Spectroelectrochemistry of hollow spherical CdSe quantum dot assemblies in water

The hollow spherical CdSe QD assemblies were synthesized via a sonochemical approach that utilizes β-cyclodextrin as a template reagent in aqueous solution. The hollow nanospheres have an average diameter of 70 nm and are found to consist of an assembly of monodispersed 5 nm sized CdSe quantum dots. Following an electrochemical reaction with persulfate ions, strong electrogenerated chemiluminescence (ECL) was observed from the CdSe nanoassemblies suspended in an aqueous solution of pH ⩽ 7.95. The study indicates that the morphology of the 70 nm nanoassembly plays an important role in generating the stable ECL since individually dispersed quantum dots did not exhibit any significant ECL. The unique ECL intensity and stability of the synthesized spherical nanoassemblies could allow for potential sensor applications of CdSe quantum dots in water.     

Electrochemiluminescence immunosensor based on nanocomposite film of CdS quantum dots-carbon nanotubes combined with gold nanoparticles-chitosan

A novel and sensitive electrochemiluminescence (ECL) immunosensor based on CdS quantum dots (QDs)-carbon nanotubes (CNTs) and gold nanoparticles-chitosan (GNPs-CHIT) was presented. CdS QDs ECL was much enhanced by combing poly(diallyldimethylammonium chloride) functionalized CNTs. GNPs-CHIT nanohybrids was used to construct an effective antibody immobilization matrix with excellent stability and bioactivity. The principle of ECL detection for target human IgG is based on the increment of steric hindrance after immunoreaction, which resulted in the decrease in ECL intensity. The linear response range was between 0.006 and 150 ng mL^?1, and the detection limit was 0.001 ng mL^?1. This approach offers obvious advantages of being simpler, faster, and more stable compared with other immunosensors, which possesses great potential for protein detection in clinical laboratory.     

Recognition of DNA based on changes in the fluorescence intensity of CdSe/CD QDs–phenanthroline systems

The CdSe quantum dots (QDs) modified by mercapto-β-cyclodextrin (CD) were synthesized and characterized by transmission electron microscopy, powder X-ray diffraction, excitation and emission spectra, and fluorescence lifetime. When λ_ex = 370 nm, the fluorescence peak of CdSe/CD QDs is at 525 nm. Phenanthroline (Phen) is able to quench their fluorescence, which can be recovered by the addition of DNA. The quenching and restoration of fluorescence intensity were found to be linearly proportional to the amount of Phen and DNA, respectively. The variation of the fluorescence intensity of the CdSe/CD QDs–Phen system was studied, and it was demonstrated to result from a static mechanism due to the formation of a Phen inclusion complex with the CdSe QDs modified by mercapto-β-cyclodextrin. The fluorescence recovery was due to the binding of DNA with Phen in the inclusion complex, leading to the freeing of the CdSe/CD QDs. The binding constants and sizes of the binding sites of the Phen–DNA interaction were calculated to be 1.33 × 10⁷ mol^?1 L and 10.79 bp.     

The performance of coupled (CdS:CdSe) quantum dot-sensitized TiO2 nanofibrous solar cells

Highly porous networks and reduced grain boundaries with one-dimensional (1-D) nanofibrous morphology offer enhanced charge transport in solar cells applications. Quantum dot (QDs) decorated TiO₂ nanofibrous electrodes, unlike organic dye sensitizers, can yield multiple carrier generations due to the quantum confinement effect. This paper describes the first attempt to combine these two novel approaches, in which CdS (～18 nm) and CdSe (～8 nm) QDs are sensitized onto electrospun TiO₂ nanofibrous (diameter ～80–100 nm) electrodes. The photovoltaic performances of single (CdS and CdSe) and coupled (CdS/CdSe) QDs-sensitized TiO₂ fibrous electrodes are demonstrated in sandwich-type solar cells using polysulfide electrolyte. The observed difficulties in charge injection and lesser spectral coverage of single QDs-sensitizers are solved by coupling (CdS:CdSe) two QDs-sensitizers, resulting in a enhanced open-circuit voltage (0.64 V) with 2.69% efficiency. These results suggest the versatility of fibrous electrodes in QDs-sensitized solar cell applications.     

