Visible-light driven Photoelectrochemical Immunosensor Based on SnS2@mpg-C3N4 for Detection of Prostate Specific Antigen.

Herein, a novel label-free photoelectrochemical (PEC) immunosensor based on SnS2@mpg-C3N4 nanocomposite is fabricated for the detection of prostate specific antigen (PSA) in human serum. Firstly, mesoporous graphite-like carbon nitride (mpg-C3N4) with carboxyl groups is synthesized successfully which possesses high specific surface area and large pore volume. Then, SnS2 as a typical n-type semiconductor with weak photoelectric conversion capability is successfully loaded on carboxylated mpg-C3N4 to form a well-matched overlapping band-structure. The as-synthesized SnS2@mpg-C3N4 nanocomposite performs outstanding photocurrent response under visible-light irradiation due to low recombination rate of photoexcited electron-hole pairs, which is transcend than pure SnS2 or pure mpg-C3N4. It is worth noting that SnS2@mpg-C3N4 nanocomposite is firstly employed as the photoactive material in PEC immunosensor area. The concentration of PSA can be analyzed by the decrease in photocurrent resulted from increased steric hindrance of the immunocomplex. Under the optimal conditions, the developed PEC immunosensor displays a liner photocurrent response in the range of 50 fg·mL-1 ~ 10 ng·mL-1 with a low detection limit of 21 fg·mL-1. Furthermore, the fabricated immunosensor with satisfactory stability, reproducibility and selectivity provides a novel method for PSA determination in real sample analysis.

A visible light induced photoelectrochemical aptsensor constructed by aligned ZnO@CdTe core shell nanocable arrays/carboxylated g-C3N4 for the detection of Proprotein convertase subtilisin/kexin type 6 gene.

It was reported that Proprotein convertase subtilisin/kexin type 6 (PCSK6) can promote the progression of rheumatoid arthritis to a higher aggressive status. In this work, a novel visible light induced photoelectrochemical (PEC) platform was designed to detect PCSK6 gene. ZnO@CdTe nanocable arrays/carboxylated g-C3N4 used as the PEC signal generator. Hexagonal ZnO nanorods grew on ITO electrode firstly. CdTe were then electrodeposited on the ZnO nanorods surface to enhance the photogenerated h(+)/e(-) separation efficiency. Carboxylated g-C3N4 was utilized to improve h(+)/e(-) separation efficiency and anchor the capture probes of PCSK6 gene by the covalent bonding effect. The 5' and 3' primers captured PCSK6 ssDNA by the specific recognition. The linear range was 10 pg/mL to 20.0 ng/mL with a detection limit of 2 pg/mL.

A biomimetic mussel-inspired photoelectrochemical biosensing chip for the sensitive detection of CD146.

A photoelectrochemical biosensing chip was constructed through the mussel-inspired polydopamine coating strategy, which demonstrated improved photo-to-electric conversion performance for the CdS/TiO2-ITO chip, and was used for the direct immobilization of captured antibodies and the detection of CD146 in the absence of additional electron donors/acceptors.

CdSe quantum dot-functionalized TiO2 nanohybrids as a visible light induced photoelectrochemical platform for the detection of proprotein convertase subtilisin/kexin type 6.

Proprotein convertase subtilisin/kexin type 6 (PCSK6) plays a major role in promoting the progression of rheumatoid arthritis to a higher aggressive status. A novel highly sensitive photoelectrochemical platform was developed for the detection of PCSK6 by using CdSe quantum dots (QDs)-functionalized TiO2 nanoparticles (NPs) nanohybrids (TiO2@CdSe) as the photo-to-electron conversion medium. TiO2@CdSe showed excellent visible-light absorbency, and much higher photoelectrochemical activity than both CdSe QDs and TiO2 NPs. The 5' and 3' primers of PCSK6 ssDNA acted as capture probes to realize the detection of PCSK6 ssDNA by the specific recognition. The capture probes can be fixed by poly-l-lysine (PLL) through positively strong electrostatic attraction and the carboxyl group of TiO2@CdSe nanohybrids. PLL was electropolymerized on ITO electrode by cyclic voltammetry (CV). Simultaneously, the amino group of PLL can interact with the carboxyl group of TiO2@CdSe nanohybrids to enhance the stability of the photoelectrochemical signal. The fabricated aptsensor exhibited excellent performance towards PCSK6 with a wide linear range (0.5 pg/mL to 80.0 ng/mL) and a detection limit of 0.1 fg/mL. This work opens up a new detection platform for PCSK6 with good sensitivity, reproducibility and stability.

