Guang-Li Wang

Label-free photoelectrochemical immunoassay for α-fetoprotein detection based on TiO2/CdS hybrid

A novel photoelectrochemical immunosensor based on TiO(2)/CdS hybrid modified electrode was developed. The TiO(2)/CdS hybrid modified electrode was obtained by alternately dipping the TiO(2) modified indium-tin oxide (ITO) electrode into the [Cd(NH(3))(4)](2+) and S(2-) solution repeatedly. Compared with the routine method using Cd(2+) solution for CdS deposition, the as obtained TiO(2)/CdS electrode showed enhanced photocurrent intensity with fewer coating times. After the ITO/TiO(2)/CdS electrode was coated with chitosan (CS), alpha-fetoprotein (AFP) antibodies were covalently conjugated on the surface of the electrode. Thus, a label-free photoelectrochemical immunosensor for the detection of AFP was developed by monitoring the changes in the photocurrent signals of the electrode resulting from the immunoreaction. The immunosensor displayed a linear response to AFP in the ranges from 50pg/mL to 50ng/mL with a relatively low detection limit of 40pg/ml. The photoelectrochemical results for the detection of AFP in five human sera showed acceptable accuracy. The method is simple, sensitive and specific. Moreover, the studied immunosensor possessed acceptable reproducibility and storage stability. The proposed methodology was potentially attractive for clinical immunoassay.

Dopamine sensitized nanoporous TiO2 film on electrodes: Photoelectrochemical sensing of NADH under visible irradiation

Dopamine-coordinated photoactive TiO(2) nanoporous films with a wide excitation range of light in the visible region (up to 580 nm) were prepared and used for sensitive detection of NADH. Colloidal TiO(2) was firstly covered on an indium-tin oxide (ITO) electrode surface and sintered at 450 degrees C to form a nanoporous TiO(2) film, then the electrode was dipped in a dopamine solution to form a dopamine-TiO(2) charge transfer complex via coordinating dopamine with undercoordinated titanium atoms on the electrode surface. This charge transfer complex provided an anodic photocurrent under visible light and the photocurrent could be largely enhanced by NADH. The photocurrent enhancement might be due to the electron transfer between NADH and the holes localized on dopamine. A new photoelectrochemical methodology for sensitive detection of NADH at a relatively low potential was developed. The detection limit of NADH was 1.4x10(-7) M, and the detection range could extend up to 1.2x10(-4) M. The dopamine-TiO(2) modified electrode exhibits its major advantages such as effective electronic transducer, fast response and easy fabrication for photoelectrochemical determination of NADH. This strategy largely reduces the destructive effect of UV light and the photogenerated holes of illuminated TiO(2) to biomolecules and opens a new avenue for the applications of TiO(2) in photoelectrochemical biosensing.

A photoelectrochemical sensor based on CdS-polyamidoamine nano-composite film for cell capture and detection

We demonstrated herein a newly developed photoelectrochemical cell-sensor for the determination of SMMC-7721 human hepatoma carcinoma cells (SMMC-7721 cells) by using a photosensitive CdS-polyamidoamine (G4) nano-composite film (CdS-PAMAM). The film was generated by electrodeposition method. The presence of PAMAM in the film eliminated the surface defects of CdS nanoparticles and therefore resulted in a greatly enhanced photocurrent and a reduced dark current. In the presence of the electron donor ascorbic acid (AA), the photoexcitation of this modified electrode potentiostated at 0 V versus Ag/AgCl led to an anodic photocurrent. As a result of the covalent coupling reactions, a layer of concanavalin A (ConA) was firmly bound to the functionalized CdS-PAMAM film via glutaraldehyde bridges. The resulting modified electrodes were tested as sensors for SMMC-7721 cell capture and detection via affinity interactions between ConA and mannosyl groups on cell surface. The cell concentration was measured from 5.0 x 10(3) to 1.0 x 10(7) cells mL(-1) through the decrease in photocurrent intensity resulting from its specific binding onto the photosensitive film, the detection limit being 5.0 x 10(3) cells mL(-1).

