A highly sensitive competitive immunosensor based on the electrochemiluminescence (ECL) of quantum dots (QDs) was proposed by coupling with an enzymatic amplification. The fabrication process of the immunosensor was traced with atomic force microscopic images and electrochemical impedance spectra. The strong cathodic ECL emission of the immobilized QDs could be detected at a relatively low emission potential. The reduction of dissolved oxygen during the cathodic process provided a self-produced coreactant, H(2)O(2), for the ECL emission. Using human IgG (HIgG) as a model protein, upon the immuno-recognition of the immobilized HIgG to its antibody labeled simply with horseradish peroxidase, the ECL intensity decreased due to the steric hindrance of the proteins to electron transfer. The decrease could be greatly amplified by an enzymatic cycle to consume the self-produced coreactant, leading to a wide calibration range of 0.05 ng mL(-1) approximately 5 microg mL(-1) and a low limit of detection for the competitive immunoassay of HIgG. This immunosensor showed good stability and fabrication reproducibility. The immunoassays of practical samples showed acceptable results. This facile immunosensing strategy opened a new avenue for detection of proteins and application of QDs in ECL biosensing.

A novel electrochemiluminescent (ECL) sensing system was constructed for low-potential detection of metal ion by immobilizing surface-unpassivated CdTe quantum dots (QDs) on a glassy carbon electrode. The surface-unpassivated CdTe QDs were prepared using meso-2,3-dimercaptosuccinic acid (DMSA) as a stabilizer to cap CdTe QDs and characterized with scanning electron micrograph and X-ray photoelectron spectroscopy. The immobilized QDs showed a strong cathodic ECL emission peak at -0.87 V with an onset potential at -0.64 V (vs Ag/AgCl/saturated KCl) in air-saturated, pH 9.0 HCl-Tris buffer. On the basis of the competition of metal ion to the stabilizer, the quenching effect of metal ion on ECL emission was observed, which led to a sensitive chemical sensing application. Using cupric cation as a model analyte, the sensor showed a linear range from 5.0 nM to 7.0 muM with a detection limit of 3.0 nM and had been successfully applied in the detection of copper in human hair. It could be extended to detect other metal ions with stronger metal-S interaction than with the Cd-S bond. As an example, the sensor could be used to detect Hg(2+) down to 1.4 nM. The bidentate chelate QD-based sensor exhibited a promising platform for rapid detection of cations with strong metal-S interaction and could be further applied for development of other low-potential electrochemical sensing systems.

Anodic electrochemiluminescence (ECL) of CdSe quantum dots (QDs) in a neutral system was for the first time observed at a relatively low potential by using sulfite as a co-reactant to produce the ECL emission at an indium tin oxide (ITO) electrode, which could be used for the sensitive detection of ECL quenchers using dopamine (DA) as a model molecule.

Bidentate chelation, meso-2,3-dimercaptosuccinic acid (DMSA), was used as a stabilizer for the synthesis of CdTe quantum dots (QDs). The bidentate chelate QDs, characterized with FT-IR, PL, and UV/Vis spectroscopy; element analysis; and high-resolution transmission electron microscope, exhibited surface traps due to the large surface/volume ratio of QD particle and the steric hindrance of the DMSA molecule. The unpassivated surface of the QDs produced a narrower band gap than the core and electrochemiluminescent (ECL) emission at relatively low cathodic potential. In air-saturated pH 7.0 buffer, the QDs immobilized on electrode surface showed an intense ECL emission peak at -0.85 V (vs. Ag/AgCl). H(2)O(2) produced from electrochemical reduction of dissolved oxygen was demonstrated to be the co-reactant, which avoided the need of strong oxidant as the co-reactant and produced a sensitive analytical method for peroxidase-related analytes. Using hydroquinone/horseradish peroxidase/H(2)O(2) as a model system, a new, reagentless, phenolic, ECL biosensor for hydroquinone was constructed, based on the quenching effect of ECL emission of QDs by consumption of co-reactant H(2)O(2). The biosensor showed a linear range of 0.2-10 μM with acceptable stability and reproducibility. This work opens new avenues in the search for new ECL emitters with excellent analytical performance and makes QDs a more attractive alternative in biosensing.

A facile label-free electrochemiluminescent (ECL) DNA sensor was designed using a molecular beacon with a guanine-rich stem as a recognition probe. The ECL emission was produced from surface unpassivated CdTe quantum dots (QDs) co-immobilized with colloidal gold nanoparticles (AuNPs) on a chitosan-modified electrode surface. The molecular beacon was adsorbed onto the AuNPs by the thiolated stem. Upon the hybridization of the molecular beacon with target DNA to open the cycle in the presence of hemin, the dissociated guanine-rich sequence could conjugate hemin to form a G-quadruplex architecture. The formed DNAzyme then catalyzed the reduction of dissolved oxygen, the endogenous coreactant for ECL emission of QDs, leading to a decrease in ECL signal. The variations in surface morphology during the fabrication and recognition processes of the ECL sensor were characterized by atomic force microscopy and electrochemical impedance spectroscopy. The ECL signal inhibition depended linearly on the logarithmic value of DNA concentration ranging from 5.0 fM to 0.1 nM, with a detection limit of 0.9 fM. This proposed label-free method is a promising application of QDs-based ECL emission for ultrasensitive DNA assay.