Anodic electrochemiluminescence of CdSe nanoparticles coreacted with tertiary amine and halide induced quenching effect

The novel anodic electrochemiluminescence (ECL) behaviors of the CdSe nanoparticles coreacted with tertiary amine were observed. The ECL intensity peak located near +1.2 V, accompanied with a shoulder above +1.5 V. The ECL emission peak estimated at about 580 nm was almost identical with that of the photoluminescence (PL), indicating the passivation of the surfaces of the nanoparticles. The dependence of the ECL on system pH and the concentration of the coreactants were also discussed. The halide ions could quench ECL, with the effective order I^? > Br^? > Cl^?. Based on these results the possible ECL processes were proposed.     

Electrogenerated chemiluminescence aptamer-based biosensor for the determination of cocaine

A novel electrogenerated chemiluminescence aptamer-based (ECL-AB) biosensor for the determination of a small molecule drug is designed employing cocaine-binding aptamer as molecular recognition element for cocaine as a model analyte and ruthenium complex served as an ECL label. A 5′-terminal cocaine-binding aptamer with the ECL label at 3′-terminal of the aptamer was utilized as an ECL probe. The ECL-AB biosensors were fabricated by immobilizing the ECL probe onto a gold electrode surface via thiol-Au interactions. An enhanced ECL signal is generated upon recognition of the target cocaine, attributed to a change in the conformation of the ECL probe from random coil-like configuration on the probe-modified film to three-way junction structure, in close proximity to the sensor interface. The integrated ECL intensity versus the concentration of cocaine was linear in the range from 5.0 × 10⁻⁹ to 3.0 × 10⁻⁷ M. The detection limit was 1.0 × 10⁻⁹ M. This work demonstrates that the combination of a highly binding aptamer to analyte with a highly sensitive ECL technique to design ECL-AB biosensor is a great promising approach for the determination of small molecule drugs.     

Electrochemiluminescent biosensor based on multi-wall carbon nanotube/nano-Au modified electrode

The electrochemiluminescent (ECL) behavior of lucigenin on a multi-wall carbon nanotube/nano-Au modified glassy carbon electrode (MWNT/nano-Au/GCE) was studied in this paper. Compared with the bare GCE, the ECL intensity of lucigenin can be greatly enhanced at MWNT/nano-Au/GCE. Based on the fact that superoxide dimutase (SOD) could obviously inhibit the ECL of lucigenin at MWNT/nano-Au/GCE, a sensitive ECL biosensor for determination of SOD was developed with a wide linear range of 5.0 × 10⁻⁸–5.0 × 10⁻⁶ mol/L with detection limit of 2.5 × 10⁻⁸ mol/L.     

Ag2S quantum dot-sensitized solar cells

We present a new photosensitizer – Ag₂S quantum dots (QDs) – for solar cells. The QDs were grown by the successive ionic layer adsorption and reaction deposition method. The assembled Ag₂S-QD solar cells yield a best power conversion efficiency of 1.70% and a short-circuit current of 1.54 mA/cm² under 10.8% sun. The solar cells have a maximal external quantum efficiency (EQE) of 50% at λ = 530 nm and an average EQE of ～ 42% over the spectral range of 400–1000 nm. The effective photovoltaic range covers the visible and near-infrared spectral regions and is ～ 2–4 times broader than that of the cadmium chalcogenide systems — CdS and CdSe. The results show that Ag₂S QDs can be used as a highly efficient and broadband sensitizer for solar cells.     

