Search

A novel photoelectrochemical (PEC) biosensor based on an enzyme-free nucleic acid dual-amplification strategy combined with a mimic enzyme to catalyze the deposition of a quencher is reported for the ultrasensitive detection of miRNA-21. A limited amount of target miRNA-21 can trigger the formation of long DNA duplexes on the electrode, owing to the synergistic effect of the enzyme-free nucleic acid dual-amplification strategy of entropy-driven strand displacement reaction (ESDR) amplification and hybridization chain reaction (HCR) amplification. The embedded manganese porphyrin (MnPP) in the long DNA duplexes acts as a horseradish peroxidase (HRP)-mimicking enzyme to catalyze the transformation of benzo-4-chlorohexadienone on the electrode surface, resulting in a significant reduction in photocurrent intensity. As a photosensitive material, BiOCl-BiOI is used as a tag to provide strong initial PEC signals. Based on the cascade integration of the enzyme-free nucleic acid dual-amplification strategy and the mimic enzyme-catalyzed precipitation reaction, the current PEC biosensor exhibits outstanding performance for miRNA-21 detection with an ultralow detection limit (33 aM) and a wide quantification range (from 100 aM to 1 nM). This work provides a new avenue toward the ultrasensitive detection of miRNAs, and is expected to be used for clinical and biochemical samples. A unique PEC biosensor with the BiOCl-BiOI composite, as the photosensitive material, has been developed for ultrasensitive miRNA-21 determination based on the combination of an enzyme-free nucleic acid dual-amplification strategy and mimic enzyme catalytic precipitation reaction.

A facile and sensitive self-powered cathodic photoelectrochemical (PEC) aptasensor is reported for the detection of prostate-specific antigen (PSA) based on CuO-Cu2O nanowire array grown on Cu mesh (CuO-Cu2O NWA/CM) as electrode. The mixed narrow band gaps of the CuO-Cu2O heterostructure ensured its wide absorption band, effective electron/hole separation, and high photocatalytic activity in the visible region. In addition, nanowires directly grown on the substrate provided high specific surface area and exposed abundant active sites, thus guaranteeing its high photocatalytic efficiency. Therefore, the self-powered sensor exhibited favorable analytical performance with fast response, wide linear ranges of 0.01 to 5 ng/mL and 5 to 100 ng/mL, an acceptable detection limit of 3 pg/mL, and reasonable selectivity and stability. The proposed CuO-Cu2O NWA/CM can be considered a promising visible light-responsive photoactive material for fabrication of PEC aptasensor with high performance.

Flower-like graphene/CuO@Cu-BTC (GR/CuO@Cu-BTC) composite was employed as electrode material for the voltammetric determination of caffeic acid (CA) in the wine. The composite material was prepared via the self-template method. In this synthetic process, budlike CuO not only acts as the template, but also provides Cu2+ ions for in situ growth of the Cu-BTC shell. The utilization of GR as petal greatly boosts the stability and electronic conductivity of CuO@Cu-BTC. The GR/CuO@Cu-BTC composite possesses unique structural features with high specific surface area and good conductivity, exhibiting excellent electrocatalytic activity towards the oxidation of CA. Under optimized conditions, the sensor shows a good linear response to CA concentration over the range 0.020–10.0 μM, together with a low limit of detection (LOD) of 7.0 nM. Selectivity, reproducibility, and stability were investigated, and the method has been applied for the determination of CA in wine samples.

The authors have synthesized spindle-like ZnO nanorods closely anchored to CdS nanoparticles (NPs) placed on gold NPs (ZnO-CdS@Au). It is shown that the ZnO-CdS@Au nanocomposite can serve as a photoactive material for use in photoelectrochemical (PEC) detection by efficiently absorbing light and then promoting electron transfer. A visible light-driven PEC detection platform for tetracycline (TET) was fabricated by placing the nanocomposite on an ITO and immobilizing the TET-binding aptamer as biorecognition element. PEC can be quantified by applying a bias potential of + 0.4 V (vs. SCE) and visible light irradiation. The aptamer on the electrode specifically captures the TET present in the solution to produce a restored photocurrent signal through the reaction between the captured TET and the photogenerated holes. The electrode has a linear response in the 50 to 200 nM TET concentration range, with a 4.5 nM detection limit (at an S/N ratio of 3). In our perception, this novel PEC detection strategy based on ZnO-CdS@Au nanocomposite demonstrated an ultrasensitive method for TET detection with high selectivity and good stability.

