiency than traditional CHA. The resulting 3D nanonetworks could load a large amount of Ru(phen)32+, significantly enhancing its ECL signal, and exhibit detection limits for both miR-21 and miR-141 at the femtomolar level. The biosensor based on modular logic gates facilitated the distinction and quantification of cancer cells and normal cells based on miR-21 levels, combined with miR-141 levels, to further identify different subtypes of breast cancer cells. Overall, this study provides potential applications in miRNA-related clinical diagnostics.

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.

Molecular imprinting-based Ru@SiO2-embedded covalent organic frameworks composite for electrochemiluminescence detection of cyanidin-3-O-glucoside

Cyanidin-3-O-glucoside (C3G), a natural antioxidant, plays multiple physiological or pathological roles in maintaining human health; thereby, designing advanced sensors to achieve specific recognition and high-sensitivity detection of C3G is significant. Herein, an imprinted-type electrochemiluminescence (ECL) sensing platform was developed using core-shell Ru@SiO2-CMIPs, which were prepared by covalent organic framework (COF)-based molecularly imprinted polymers (CMIPs) embedded in luminescent Ru@SiO2 cores. The C3G-imprinted COF shell not only helps generate a steady-enhanced ECL signal, but also enables specific recognition of C3G. When C3G is bound to Ru@SiO2-CMIPs with abundant imprinted cavities, resonance energy transfer (RET) behavior is triggered, resulting in a quenched ECL response. The constructed Ru@SiO2-CMIPs nanoprobes exhibit ultra-high sensitivity, absolute specificity, and an ultra-low detection limit (0.15 pg mL−1) for analyzing C3G in food matrices. This study provides a means to construct an efficient and reliable molecular imprinting-based ECL sensor for food analysis.

Hollow graphitic carbon nitride with tunable shell thickness for electrochemiluminescence and photoelectrochemistry dual-mode detection of cardiac troponin I

An electrochemiluminescence (ECL) and photoelectrochemistry (PEC) dual-mode immunosensor based on hollow graphitic carbon nitride (H-C3N4) as dual-signal indicator was constructed for sensitive and accurate detection of cardiac troponin I (cTnI). Studied have been demonstrated that hollow structures rather than bulk nanomaterials can be able to decrease the inner filter effect and reduce the migration of photogenerated charges. Herein, we precisely control the shell thickness of H-C3N4 from 15.3 to 34.7 nm and clearly explore their correlating ECL-PEC performances. Notably, ECL and PEC performances of the optimal shell thickness of H-C3N4 (25.1 nm) is 2.7 and 4.4 times higher than that of solid C3N4, which leaves enormous room for optimization the performances of H-C3N4. Furthermore, TiO2 not only is a coreaction accelerator, but also possesses well-matched band structure with H-C3N4. By integrating TiO2 with the optimal H-C3N4, the obtained H-C3N4@TiO2 shows the highest ECL and PEC response. As a result, the established immunosensor shows the sensitive detection of cTnI with a desirable detection limit of 0.65 fg mL−1 (ECL) and 0.63 fg mL−1 (PEC), respectively. This work shows an effective strategy to develop a dual-mode immunosensor which allows signal cross-checking and presents a reliability detection in bioanalysis.

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.

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.

Detection of acetamiprid residues in vegetables by a self-enhanced bimetallic luminescent MOF-based electrochemiluminescence-electrochemistry dual-mode aptasensor