The investigation of the interactions between CdSe quantum dots and human serum albumin by resonance Rayleigh scattering and second-order scattering spectra

Human serum albumin (HSA) was the most abundant protein in human plasma and has significant physiological function. In Tris–HCl buffer solution (pH 7.4), water-soluble semiconductor CdSe quantum dots (QDs) reacted with HSA and the products resulted in a great enhancement of the intensity of resonance Rayleigh scattering (RRS) and second-order scattering (SOS). Based on this, a new method was developed to investigate the interactions between QDs and HSA. The parameters with regard to determination were optimized, and the reaction mechanism was discussed. Under optimal conditions, the increments of scattering intensity (ΔI) were directly proportional to the concentrations of HSA in the range of 0.4–48.0 μmol L^?1. The detection limits were 0.10 μmol L^?1 for RRS method and 0.25 μmol L^?1 for SOS method. The proposed method was sensitive, simple and rapid. It has been successfully applied to the determination of HSA in human urine samples. Analytical results obtained with this novel assay were satisfactory.     

Anodic electrochemiluminescent behavior of lucigenin on MWNT/GCE

The electrochemiluminescent (ECL) behavior of lucigenin on a multiwall carbon nanotubes modified glassy carbon electrode (MWNT/GCE) during anodic scanning was studied. A strong and stable anodic ECL signal was found on MWNT modified electrode, which results from the oxidation reaction between lucigenin and the oxidation production of OH^-. The effects of electrode materials, pH and scan rate on the ECL intensity were studied, and the possible ECL mechanism was also proposed. Under the optimized conditions, the ECL intensity was found to be linear with concentration of lucigenin in the range of 5.0 × 10^?7–5.0 × 10^?6 mol/L with a detection limit of 2.0 × 10^?7 mol/L. Superoxide dimutase (SOD) was found to be able to inhibit this ECL system, based on which a sensitive ECL methods for detection of SOD had been established.     

Enhanced electrochemiluminescence based on Ru(bpy)32+-doped silica nanoparticles and graphene composite for analysis of melamine in milk

A sensitive electrochemiluminescence (ECL) sensor for melamine analysis was fabricated based on Ru(bpy)₃²⁺-doped silica (Ru(bpy)₃²⁺@SiO₂) nanoparticles and graphene composite. Spherical Ru(bpy)₃²⁺@SiO₂ nanoparticles with uniform size about 55 nm were prepared by the reverse microemulsion method. Since per Ru(bpy)₃²⁺@SiO₂ nanoparticle encapsulated a great deal of Ru(bpy)₃²⁺, the ECL intensity has been greatly enhanced, which resulted in high sensitivity. Due to its extraordinary electric conductivity, graphene improved the conductivity and accelerated the electron transfer rate. In addition, graphene could work as electronic channel improving the efficient luminophor amount participating in the ECL reaction, which further enhanced the ECL signal. This proposed sensor was used to melamine analysis and the ECL intensity was proportional to logarithmic melamine concentration range from 1 × 10⁻¹³ M to 1 × 10⁻⁸ M with the detect limit as low as 1 × 10⁻¹³ M. In application to detect melamine in milk, satisfactory recoveries could be obtained, which indicated this sensor having potential application in melamine analysis in real samples.     

Electrochemiluminescence for probing interactions between a mimic enzyme and biological molecules

The present work proposed a novel ECL protocol to probe the interactions between mimic enzymes and small biological molecules. Iron(II) phthalocyanine (FePc) and two imidazoles (imidazole and histidine) were chosen as model molecules of mimic enzyme and small biological molecules, respectively. The interactions between FePc and the imidazoles were probed by a sensitive luminol–O₂ ECL system. Before complexing with the imidazoles, FePc can inhibit luminol–O₂ ECL due to its electrocatalysis towards O₂, however, after complexing with the imidazoles, FePc decreases the electrocatalysis, leading to the observation of an enhanced luminol–O₂ ECL. Additionally, the proposed protocol enables detection limits of 1.0 × 10^?8 mol L^?1 and 1.0 × 10^?7 mol L^?1 to be achieved, respectively, for imidazole and histidine under the physiological pH condition (pH 7.4).     

