Dual-potential Electrochemiluminescence Research Articles

Dual-potential electrochemiluminescence cytosensor based on a metal-organic framework and ABEI-PEI-Au@AgNPs for the simultaneous determination of phosphatidylserine and epidermal growth factor receptors on an apoptotic cell surface.

A new electrochemiluminescence (ECL) cytosensor is proposed for the simultaneous determination of phosphatidylserine (PS) and epidermal growth factor receptor (EGFR) based on the ECL signals of metal-organic framework-5 (MOF-5) loaded CdS quantum dots and N-(aminobutyl)-N-(ethylisoluminol)-polyethylenimine capped Au and Ag nanoparticles. Apoptosis promotes the exposure of PS and reduces the expression of EGFR in cell membranes. Two spatially resolved areas on dual-disk glassy carbon electrodes were designed to eliminate the interference from different ECL probes. Using HepG2 cells treated with resveratrol to induce apoptosis, thecytosensor exhibited high sensitivity, simplicity, and high reproducibility, demonstrating its potential in drug screening and rapid apoptotic cell detection. The strategy reported provides a promising platform for the highly sensitive cytosensing and convenient screening of clinically relevant anticancer drugs.

An ultrasensitive ratiometric aptasensor based on the dual-potential electrochemiluminescence of Ru(bpy)32+ in a novel ternary system for detection of Patulin in fruit products.

To sensitively monitor trace-level of toxic patulin (PAT), an ultrasensitive PAT ratiometric aptasensor based on the dual-potential electrochemiluminescence (ECL) of Ru(bpy)32+ was first proposed. Noteworthily, Ru(bpy)32+-doped trimetallic nanocube (Ru@Tri) innovatively integrated the luminophore and cathode coreaction accelerator (CCA), which could generate strong cathodic ECL in the existence of low concentration of K2S2O8. Simultaneously, anthocyanin-derived carbon quantum dots (anth-CQDs) prepared from purple potato skins was first served as a green anodic coreactant. And SiO2-coated anth-CQDs (anth-CQDs@SiO2) exhibited excellent performance for enhancing anodic ECL of Ru@Tri. Based on this, a novel ternary ECL system was established. In the presence of PAT, the ECL intensity ratio of anode to cathode (IECL-A/IECL-C) was significantly increased, and a low detection limit of 0.05pgmL-1 was obtained. Moreover, when proposed method and high performance liquid chromatography (HPLC) were simultaneously applied to series of fruit products, the obtained results were completely consistent, reflecting its practicability.

Dual-channel molecularly imprinted sensor based on dual-potential electrochemiluminescence of Zn-MOFs for double detection of trace chloramphenicol

Functionalized metal organometallic frameworks (MOFs) offer unique advantages in the field of sensing due to their versatility and tunable optical properties. In this work, a new dual-potential electrochemiluminescence (ECL) molecularly imprinted sensor using single Zn-MOF signal probe was designed for double detection of trace chloramphenicol (CAP). As dual-signal ECL emitters, Zn-MOFs were firstly modified on the electrode, showing excellent ECL emission in both cathodic and anodic potential. Then the molecularly imprinted polymer (MIP) was electrochemically prepared using o-phenylenediamine (O-PD) and CAP as a template molecule on the Zn-MOFs/electrode. After CAP as a molecular recognition element was eluted and removed from the Zn-MOFs/MIP/electrode, a new ECL sensor was developed for CAP detection by re-adsorption of CAP on the MIP, resulting in “off” of ECL signal. Compared with the conventional single-signal luminophores, Zn-MOFs show more stable and excellent dual ECL signals, which greatly improve the discriminability and accuracy of CAP trace detection. Under the optimal conditions, the linear range of CAP detection was 1 × 10-14−1 × 10-8 M, and the minimum limits of detection (LOD) were 2.1 fM and 2.5 fM for cathode and anode ECL, respectively. This is the first time that Zn-MOFs are used as dual-ECL emitters for molecular sensing systems, and the proposed dual-channel sensing system is flexibly applicable to sensitive detection of other antibiotics, which has broad practical application in food safety.

Particle Size-Controlled Oxygen Reduction and Evolution Reaction Nanocatalysts Regulate Ru(bpy)32+'s Dual-potential Electrochemiluminescence for Sandwich Immunoassay.