A signal-off sandwich photoelectrochemical immunosensor using TiO2 coupled with CdS as the photoactive matrix and copper (II) ion as inhibitor.

In this work, a novel sandwich photoelectrochemical (PEC) biosensor was developed based on a signal-off strategy using TiO2 coupled with CdS quantum dots (QDs) as the photoactive matrix and copper (II) ion (Cu(2+)) as inhibitor. TiO2/CdS modified indium tin oxide (ITO) electrode was employed for primary antibody (Ab1) immobilization and the subsequent sandwich-type antibody-antigen (Ab-Ag) affinity interactions. Flower-like copper oxide (CuO) was used as labels of secondary antibody (Ab2) and immobilized on the modified electrode via specific affinity interactions between Ab2 and Ag. Cu(2+) was released by dissolving CuO with HCl, and then reacted with CdS to form CuxS (x=1, 2), which would create new energy levels for electron-hole recombination and resulted in a decrease of the photocurrent. CuO, as the labels of Ab2, was first applied in PEC biosensor based on the signal-off strategy of the Cu(2+) for CdS. Greatly enhanced sensitivity was achieved through the coupling of CdS QDs with TiO2. Besides, the introduction of polythiophene (PT-Cl) on the surface of TiO2 made the PEC signal more stable. Under 405nm irradiation at 0.1V, the PEC biosensor for H-IgG determination exhibited a linear range from 0.1pgmL(-1) to 100ngmL(-1) with a low detection limit of 0.03pgmL(-1). The proposed biosensor showed high sensitivity, stability and selectivity, which opens up a new promising signal-off PEC platform for future bioassay.

Construction of dentate bonded TiO2-CdSe heterostructures with enhanced photoelectrochemical properties: versatile labels toward photoelectrochemical and electrochemical sensing.

A facile synthetic route for TiO2-CdSe heterostructures was proposed based on dentate binding of TiO2 to carboxyl. Carboxyl functionalized CdSe quantum dots (CF-CdSe QDs) were successfully bonded onto TiO2 nanoparticles (NPs), which could significantly improve the photoelectrochemical (PEC) properties of TiO2 NPs. This is ascribed to the fact that CdSe QDs with a narrow band gap could be stimulated under visible light irradiation, and the energy levels of TiO2 NPs and CF-CdSe QDs are aligned with an electrolyte solution. High resolution transmission electron microscopy images revealed the heterostructures of the TiO2-CdSe composites. Ultraviolet visible spectroscopy, photoluminescence emission spectroscopy and electrochemical impedance spectroscopy analysis exhibited that the prepared TiO2-CdSe heterostructures have improved light absorption, charge separation efficiency and electron transfer ability in the visible light region. TiO2-CdSe heterostructures were used as versatile labels for fabrication of PEC and electrochemical immunosensors, and human immune globulin G (HIgG) was used as a model analyte. The immunosensor showed high sensitivity, a low detection limit and a wide linear range, which could be applied in practical serum sample analysis. The constructed TiO2-CdSe heterostructures would have potential applications in photocatalysis, aptasensors, cytosensors and other areas of nanotechnology.

Label-free photoelectrochemical immunosensor for sensitive detection of Ochratoxin A.

A general label-free photoelectrochemical (PEC) platform was manufactured by assembly of CdSe nanoparticles (NPs) sensitized anatase TiO2-functionalized electrode via layer-by-layer (LBL) strategy. CdSe NPs were assembled on anatase TiO2-functionalized electrode through dentate binding of TiO2 NPs to -COOH groups. Ascorbic acid (AA) was used as an efficient electron donor for scavenging photogenerated holes under visible-light irradiation. The photocurrent response of the CdSe NPs modified electrode was significantly enhanced as a result of the band alignment of CdSe and TiO2 in electrolyte. Ochratoxin A (OTA), as model analyte, was employed to investigate the performance of the PEC platform. Antibodies of OTA were immobilized on CdSe sensitized electrode by using the classic 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride coupling reactions between -COOH groups on the surfaces of CdSe NPs and -NH2 groups of the antibody. Under the optimized conditions, the photocurrent was proportional to OTA concentration range from 10pg/mL to 50ng/mL with detection limit of 2.0pg/mL. The employed PEC platform established a simple, fast and inexpensive strategy for fabrication of label-free biosensor, which might be widely applied in bioanalysis and biosensing in the future.