An electrically heated ionic-liquid/multi-wall carbon nanotube composite electrode and its application to electrochemiluminescent detection of ascorbic acid

A heated composite electrode consisted of multi-wall carbon nanotube (MWNT) and ionic liquids (ILs) was designed and fabricated. The non-conductive binders were replaced by a conductive IL, n-octylpyridinum hexafluorophosphate (OPFP). This heated OPFP/MWNT composite electrode was applied for electrochemiluminescent (ECL) sensor, and the performance of ECL sensor was evaluated by ascorbic acid (AA)/lucigenin ECL system. The new heated electrode combines the advantages of ILs/CNT and heated electrode, showing high thermal stability and conductivity, simple heating setups, improved reproducibility, renewable surface, simplicity of fabrication and enhanced sensitivity with detection limit (S/N = 3) of 0.01 μmol/L for AA.     

Photoelectrochemical determination of inorganic mercury ions based on energy transfer between CdS quantum dots and Au nanoparticles

A novel photoelectrochemical (PEC) sensor for mercury ions (Hg^2 +) was fabricated based on the energy transfer (ET) between CdS quantum dots (QDs) and Au nanoparticles (NPs) with the formation of T–Hg^2 +–T pairs. In the presence of Hg^2 + ions, a T-rich single-strand (ss) DNA labeled with Au NPs could hybridize with another T-rich ssDNA anchored on the CdS QDs modified electrode, through T–Hg^2 +–T interactions, rendering the Au NPs in close proximity with the CdS QDs and hence the photocurrent decrease due to the ET between the CdS QDs and the Au NPs. Under the optimal condition, the photocurrent decrease was proportional to the Hg^2 + concentration, ranging from 3.0 × 10^− 9 to 1.0 × 10^− 7 M, with the detection limit of 6.0 × 10^− 10 M.     

Highly efficient electrogenerated chemiluminescence of natural chlorophyll a

Highly efficient electrogenerated chemiluminescence (ECL) of natural chlorophyll a (Chl a) was observed in acetonitrile with 1-butyl-3-methylimidazolium hexafluorophosphate as electrolyte and tri-n-propylamine (TPrA) as a coreactant. The collected ECL spectrum displayed a maximum emission peak at ca. 670 nm, suggesting that the same excited states with the photo-excitation processes were generated. The possible ECL reaction mechanism of this Chl a–TPrA system was discussed and established. ECL intensity of Chl a was proportional to its concentration over the range of 0.1–11 μM, and a high ECL efficiency (Φ_ecl) of 0.86 was calculated using Ru(bpy)₃^2 + as the standard (Φ_ecl = 1). Herein, an important property of natural Chl a was expanded and a new kind of ECL luminophores was developed. Moreover, it is expected that this high ECL efficiency of natural porphyrin complex has great potential to expand its ECL sensing application.     

Quantum dot-based electrochemical DNA biosensor using a screen-printed graphite surface with embedded bismuth precursor

This work reports the development of screen-printed quantum dots (QDs)-based DNA biosensors utilizing graphite electrodes with embedded bismuth citrate as a bismuth precursor. The sensor surface serves both as a support for the immobilization of the oligonucleotide and as an ultrasensitive voltammetric QDs transducer relying on bismuth nanoparticles. The utility of this biosensor is demonstrated for the detection of the C634R mutation through hybridization of the biotin-tagged target oligonucleotide with a surface-confined capture complementary probe and subsequent reaction with streptavidin-conjugated PbS QDs. The electrochemical transduction step involved anodic stripping voltammetric determination of the Pb(II) released after acidic dissolution of the QDs. Simultaneously with the electrolytic accumulation of Pb on the sensor surface, the embedded bismuth citrate was converted in situ to bismuth nanoparticles enabling ultra-trace Pb determination. The biosensor showed a linear relationship of the Pb(II) peak current with respect to the logarithm of the target DNA concentrations from 0.1 pmol L^− 1 to 10 nmol L^− 1, and the limit of detection was 0.03 pmol L^− 1. The biosensor exhibited effective discrimination between a single-base mismatched sequence and the fully complementary target DNA. These “green” biosensors are inexpensive, lend themselves to easy mass production, and hold promise for ultrasensitive bioassay formats.     