Multiple signal strategies remarkably improve the accuracy and efficiency of electrochemiluminescence (ECL) immunoassays, but the lack of potential-resolved luminophore pairs and chemical cross talk hinders their development. In this study, we synthesized a series of gold nanoparticles (AuNPs)/reduced graphene oxide (Au/rGO) composites as adjustable oxygen reduction reaction and oxygen evolution reaction catalysts to promote and modulate tris(2,2'-bipyridine) ruthenium(II) (Ru(bpy)32+)'s multisignal luminescence. With the increase in the diameter of AuNPs (3 to 30 nm), their ability to promote Ru(bpy)32+'s anodic ECL was first impaired and then strengthened, and cathodic ECL was first enhanced and then weakened. Au/rGOs with medium-small and medium-large AuNP diameters remarkably increased Ru(bpy)32+'s cathodic and anodic luminescence, respectively. Notably, the stimulation effects of Au/rGOs were superior to those of most existing Ru(bpy)32+ co-reactants. Moreover, we proposed a novel ratiometric immunosensor construction strategy using Ru(bpy)32+'s luminescence promoter rather than luminophores as tags of antibodies to achieve signal resolution. This method avoids signal cross talk between luminophores and their respective co-reactants, which achieved a good linear range of 10-7 to 10-1 ng/ml and a limit of detection of 0.33 fg/ml for detecting carcinoembryonic antigen. This study addresses the previous scarcity of the macromolecular co-reactants of Ru(bpy)32+, broadening its application in biomaterial detection. Furthermore, the systematic clarification of the detailed mechanisms for converting the potential-resolved luminescence of Ru(bpy)32+ could facilitate an in-depth understanding of the ECL process and should inspire new designs of Ru(bpy)32+ luminescence enhancers or applications of Au/rGOs to other luminophores. This work removes some impediments to the development of multisignal ECL biodetection systems and provides vitality into their widespread applications.

Dual-potential electrochemiluminescence of single luminophore for detection of biomarker based on black phosphorus quantum dots as co-reactant.

Simultaneous cathodic and anodic electrochemiluminescence (ECL) emissions of needle-like nanostructures of Ru(bpy)32+ (RuNDs) as the only luminophore arereported based on different co-reactants. Cathodic ECL was attained from RuNDs/K2S2O8 system, while anodic ECL was achieved from RuNDs/black phosphorus quantum dots (BPQDs) system. Ferrocene attached to the hairpin DNA could quench the cathodic and anodic ECL simultaneously. Subsequently, the ECL signals recovered in the presence of tumor marker mucin 1 (MUC1), which made it possible to quantitatively detect MUC1. The variation of ECL signal was related linearly to the concentrations of MUC1 in the range 20pgmL-1 to 10ngmL-1, and the detection limits were calculated to 2.5pgmL-1 (anodic system, 3σ) and 6.2pgmL-1 (cathodic system, 3σ), respectively. The recoveries were 97.0%, 105%, and 95.2% obtained from three human serum samples, and the relative standard deviation (RSD) is 5.3%. As a proof of concept, this work realized simultaneous ECL emission of asingle luminophore, which initiates a new thought in biomarker ECL detection beyond the traditional ones. Simultaneous cathodic and anodic ECL emissions of RuNDs were reported based on different co-reactants. Ferrocene could quench the ECL emission in the cathode and the anode simultaneously. Thus, an aptasensor was constructed based on the variation of ECL intensity. As a proof of concept, this work realized simultaneous ECL emission of a single luminophore, which initiates a new thought in biomarker ECL detection beyond the traditional ones by avoiding the false positive signals.

Dual-potential electrochemiluminescence from black phosphorus and graphitic carbon nitrides for label-free enzymatic biosensing.

Simultaneous anodic and cathodic electrochemiluminescence (ECL) emissions of black phosphorus nanosheets (BPNSs) and graphitic carbon nitrides (g-C3N4) were reported based on the co-existence of different co-reactants. Anodic ECL was obtained at the BPNSs modified electrode with tripropylamine (TPrA) as a co-reactant, while g-C3N4 was selected as another emitter to obtain cathodic ECL emission with K2S2O8 as co-reactant. Employing the superiority of two separate ECL systems, a facile ECL method was developed for cholesterol detection based on cholesterol oxidase (ChOx) immobilized g-C3N4/BPNSs modified glassy carbon electrode (g-C3N4/BPNSs/GCE). False positive signals can be significantly reduced based on the separation of anode and cathode ECL signals from BPNSs and g-C3N4, respectively. The proposed biosensor provided a quantitative readout proportional to cholesterol concentrations in the range from 0.5 μM to 0.5 mM with a detection limit of 0.14 μM (cathodic system, 3σ, n = 6) and 0.32 μM (anodic system, 3σ, n = 6). The proposed biosensor demonstrated excellent analytical performance with remarkable sensitivity, manifesting its potential application in enzymatic biosensing field.