In this study, a dual-mode aptasensor based on the competition mechanism was constructed to detect acetamiprid (ACE) residues in vegetables. With 3,5-dicarboxyphenylboronic acid (5-bop) as a ligand, a bimetallic RuZn-based metal-organic framework (RuZn-MOF) was synthetized by applying a hydrothermal method to achieve efficient electrochemiluminescence (ECL) and electrochemistry (EC) dual-mode detection of ACE. Compared with the monometallic Zn-based metal-organic framework (Zn-MOF) of the same structure, the bimetallic RuZn-MOF exhibited a greater ability to transfer electrons due to the synergistic effect between different metal and the 5-bop ligand. Meanwhile, the complementary DNA (cDNA) probe for bonding the ACE aptamer was modified with ferrocene (Fc) and methylene blue (MB). When the target pesticide of ACE was present, ACE competed with the cDNA probe, so that the ECL achieved the "signal on" and the EC achieved the "signal off". ECL and EC detection being combined, the results showed that the two detection methods corroborated each other and worked synergistically, i.e., they effectively reduced the systematic errors and background signals, and improved the reliability of the detection. The linear ranges of the ECL and EC aptasensors were 1 pg/mL-1 μg/mL with the limit of detection (LOD) of 0.33 pg/mL, and 1 fg/mL-1 ng/mL with LOD of 0.33 fg/mL (S/N=3), respectively. The dual-mode strategy had good stability and specificity, providing some valuable support for the detection and analysis of other substances.

Electrochemiluminescence detection of diazinon in vegetables based on the synergistic interaction of WO3-x dots with Au@SiO2 nanocapsules

In this work, a simple synthesis of low-toxicity transition metal material of WO3-x dots was used as a co-reactant with Au@SiO2 as a core-shell material and a signal amplification factor to collaboratively promote Ru(bpy)32+ electrochemiluminescence (ECL) for the construction of a highly sensitive aptasensor for the detection of diazinon (DZN) in vegetables. Electrodes modified with multi-walled carbon nanotubes-chitosan composite membranes (MWCNTs-CS) were used to load and immobilize more Ru(bpy)32+.can load more Ru(bpy)32+. WO3-x dots synthesized by a simple method showed excellent ECL efficiency as a novel co-reactant for Ru(bpy)32+. Under optimized conditions, this aptasensor for DZN has a wide detection range (10 pg mL−1 - 1 μg mL−1.) and a low detection limit (0.0197 ng L−1). The aptasensor has shown good results in the analysis of real samples in the experiment. This work provides a new approach to the construction of a novel electrochemiluminescence sensor for the detection of pesticides.

A dual-mode biosensor based on silica inverse opal photonic crystals modulated electrochemiluminescence and dye displacement colorimetry for the sensitive detection of synthetic cathinone in water environment

To address the challenges posed by signal capacity limitations and the reliance of sensing methods on single analytical information, this study developed an electrochemiluminescence (ECL) and colorimetric dual-mode sensing platform for the precise detection of 4-chloroethcathinone (4-CEC) in water environments. Firstly, the accurate alignment of the reflection wavelength of appropriately sized silica inverse opal photonic crystals (SIOPCs) with the ECL emission wavelength of luminescent metal-organic frameworks (PCN-224) has been achieved via diameter modulation. This innovative design, which cleverly utilized the band-edge effect, improved the luminous intensity of the ECL sensor, leading to a significant boost in analytical performance. Secondly, the establishment of a colorimetric detection method for confirming the presence of 4-CEC in samples through visual observation of color changes was achieved by employing an aptamer-based dye displacement reaction, utilizing differential binding affinities between the aptamer and both the sulforhodamine B (SRB) and 4-CEC. Under the optimal experimental conditions, the dual-mode sensor demonstrated ECL detection of limits (LOD) of 2.6 × 10−13 g/L and colorimetric LOD of 6.5 ng/L for 4-CEC. These findings highlighted the tremendous potential of developing streamlined and efficient dual-signal readout platforms using ECL aptamer sensors for the precise determination of other Synthetic cathinones (SCs) in water environments.