A luminescent metal organic framework (LMOF) of type UiO-66-NH2 was chosen for specific and sensitive detection of trace levels of hypochlorite. Hypochlorite causes the quenching of the blue fluorescence of nano-UiO-66-NH2 (with excitation/emission maxima at 325/430 nm), and this finding forms the basis for a fluorometric assay for hypochlorite. The method overcomes disadvantages of conventional redox-probes which are interfered by oxidants with oxidation capability stronger than that of hypochlorite. Compared with other fluorescent probes for sensing hypochlorite, UiO-66-NH2 has a comparable detection limit of 0.3 μmol L−1 and a broad linearity relationship in the range of 1–8 μmol L−1. The probe was successfully applied to the detection of hypochlorite in complex water samples and living Hela cells.

An enzyme-free electrochemical method is described for the determination of trace levels of malathion. It is based on a nanostructured copper-cerium oxide (CuO-CeO2) composite prepared by calcination of a Cu(II)/Ce(III) metal-organic framework. The morphology, crystal structure and elemental composition of composite was studied by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The principle for malathion determination is based on the fact that the redox signal of CuO (best measured at around −0.1 V vs. SCE) (at 100 mV/s) is inhibited by malathion due to affinity between CuO and the sulfur groups of malathion. The introduction of CeO2 into the composite system further improves the analytical performance. This is attributed to the unique microstructure and the synergistic effect between CuO and CeO2. Experimental parameters like solution pH value, Cu/Ce molar ratio, accumulation potential, accumulation time, and CuO-CeO2 volume on the electrode were optimized. The assay has a linear range of 10 fM to 100 nM and a 3.3 fM detection limit (at S/N = 3). The electrode is selectively inhibited by malathion even in the presence of potentially interfering substances.

A photoelectrochemical (PEC) method has been developed for sensitive detection of trypsin. It is based on the use of a composite consisting of MoS2 nanosheets and TiO2 nanorods (MoS2-TiO2). The material has a high specific surface area, superior electrical conductivity, excellent biocompatibility and good band gap matching. The composite was synthesized by a one-pot method using TiO2 as a template. This results in a uniform distribution of the MoS2 nanosheets (

Nanosheets of tungsten disulfide (WS2) were used to improve the physicochemical properties of reduced graphene oxide aerogel (rGA). The nanosheets were directly integrated into 3D hybrid architecture of rGA by a solvothermal mixing method by which the WS2 sheets were assembled onto the conductive graphene network. WS2 with highly exfoliated and defect-rich structure made the WS2/rGA composite possess plentiful active sites, and this enhanced the electrocatalytic capability of the composite. The introduction of poorly conductive WS2 into 3D rGA system decreases the background current of rGA when used as electrode material. This is advantageous in terms of signal to-noise ratio and analytical performance in general. The WS2/rGA electrode, best operated at a potential of 0.68 V (vs. SCE) has a linear response in the 0.01 to 130 μM nitrite concentration range with a low detection limit of 3 nM (at S/N = 3). It is selective, reproducible, stable and is successfully applied to the determination of nitrite in spiked bacon samples.

A fluorometric turn-on assay is described for ascorbic acid (AA). It is based on the controlled release of polyallylamine-stabilized gold nanoclusters (polyallylamine-AuNCs) from MnO2 nanosheets. In an aqueous solution of near-neutral pH value, the positively charged capped AuNCs are adsorbed on the surface of the negatively charged MnO2 nanosheets. The adsorption leads to the quenching of the fluorescence of the AuNCs. However, in the presence of AA, MnO2 is reduced to Mn2+. This causes the destruction of the MnO2 nanosheets. As a result, the fluorescence of the polyallylamine-AuNCs at 615 nm is recovered. This method for determination of AA is inexpensive, sensitive, and selective. It works in the 0.01 to 200 μM concentration range and has a 3.2 nM detection limit (for S/N = 3).