A dual-potential electrochemiluminescence sensor for ratiometric detection of carcinoembryonic antigen based on single luminophor

Ratiometric electrochemiluminescence (ECL) assays have attracted widespread attentions in biosensing owing to their precise measurements by eliminating the environmental interferences. However, they mostly needed two eligible luminophors, increasing the complexity of the systems and limiting their practical applications. Herein, using luminol as single luminophor, a dual-potential ratiometric ECL strategy was proposed to detect carcinoembryonic antigen (CEA). The luminol exhibited cathodic and anodic emissions on graphene-ionic liquid-platinum (GR-IL-Pt) composites and Ti3C2 MXenes-Au NPs hybrids, respectively. Then, a sandwich ECL sensor was fabricated using GR-IL-Pt composites as matrix to immobilize the primary antibodies of CEA and Ti3C2 MXenes-Au NPs hybrids as platform to load the secondary antibodies. With the presence of CEA, the ratio of anodic ECL to cathodic ECL (ECLanodic/ECLcathodic) increased obviously, realizing sensitive ratiometric detection of CEA. In addition, the ECLanodic/ECLcathodic was independent with the concentrations of H2O2, greatly improving the test reliability. The developed ECL sensor exhibited a sensitive detection toward CEA, performing a wide linearity in the range of 0.1 pg mL−1 - 10 ng mL−1 with a low detection limit of 34.58 fg mL-1 (S/N = 3). Furthermore, this strategy exhibited a good practicality to detect CEA in human serums, providing a promising strategy in ECL bioanalysis.

Gold nanoparticles decorated carbon nitride nanosheets as a coreactant regulate the conversion of the dual-potential electrochemiluminescence of Ru(bpy)32+ for Hg2+ detection.

Gold nanoparticles (AuNPs) decorated carbon nitride nanosheets (Au-g-C3N4 NSs) could work as an excellent on-electrode cathodic coreactant for Ru(bpy)32+. Based on the regulation effect of AuNPs and mercury (Hg2+) for the dual-potential electrochemiluminescence (ECL) of Ru(bpy)32+, a simple, sensitive and selective ECL system was created for the ratiometric sensing of Hg2+.

Synergistically mediated enhancement of cathodic and anodic electrochemiluminescence of graphene quantum dots through chemical and electrochemical reactions of coreactants

We for the first time propose a new concept where a greater enhancement in dual potential electrochemiluminescence (ECL) of a single graphene quantum dot (GQD) emitter can be achieved through the coupling between chemical and electrochemical reactions of two different coreactants of K2S2O8 and Na2SO3.

A dual-potential electrochemiluminescence ratiometric sensor for sensitive detection of dopamine based on graphene-CdTe quantum dots and self-enhanced Ru(II) complex

A novel dual-potential ratiometric electrochemiluminescence (ECL) sensor was designed for detecting dopamine (DA) based on graphene-CdTe quantum dots (G-CdTe QDs) as the cathodic emitter and self-enhanced Ru(II) composite (TAEA-Ru) as the anodic emitter. TAEA-Ru was prepared by linking ruthenium(II) tris(2,2′-bipyridyl-4,4′-dicarboxylato) with tris(2-aminoethyl)amine. Firstly, 3-aminopropyltriethoxysilane founctionalized G-CdTe QDs was used as the substrate for capturing target DA via the specific recognition of the diol of DA to the oxyethyl group of APTES. Then, Cu2O nanocrystals supported TAEA-Ru was further bound by the strong interaction between amino groups of DA and carboxyl groups of the Cu2O-TAEA-Ru. With the increase in DA concentration, the loading of Cu2O-TAEA-Ru at the electrode increased. As a result, the anodic ECL signal from TAEA-Ru increased, and the cathodic ECL signal from G-CdTe QDs/O2 system decreased correspondingly. Such a decrease was resulted from the ECL resonance energy transfer (RET) from G-CdTe QDs to TAEA-Ru as well as the dual quenching effects of Cu2O to G-CdTe QDs, namely the ECL-RET from G-CdTe QDs to Cu2O and the consumption of coreactant O2 by Cu2O. Based on the ratio of two ECL signals, the determination of DA was achieved with a linear range from 10.0 fM to 1.0nM and a detection limit low to 2.9 fM (S/N=3). The combination of G-CdTe QDs/O2 and TAEA-Ru would break the limitation of the same coreatant shared in previous ECL ratiometric systems and provide a potential application of ECL ratiometric sensor in the detection of biological small molecules with the assistance of the dual molecular recognition strategy.