Hollow-microsphere-integrated optofluidic immunochip for myocardial infarction biomarker microanalysis

This work developed an optofluidic immunochip that uses whispering gallery mode with fiber laser enhancement, for the rapid detection of a key biomarker cardiac troponin I for acute myocardial infarction (AMI). The immunochip adopted an innovative design, using perforated hollow glass microspheres (HGMS) as carriers, with antibodies immobilized on the inner surface of the HGMS, thereby achieving ultra-low sample consumption. The performance of the immunochip was improved by fiber laser, including spectral width compression to 0.019 nm, optical signal-to-noise ratio amplification to 63.17 dB, and an enhancement in the limit of detection to 5 pg/mL. Moreover, this immunochip can provide results within 15 minutes, making it highly suitable for early AMI risk management. Compared to the standard electrochemiluminescence detection method, although some differences exist in the results of the immunochip due to the principle of detection and differences in antibody affinity, its positive reference value can be calculated as 0.0754 ng/mL, with a successful recognition rate of 88% for positive patients. The immunosensor is integrated on a polydimethylsiloxane substrate, with a compact size suitable for use in point-of-care devices and AMI self-screening, as well as rapid disease screening and microanalysis of various biomarkers, offering new possibilities for applications in these fields.

Molecularly imprinted electrochemiluminescence sensor based on a novel luminol derivative for detection of human serum albumin via click reaction.

Anovel luminol derivative of N-(1,4-dioxo-1,2,3,4-tetrahydrophthalazin-5-yl)acrylamide (DTA) with excellent luminescence efficiency was designed and synthesized. Furthermore, a molecularly imprinted electrochemiluminescence sensor (MIECLS) was fabricated to detect ultratrace levels of human serum albumin (HSA) with high sensitivity and selectivity via a click reaction. The molecularly imprinted polymers (MIPs) were formed on the electrode surface via electropolymerization with HSA as a template molecule and catechol as a monomer. In the detection process, the -SH group of HSA on the electrode and the C = C bond of acryloyl group in DTA formed a new C-S bond via the Michael addition reaction to construct the MIECLS. The higher the concentration of HSA, the greater electrochemiluminescence (ECL) intensity measured. Taking advantage of MIECLS for ECL detection (scanning potential, - 0.4 to 0.5V), there was a good linear relationship between ECL intensity and the logarithm of HSA concentration in the range 5 × 10-9 to 1 × 10-13mgmL-1. The limit of detection (LOD) of the sensor was 1.05 × 10-15mgmL-1. The sensor exhibited outstanding selectivity and stability. Thesensor was applied to detect HSA in human serum with good recoveries of 97.7-105.2%. Theconcentration of HSA was detected by electrochemical method using the gating effect of MIP.

Europium Metal-Organic Framework with a Tetraphenylethylene-Based Ligand: A Dual-Mechanism Quenching Immunosensor for Enhanced Electrochemiluminescence via the Coordination Trigger.

The effective applications of electrochemiluminescence (ECL) across various fields necessitate ongoing research into novel luminophores and ECL strategies. In this study, self-luminous flower-like nanocomposites (Eu-tcbpe-MOF) were prepared by coordination self-assembly using the aggregation-induced emission material 1,1,2,2-tetrakis(4-carboxyphenyl)ethylene (H4TCBPE) and Eu(III) ions as the precursors. Compared with the monomers and aggregates of H4TCBPE, Eu-tcbpe-MOF exhibits stronger ECL emission. Such enhanced electrochemiluminescence is due to coordination as the coordination-triggered electrochemiluminescence (CT-ECL) enhancement effect. In this study, a cubic-structured nanocomposite (Co9S8@Au@MoS2) was used as an efficient quencher, and a more sensitive ECL detection platform was achieved by two quenching mechanisms: resonance energy transfer and competitive consumption of coreactants. N,N-Diethylethanolamine (DBAE) was used as a coreactant, and DBAE has a faster electron transfer rate and stronger energy supply efficiency than the traditional anodoluminescent coreactant tripropylamine, which effectively improves the ECL signal intensity of Eu-tcbpe-MOF. Hence, a sandwich-type ECL immunosensor was prepared by employing a dual-quenching mechanism, utilizing Eu-tcbpe-MOF as the detection probe and Co9S8@Au@MoS2 as the quencher, achieving precise detection of carcinoembryonic antigen from 0.1 pg·mL-1 to 100 ng·mL-1 with a detection limit of 35.1 fg·mL-1.