A new approach to light up the application of semiconductor nanomaterials for photoelectrochemical biosensors: using self-operating photocathode as a highly selective enzyme sensor.

Due to the intrinsic hole oxidation reaction occurred on the photoanode surface, currently developed photoelectrochemical biosensors suffer from the interference from coexisting reductive species (acting as electron donor) and a novel design strategy of photoelectrode for photoelectrochemical detection is urgently required. In this paper, a self-operating photocathode based on CdS quantum dots sensitized three-dimensional (3D) nanoporous NiO was designed and created, which showed highly selective and reversible response to dissolved oxygen (acting as electron acceptor) in the electrolyte solution. Using glucose oxidase (GOD) as a biocatalyst, a novel photoelectrochemical sensor for glucose was developed. The commonly encountered interferents such as H2O2, ascorbic acid (AA), cysteine (Cys), dopamine (DA), etc., almost had no effect for the cathodic photocurrent of the 3D NiO/CdS electrode, though these substances were proved to greatly influence the photocurrent of photoanodes, which indicated greatly improved selectivity of the method. The method was applied to detect glucose in real samples including serum and glucose injections with satisfactory results. This study could provide a new train of thought on designing of self-operating photocathode in photoelectrochemical sensing, promoting the application of semiconductor nanomaterials in photoelectrochemistry.

Intrinsic enzyme mimicking activity of gold nanoclusters upon visible light triggering and its application for colorimetric trypsin detection

In this research, a novel enzyme mimetics based on the photochemical property of gold nanoclusters was demonstrated. It was found that the bovine serum albumin (BSA) stabilized red or blue emitting gold nanoclusters (Au NCs) exhibited enzyme-like activity under visible light irradiation. The BSA-Au NCs had better stability against stringent conditions compared to natural enzyme. In addition, the photostimulated enzyme mimetics of BSA-Au NCs showed several unprecedented advantages over natural peroxidase or other existing alternatives based on nanomaterials, such as the independence of hydrogen peroxide on activity and the easily regulated activity by light irradiation. The mechanism of the photoresponsive enzyme-like activity of BSA-Au NCs was investigated. The photoactivated BSA-Au NCs was designed to develop a facile, cheap, and rapid colorimetric assay to detect trypsin through trypsin digestion of the protein template of BSA-stabilized Au NCs. The limit of detection for trypsin was 0.6 μg/mL, which was much lower than the average level of trypsin in patients urine or serum.

A novel photoelectrochemical sensor based on photocathode of PbS quantum dots utilizing catalase mimetics of bio-bar-coded platinum nanoparticles/G-quadruplex/hemin for signal amplification.

Photocathode based on p-type PbS quantum dots (QDs) combing a novel signal amplification strategy utilizing catalase (CAT) mimetics was designed and utilized for sensitive photoelectrochemical (PEC) detection of DNA. The bio-bar-coded Pt nanoparticles (NPs)/G-quadruplex/hemin exhibited high CAT-like activity following the Michaelis-Menten model for decomposing H2O2 to water and oxygen, whose activity even slightly exceeded that of natural CAT. The bio-bar-code as a catalytic label was conjugated onto the surface of PbS QDs modified electrodes through the formed sandwich-type structure due to DNA hybridization. Oxygen in situ generated by the CAT mimetics of the bio-bar-code of Pt NPs/G-quadruplex/hemin acted as an efficient electron acceptor of illuminated PbS QDs, promoting charge separation and enhancing cathodic photocurrent. Under optimal conditions, the developed PEC biosensor for target DNA exhibited a dynamic range of 0.2pmol/L to 1.0nmol/L with a low detection limit of 0.08pmol/L. The high sensitivity of the method was resulted from the sensitive response of PbS QDs to oxygen and the highly efficient CAT-like catalytic activity of the bio-bar-coded Pt NPs/G-quadruplex/hemin.