Ultrasensitive electrochemical immunosensor for squamous cell carcinoma antigen detection using lamellar montmorillonite-gold nanostructures as signal amplification.

Sodium montmorillonites (Na-Mont), which could be transformed from nano-montmorillonites, have large surface area, chemical stability, nontoxicity, high cation exchange property and superior adsorption ability. In this paper, Na-Mont were used as a support of polyaniline (PANI) and gold nanoparticles (AuNPs) via the interaction of aniline and HAuCl4 solution. A sandwich-type electrochemical immunosensor was developed to detect squamous cell carcinoma antigen (SCC-Ag). It used nitrogen-doped graphene sheets (N-GS) for the immobilization of primary anti-SCC antibodies (Ab1) and the combined Na-Mont-PANI-AuNPs nanocomposites as labels. Na-Mont-PANI-AuNPs have excellent catalytic ability towards the reduction of H2O2, thus enhance the sensitivity of the immunosensor. The immunosensor exhibits a wide linear range (1 pg/mL-5 ng/mL), a low detection limit (0.3 pg/mL), good reproducibility, selectivity and stability. This new type of immunosensor with Na-Mont-PANI-AuNPs as labels may provide potential application for the detection of SCC-Ag.

Preparation of Au-Pt nanostructures by combining top-down with bottom-up strategies and application in label-free electrochemical immunosensor for detection of NMP22.

A novel label-free amperometric immunosensor for sensitive detection of nuclear matrix protein 22 (NMP22) was developed based on Au-Pt bimetallic nanostructures, which were prepared by combining top-down with bottom-up strategies. Nanoporous gold (NPG) was prepared by "top-down" dealloying of commercial Au/Ag alloy film. After deposition of NPG on an electrode, Pt nanoparticles (PtNPs) were further decorated on NPG by "bottom-up" electrodeposition. The prepared bimetallic nanostructures combine the merits of both NPG and PtNPs, and show a high electrocatalytic activity towards the reduction of H2O2. The label-free immunosensor was constructed by directly immobilizing antibody of NMP22 (anti-NMP22) on the surface of bimetallic nanostructures. The immunoreaction induced amperometric response could be detected and negatively correlated to the concentration of NMP22. Bimetallic nanostructure morphologies and detection conditions were investigated to obtain the best sensing performance. Under the optimal conditions, a linear range from 0.01ng/mL to 10ng/mL and a detection limit of 3.33pg/mL were obtained. The proposed immunosensor showed high sensitivity, good selectivity, stability, reproducibility, and regeneration for the detection of NMP22, and it was evaluated in urine samples, receiving satisfactory results.

Ultrasensitive dual amplification sandwich immunosensor for breast cancer susceptibility gene based on sheet materials.

A new electrochemical dual amplification sandwich immunosensor (DASI) was designed for ultrasensitive and accurate detection of the breast cancer susceptibility gene based on the combination of N-doped graphene, hydroxypropyl chitosan and Co3O4 mesoporous nanosheets. N-doped graphene has better electroconductibility than traditional graphene. It is an ideal electrochemical material with a large specific surface area and low resistance. Hydroxypropyl chitosan replaces the pure chitosan in immobilization of the sensor to achieve the sensitivity increase. Co3O4 mesoporous nanosheets can enhance the effective area of the immunoreaction. This kind of dual amplification sandwich immunosensor was first used for the detection of the breast cancer susceptibility gene. It has a wide linear response range of 0.001-35 ng mL(-1) and a minimum detection limit of 0.33 pg mL(-1). It was demonstrated that the stability, selectivity and reproducibility of the sensor were acceptable. The fabricated immunosensor shows great potential applications in early disease diagnosis.

Radially aligned microchannels prepared from ordered arrays of cracks on colloidal films.

Arrayed microchannels with dimensions of tens to hundreds of micrometres show great potential for application in microfluidics, microreactor devices and other areas. In this work, we report the formation of ordered arrays of cracks on solution-cast colloidal films, and the preparation of radially aligned microchannels. The polymer film coating enables the colloidal film to be detached from the substrate, retaining the crack patterns on the bottom side. The subsequent chemical corrosion converts the cracks into microchannels. Crack-patterned colloidal films are also used as structured substrates for the preparation of honeycomb films by the breath figure method. Hierarchical honeycomb structures are obtained, giving rise to improved support for colloidal films.