Determination of catechol in tea based on the inhibition of CS@Cd composites electrochemiluminescence

To address growing concerns about food safety, sensors for catechol (CA) have been urgently needed. In this work, cadmium-coated carbon spheres (CS@Cd) composites are prepared via hydrothermal synthesis and further used to fabricate a CS@Cd modified glassy carbon electrode (CS@Cd/GCE). Importantly, CS@Cd has good sensitization effect on the electrochemiluminescence (ECL) of luminol-H2O2 system. Besides, CA is able to inhibit the ECL of CS@Cd/GCE owing to the consumption of H2O2 induced by CA, and thus a novel strategy for ECL detection of CA is formulated. At optimum conditions, CS@Cd/GCE exhibits good linear relationship in the range of 1.0 × 10-11 ∼ 1.0 × 10-4 mol·L-1 with a low limit of detection of 2.5 × 10-12 mol·L-1 (S/N = 3). Finally, this method achieves a satisfactory outcome for the detection of CA in tea samples.

Solid Electrochemiluminescence Sensor by Immobilization of Emitter Ruthenium(II)tris(bipyridine) in Bipolar Silica Nanochannel Film for Sensitive Detection of Oxalate in Serum and Urine.

Convenient and highly sensitive detection of oxalate ions in body fluids is of crucial significance for disease prevention, diagnosis, and monitoring of treatment effectiveness. Establishing a simple solid-state electrochemiluminescence (ECL) sensing system for highly sensitive detection of oxalate ions is highly desirable. In this work, a solid ECL sensor was fabricated by immobilizing the commonly used emitter ruthenium(II)tris(bipyridine) (Ru(bpy)32+) on a double-layered bipolar silica nanochannel array film (bp-SNA)-modified electrode, enabling sensitive detection of oxalate ions in serum or urine samples. Cost-effective and readily available indium tin oxide (ITO) was used as the supporting electrode. Convenient fabrication of multiple negatively charged SNA (n-SNA)-modified ITO electrodes was achieved through the one-step Stöber solution growth method. Subsequently, a positive outer layer film (p-SNA) was rapidly prepared using an electrochemical-assisted self-assembly method. The double-layered bipolar silica nanochannel array film achieved stable immobilization of Ru(bpy)32+ on the electrode surface, facilitated by the electrostatic adsorption of Ru(bpy)32+ by n-SNA and the electrostatic repulsion by p-SNA. Utilizing oxalate ions as a co-reactant for Ru(bpy)32+, combined with the electrostatic enrichment of oxalate ions by p-SNA, the constructed sensor enabled highly sensitive detection of oxalate ions ranging from 1 nM to 25 μM and from 25 μM to 1 mM, with a detection limit (LOD) of 0.8 nM. The fabricated ECL sensor exhibited high selectivity and good stability, making it suitable for ECL detection of oxalate ions in serum and urine samples.

A Controlled Release Aptasensor Utilizing AIE-Active MOFs as High-Efficiency ECL Nanoprobe for the Sensitive Detection of Adenosine Triphosphate.

