A highly sensitive photoelectrochemical biosensor for CEA analysis based on hollow NiS@NiO/TiO2 composite with typal p-n heterostructure.

Heterostructured construction is regarded as a valuable approach to improve photoelectrochemical (PEC) performances. Herein, porous hollow NiS@NiO spheres were prepared derived from the Ni(TCY) MOFs precursor. Photoactive TiO2 was coupled with as-prepared NiS@NiO to form a close heterojunction interface of NiS@NiO/TiO2. NiS@NiO/TiO2 modified ITO electrode (NiS@NiO/TiO2/ITO) displayed fiercely enhanced photocurrent response, which was 4687-fold than that of NiS@NiO/ITO (0.008 µA) and 8.5-fold than that of TiO2/ITO (4.41 µA), respectively. Remarkable PEC property could be ascribed to the hollow NiS@NiO spheres with thin-shell structure provided there is a larger active surface area for harvesting the visible light. Most importantly, the p-n type NiS@NiO/TiO2 heterojunction could lead to generating more photo-excited charge carriers (e-/h+) and efficiently hinder the recombination of carriers, resulting in significantly augmented photocurrent output. Based on this outstanding PEC property, NiS@NiO/TiO2/ITO electrode fabricated sensing platform (BSA/anti-CEA/NiS@NiO/TiO2/ITO, BSA=Bovine serum albumin) exhibited high sensitivity for monitoring CEA (Carcinoembryonic antigen). Wide linear detection range was from 0.001 to 45 ng mL-1 and with a low detection limit of 1.67 × 10-4 ng mL-1 (S/N = 3). Prepared biosensors also showed good reproducibility, stability and had satisfying specificity. Thus, the proposed NiS@NiO/TiO2 heterostructured composite afforded well-design and synthesis strategy for constructing high-performance photoactive materials from MOFs-derivate.

In-situ construction of hollow double-shelled CoSx@CdS nanocages with prominent photoelectric response for highly sensitive photoelectrochemical biosensor.

In this work, we demonstrate a delicate design and construction of hollow double-shelled CoSx@CdS nanocages (CoSx@CdS-HDSNCs) as an efficient and stable photoactive material of photoelectrochemical (PEC) biosensor for detecting cardiac troponin I (cTnI). The novel self-templated strategy started with ZIF-67, in which two distinct sulfide semiconductors were integrated into a hollow heterojunction with uniform interfacial contacts after sequential anion and cation exchange. The unique thin double shell hollow structure, suitable energy band arrangement and stable electron transmission vastly enhanced the ability of light capture and photogenerated electron-hole separation of biosensor. Subsequently, the photoelectric performance of the heterojunction was further enhanced by the deposition of Au nanoparticles (NPs) on the surface of the CoSx@CdS-HDSNCs resulting in surface plasmon resonance (SPR) effect. Based on the excellent CoSx@CdS-HDSNCs, the biosensor exhibits a high sensitivity for detection of cTnI with a wide linear range (0.00016-16 ng mL-1) and low detection limit (38.6 fg mL-1). Besides, the PEC biosensor exhibited satisfactory stability, selectivity, and reproducibility in human serum. And more importantly, our work may provide more unique inspiration for the design of photoactive materials for the future PEC sensing applications.

Sensitive photoelectrochemical detection of colitoxin DNA based on NCDs@CuO/ZnO heterostructured nanocomposites with efficient separation capacity of photo-induced carriers.

A metal-organic framework (MOF) of Cu-TPA (terephthalic acid) microsphere was prepared, followed by calcinating the MOF precursor of Cu-TPA/ZIF-8 mixture to obtain the CuO/ZnO. N-doped carbon dots (NCDs) were employed to combine the CuO/ZnO composite to form a tripartite heterostructured architecture of NCDs@CuO/ZnO, which led to a fierce enlargement of the photocurrent response. This  was ascribed to the thinner-shell structure of the CuO microsphere and the fact that hollow ZnO particles could sharply promote the incidence intensity of visible light. The more porous defectiveness exposed on CuO/ZnO surface was in favor of rapidly infiltrating electrolyte ions. The p-n type CuO/ZnO composite with more contact interface could abridge the transfer distance of photo-induced electron (e-1)/hole (h+) pairs and repress their recombination availably. NCDs not only could boost electron transfer rate on the electrode interface but also successfully sensitized the CuO/ZnO composite, which resulted in high conversion efficiency of photon-to-electron. The probe DNA (S1) was firmly assembled on the modified ITO electrode surface (S1/NCDs@CuO/ZnO) through an amidation reaction. Under optimal conditions, the prepared DNA biosensor displayed a wide linear range of 1.0 × 10-6 ~ 7.5 × 10-1 nM and a low limit of detection (LOD) of 1.81 × 10-7 nM for colitoxin DNA (S2) measure, which exhibited a better photoelectrochemistry (PEC) analysis performance than that obtained by differential pulse voltammetry techniques. The relative standard deviation (RSD) of the sensing platform for target DNA detection of 5.0 × 10-2 nM was 6.3%. This proposed DNA biosensor also showed good selectivity, stability, and reproducibility, demonstrating that the well-designed and synthesized photoactive materials of NCDs@CuO/ZnO are promising candidates for PEC analysis.