Nitrogen doped graphene quantum dots based single-luminophor generated dual-potential electrochemiluminescence system for ratiometric sensing of Co2+ ion

Herein, a single luminophor dual-potential chemiluminescence (ECL) system based on nitrogen doped graphene quantum dots (NGQDs) was developed for ratiometric detection of Co2+ ion. Dissolved oxygen is changed to O2− and HO2− which participate in the anodic and cathodic ECL generating processes of NGQDs. Co2+ ion was demonstrated able to evidently amplify the anodic intensity by displaying catalytic action of the intermediate steps of anodic ECL reactions, and quench the cathodic ECL intensity because of the effective elimination on excited states (NGQDs*) generating. Hence, the target Co2+ ion could be quantified by the ratio of ECL intensities at two excitation potentials. On this basis, without any labeling and additional coreactants, an accurate and reliable sensing system based on the dual-potential ECL of NGQDs toward Co2+ ion was fabricated with excellent sensitivity and selectivity against other interferential metal ions. The developed ratiometric sensor exhibited a linear response ranging from 1.0μM to 70μM with a limit of detection of 0.2μM (S/N=3). The proposed dual-potential ratiometric NGQDs based ECL sensor was also used to detect Co2+ ion in real water samples. As single luminophor, NGQDs possessing multiple-ECL signals is simple without labeling, providing more reliable signals in sensing than other essential state dependent techniques.

A dual-potential electrochemiluminescence ratiometric approach based on graphene quantum dots and luminol for highly sensitive detection of protein kinase activity.

A novel Au NP mediated dual-potential ECL ratiometric approach for highly sensitive protein kinase activity and inhibition assay has been developed based on the simultaneous decrease of cathodic ECL from GQDs and enhancement of anodic ECL from luminol in the same bioanalysis.

Signal-On Dual-Potential Electrochemiluminescence Based on Luminol–Gold Bifunctional Nanoparticles for Telomerase Detection

Here, we report a novel type of signal-on dual-potential electrochemiluminescence (ECL) approach for telomerase detection based on bifunctionalized luminol-gold nanoparticles (L-Au NPs). In this approach, CdS nanocrystals (NCs) were first coated on glassy carbon electrode, and then thiol-modified telomerase primer was attached on CdS NCs via Cd-S bond. In the presence of telomerase and dNTPs, the primer could be extended. Telomerase primer would hybridize with its complementary DNA, and the extended part would hybridize with the capture DNA which was tagged with L-Au NPs. In the presence of coreactant H2O2, the L-Au NPs could not only enhance the ECL intensity of CdS NCs at -1.25 V (vs SCE) induced by the surface plasmon resonance (SPR) of Au NPs but also produce a new ECL signal at +0.45 V (vs SCE) that resulted from luminol in L-Au NPs. Both signals at two potentials increased with the increase of telomerase concentration. This method could be used to detect the telomerase from 100 to 9000 HL-60 cells and investigate the apoptosis of tumor cells. The ratio of the two signal increments (ΔECL(Luminol)/ΔECL(CdS NCs)), which showed a high consistency value for different numbers of cells, could be used to verify the reliability of tests. This dual-potential ECL strategy showed great promise in avoiding false positive or negative results in bioanalysis.

Electrochemiluminescence Ratiometry: A New Approach to DNA Biosensing

Inspired by dual-wavelength fluorescence ratiometric method which could reduce the influence from the environmental change, here, we present a novel dual-potential electrochemiluminescence (ECL) ratiometric sensing approach. CdS nanocrystal (NC) and luminol as two different ECL emitters are employed. ECL from CdS NCs coated on glassy carbon electrode at -1.25 V (vs SCE) could be quenched by closely contacted Pt nanoparticles (NPs) via a biological binding event, while ECL from luminol at +0.45 V (vs SCE) could be enhanced by the same Pt NPs, in the presence of their common coreactant of H₂O₂. Thus, the quenching of ECL from CdS NCs and the enhancement of ECL from luminol could indicate the same biological binding event. With the mp53 oncogene as a model DNA molecule, a molecular beacon (MB) containing a 20-base loop, which is complementary with the mp53 oncogene, is immobilized on CdS NCs/GCE first; Pt NPs are then captured on CdS NCs surface by DNA hybridization between the MB and mp53 oncogene labeled on Pt NPs. By measuring the ratio of ECL intensities at two excitation potentials, this approach could sensitively detect the concentration of target DNA in a wide range from 5.0 fM to 1.0 pM. The sensing scheme is general and can be utilized for many other biological binding events.