Improving the sensitivity in electrochemiluminescence (ECL) detection systems necessitates the integration of robust ECL luminophores and efficient signal transduction. In this study, we report a novel ECL nanoprobe (Zr-MOF) that exhibits strong and stable emission by incorporating aggregation-induced emission ligands into Zr-based metal-organic frameworks (MOFs). Meanwhile, we designed a high-performance signal modulator through the implementation of a well-designed controlled release system with a self-on/off function. ZnS quantum dots (QDs) encapsulated within the cavities of aminated mesoporous silica nanoparticles (NH2-SiO2) serve as the ECL quenchers, while adenosine triphosphate (ATP) aptamers adsorbed on the surface of NH2-SiO2 through electrostatic interaction act as "gatekeepers." Based on the target-triggered ECL resonance energy transfer between Zr-MOF and ZnS QDs, we establish a coreactant-free ECL aptasensor for the sensitive detection of ATP, achieving an impressive low detection limit of 0.033 nM. This study not only demonstrates the successful combination of ECL with controlled release strategies but also opens new avenues for developing highly efficient MOFs-based ECL systems.

Circular DNAzyme-Switched CRISPR/Cas12a Assay for Electrochemiluminescent Response of Demethylase Activity.

DNA nanostructure provides powerful tools for DNA demethylase activity detection, but its stability has been significantly challenged. By virtue of circular DNA with resistance to exonuclease degradation, herein, the circular DNAzyme duplex with artificial methylated modification was constructed to identify the target and output the DNA activators to drive the CRISPR/Cas12a, constructing an "on-off-on" electrochemiluminescence (ECL) biosensor for monitoring the activity of the O6-methylguanine-DNA methyltransferase (MGMT). Specifically, the circular DNAzyme duplex consisted of the chimeric RNA-DNA substrate ring with double activator sequences and two single-stranded DNAzymes, whose catalytic domains were premodified with the methyl groups. When the MGMT was present, the methylated DNAzymes were repaired and restored the catalytic activity to cleave the chimeric RNA-DNA substrates, followed by the output of DNA activators to initiate the CRISPR/Cas12a. Subsequently, the ECL signals of silver nanoparticle-modified SnO2 nanospheres (Ag@SnO2) were recovered by releasing the ferrocene-labeled quenching probes (Fc-DNA) from the electrode surface because of the trans-cleavage activity of CRISPR/Cas12a, thus achieving the specific and sensitive ECL detection of MGMT from 2.5 × 10-4 to 2.5 × 102 ng/mL with a low limit (9.69 × 10-5 ng/mL). This strategy affords novel ideas and insights into research on how to project stable nucleic acid probes to detect DNA demethylases beyond traditional methods.

TiO2/Ag-based photodeposited catalyst boosted electrochemiluminescence of ninhydrin-hydrogen peroxide system for ultrasensitive sensing of copper (II)

Photodeposited TiO2/Ag nanocomposites were generally used to be a friendly catalyst for degrading organic contaminant in environmental field. However, electrochemiluminescence (ECL) sensing analysis based on photocatalysts remains a significant challenge. Herein, polyvinylimide (PEI)-TiO2/Ag nanocomposites (PEI-TiO2/AgNCPs) film with reduced graphene oxide(r-GO) was constructed as a sensing interface for copper(II) ECL detection. TiO2/Ag nanocomposites was prepared by reversed phase microemulsion method and photodeposition technique. Moreover, it was discovered that a small amount of Cu2+ could obviously boost the ECL signal of ninhydrin-hydrogen peroxide system. Signal amplification was achieved by using the synergistic effect between r-GO and TiO2/Ag nanocomposites, and the efficiently concentrated effect of PEI to Cu2+. Furthermore, the investigation showed that ECL mechanism of ninhydrin-hydrogen peroxide system was attributed to the generated hydroxyl radical and superoxide anion during the several type of reactions. Thus for the first time, an ultrasensitive ECL approach for detecting Cu2+ could be performed using ninhydrin as an ECL signal probe and hydrogen peroxide as a co-reaction reagent. Under the suitable circumstances, the proposed method showed an excellent linear relationship in the concentration range of Cu2+ from 1.0 fM to 5.0 nM. Detection limit was estimated to be as low as 0.26 fM. The sensing interface expanded the application of photodeposited TiO2/Ag nanocomposites in ultrasensitive ECL detection. It has potential applications in other components and biological analysis.