In situ H2O2 generation with gold nanoflowers as the coreactant accelerator for enzyme-free electrochemiluminescent immunosensing.

In traditional electrochemiluminescence (ECL) analysis, gold nanomaterials are commonly used as a tool for signal amplification and linking antibodies due to their good electrical conductivity and biocompatibility. Here, we found that multitipped gold nanoparticles-gold nanoflowers (AuNFs) as coreactant accelerator have good catalytic activity for the reduction of dissolved oxygen (O2) to hydrogen peroxide (H2O2) using tris (hydroxymethyl) aminomethane (Tris) as electron donor. Based on this, a new enzyme-free and label-free ECL immunosensor have been constructed for the detection of α-fetoprotein (AFP). In this system, due to the unique geometric and spatial effects of AuNFs, the dissolved O2 as endogenous coreactant was catalyzed by AuNFs to produce H2O2 using Tris as an electron donor. The in situ generated H2O2 can more efficiently produce various electrogenerated reactive oxygen species (ROSs) as the important intermediates on the electrode surface. Then, oxidation of luminol reacts with ROSs significantly amplifies the luminol ECL signal. Under optimal experimental conditions, the proposed ECL immunosensor was able to detect the AFP concentration from 0.01 to 100 ng mL-1, with a low detection limit of 3.4 pg mL-1 (S/N = 3). In addition, the prepared ITO-based sensor is similar to a micro-test chip and convenient to use, thus making it suitable for clinical use as a disposable device in point-of-care tests (POCTs).

Three-dimensional Tri-SNSs-layered electrodeposited reduced graphene oxide for ECL biosensing of DNA.

In this study,we proposed a triangular silver nanosheets (Tri-SNSs)-layered, Chitosan (CS)-supported three-dimensional of reduced graphene oxide (3D-ERGO) electrochemiluminescence (ECL) biosensing platform using self-designed dual-Ru(bpy)32+ scDNA (Ru2-DNA) as capture probe for ECL biosensing of single-chain DNA (scDNA). Based on the different affinity with scDNA and double chain DNA (dcDNA), the biosensor is designed to recognize the target DNA (t-DNA), which leads to the desorption of a hybrid molecule from the surface of the biosensor, further removing the Ru2-DNA and inhibiting the ECL. Analytical results clearly showed that the electrochemical and ECL behaviors of proposed biosensing platform on the glassy carbon electrode (GCE) exhibited outstanding performance, which was due to large specific surface area, high carrier mobility and strong π-π non-covalent attraction toward single-chain DNA (scDNA) of the stable 3D platform, and ECL amplification of Tri-SNSs. Besides, based on such a system, this strategy can effectively identify full match and mismatched target DNA (M-DNA) with a wide concentration range beyond 7 orders of magnitude and detection limit down to 16.2 aM. Therefore, the 3D biosensing strategy shows potential for the application of bioassays.

A photoelectrochemical aptasensor for thrombin based on the use of carbon quantum dot-sensitized TiO2 and visible-light photoelectrochemical activity.

A photoelectrochemical (PEC) aptasensor for the highly sensitive and specific detection of thrombin is described. This aptasensor is based on an indium tin oxide (ITO) support that is covered with carbon quantum dot (CQD)-sensitized TiO2 and acts as a photoactive matrix. The ITO/TiO2/CQD electrode was prepared by impregnation assembly. It displays an enhanced and steady photocurrent response under irradiation by visible light. A carboxyl-functionalized thrombin-binding aptamer was covalently immobilized on the modified ITO to obtain a PEC aptasensor whose photocurrent decreases with increasing concentration of thrombin. Under 420 nm irradiation at a bias voltage of 0 V, the aptasensor has a linear response in the 1.0 to 250 pM thrombin concentration range, with a 0.83 pM detection limit. Conceivably, this approach can be extended to numerous other PEC aptasensors for the detection of targets for which appropriate aptamers are available. Graphical abstract Schematic of a PEC aptasensor for thrombin. It is based on the use of CQD as the sensitizer, TiO2/CQDs as the photoactive matrix, and the thrombin aptamer as the recognition element.

A novel and sensitive fluorescence sensor for glutathione detection by controlling the surface passivation degree of carbon quantum dots.

A novel fluorescence sensor based on controlling the surface passivation degree of carbon quantum dots (CQDs) was developed for glutathione (GSH) detection. First, we found that the fluorescence intensity of the CQDs which was obtained by directly pyrolyzing citric acid would increased largely after the surface passivation treatment by 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC). In the light of this phenomenon, we designed a simple, rapid and selective fluorescence sensor based on the surface passivated CQDs. A certain and excess amount of EDC were mixed with GSH, part of EDC would form a stable complex with GSH owing to the exposed sulfhydryl group of GSH. As the synthesized CQDs were added into the above mixture solution, the fluorescence intensity of the (EDC/GSH)/CQDs mixture solution could be directly related to the amount of GSH. Compared to other fluorescence analytical methods, the fluorescence sensor we design is neither the traditional fluorescent "turn on" probes nor "turn off" probes. It is a new fluorescence analytical method that target object indirectly control the surface passivation degree of CQDs so that it can realize the detection of the target object. Moreover, the proposed method manifested great advantages including short analysis time, low cost and ease of operation.