Ultra-sensitive cholesterol biosensor based on low-temperature grown ZnO nanoparticles

A high-sensitive cholesterol amperometric biosensor based on the immobilization of cholesterol oxidase (ChOx) onto the ZnO nanoparticles has been fabricated which shows a very high and reproducible sensitivity of 23.7 μA mM^?1 cm^?2, detection limit (based on S/N ratio) 0.37 ± 0.02 nM, response time less than 5 s, linear range from 1.0 to 500.0 nM and correlation coefficient of R = 0.9975. A relatively low value of enzyme’s kinetic parameter (Michaelis–Menten constant) ～4.7 mM has been obtained which indicates the enhanced enzymatic affinity of ChOx to Cholesterol. To the best of our knowledge, this is the first report in which such a very high-sensitivity and low detection limit has been achieved for the cholesterol biosensor by using ZnO nanostructures modified electrodes.     

Effective enhancement of peroxydisulfate electrochemiluminescence on C60/DDAB films

Effective enhancement of electrochemiluminescence (ECL) of peroxydisulfate on a C₆₀/didodecyldimethyl ammonium bromide (C₆₀/DDAB) film coated glassy carbon electrode (GCE) surface is reported in this paper. The C₆₀/DDAB film gave lower cathodic current in the presence of peroxydisulfate than that from a bare GCE. To our surprise, electrochemiluminescent intensity from peroxydisulfate reduction was effectively enhanced on the C₆₀/DDAB film, which was 50 times and 250 times higher than those from a DDAB film coated and bare GCE, respectively. Moreover, the ECL onset potential on the C₆₀/DDAB film was about −0.9 V, which positively shifted 200 mV compared with that from the bare GCE. Dissolved oxygen and the applied potential also affected the electrochemiluminescent intensity. The presence of oxygen decreased the intensity, and the intensity reached maximum at the applied potential of −1.7 V. The unique property will greatly enrich ECL studies and applications based on fullerenes.     

CdSe/TiO2 nanocrystalline solar cells

CdSe sensitized TiO₂ nanocrystalline solar cells were made with the participation of silicotungstic acid (STA) during the deposition of CdSe, the resulting Voc and Isc were 0.23 V cm^-2 and 10 mA cm^-2, respectively. The doping, time and microporous membrane effects were also discussed.     

Electrogenerated chemiluminescence in an electrodeposited redox hydrogel

We report the electrodeposition, under physiological conditions, of an electrochemiluminescent (ECL) Ru^2+/3+ complex-containing redox hydrogel. The ECL-hydrogels were formed by potential cycling of a solution of [poly(4-vinylpyridine)Ru(2,2′-bipyridine)²Cl^?]^+/2+, its un-coordinated backbone pyridines partially quaternized with bromoethylamine for solubility in water and for swelling to a hydrogel after crosslinking. The polymer was electrosorbed on plasma-oxidized graphite in the anodic half of the cycle and irreversibly crosslinked, to form a swelling but insoluble film, in the cathodic half cycle. The ECL resulted of the chemical reaction of electro-oxidatively produced tri-n-propylamine-radical with the hydrogel’s Ru²⁺ centers. The emission spectra of the photo-excited films and their ECL spectra were identical. The ECL-emission increased one thousand-fold, linearly with the tri-n-propylamine (TPrA) concentration, between 100 nM and 0.1 mM.