A method is described for photoelectrochemical determination of the activity of alkaline phosphatase (ALP). It employs an indium tin oxide (ITO) electrode modified a CdS quantum dots@graphene (CdS@GR) composite and hexagonal cobalt oxyhydroxide (CoOOH) nanosheets. The CdS@GR nanocomposite was synthesized by assembling the CdS quantum dots onto a GO film to receive a basic photocurrent response of the ITO. This is further improved by covering it with CoOOH nanosheets. Secondly, 2-phospho-L-ascorbic acid (AAP) is added as a substrate for ALP. Its hydrolysis yields ascorbic acid which reduces CoOOH to form cobalt(II) ion. As a result, the CoOOH nanosheets decompose. This is accompanied by a reduction of the photocurrent. The effect was used to design a selective and sensitive assay of determination of the activity of ALP. Under the optimized experimental conditions, response is linear in the 10 to 300 U·L−1ALP activity range. The detection limit is 1.5 U·L−1 at a signal-to-noise ratio of 3.

The fluorescence intensity of gold nanoclusters (AuNCs) is inversely related to the length of a peptide immobilized on its surface. This finding has been exploited to design a turn-on fluorescent method for the determination of the activity of peptidase. The β-site amyloid precursor protein-cleaving enzyme 1 (BACE1) was chosen as a model peptidase. BACE1 cleaves the peptide substrates on AuNCs, and the fluorescence intensity of the AuNCs (at exCitation/emission wavelengths of 320/405 nm) carrying the rest of the cleaved peptide is significantly higher than that of the AuNCs with uncleaved peptide. Transmission electron microscopy revealed a decrease in the size of the AuNCs which is assumed cause fluorescence enhancement. The assay was applied to the determination of BACE1 activity in spiked cell lysates, and recoveries were between 96.9 and 104.0 %.

A glassy carbon electrode was modified with an array of porous Ni3N nanosheets (Ni3N NA) and studied for its use in non-enzymatic electrochemical detection of glucose. The morphology and structure of the Ni3N NA were characterized by scanning electron microscopy and X-ray diffraction. Electrochemical studies demonstrated that the Ni3N NA acts as an efficient catalyst for the electro-oxidation of glucose at pH 13, best at a working voltage of 0.55 V (vs. Ag/AgCl). Figures of merit include (a) high sensitivity (39 μA·mM−1·cm−2), (b) a low limit of detection (0.48 μM), and (c) a linear range that extends from 2 μM to 7.5 mM. The sensor was applied to the determination of glucose levels in human serum, and satisfactory results were obtained.

The authors describe a fluorescent “turn-on” assay for detection of uric acid (UA) based on the use of graphene quantum dots coated with a shell of silver (GQD@Ag). The fluorescence of the GQDs is quenched by the silver shell. However, if the silver shell was removed via etching with H2O2 (which is produced by uricase catalyzed oxidation of UA), the fluorescence of the GQDs is restored. The resulting increase in fluorescence at 466 nm depends directly on the concentration of H2O2, which, in turn, depends on the concentration of UA. The method allows UA to be quantitated with a 2 μM detection limit. It was applied to the analysis of human urine samples and exhibited satisfactory results. The method is cost-effective, sensitive and selective for UA. In our perception, it provides a useful tool in clinical analysis and may be extended to other assays based on the use of oxidases.

The authors describe a novel method for the determination of glutathione (GSH). Detection is based on target induced release of glucose from MnO2 nanosheet-gated aminated mesoporous silica nanoparticles (MSNs). In detail, glucose is loaded into the pores of MSNs. Negatively charged MnO2 nanosheets are assembled on the MSNs through electrostatic interactions. The nanosheets are reduced by GSH, and this results in the release of glucose which is quantified by using a commercial electrochemical glucose meter. GSH can be quantified by this method in the 100 nM to 10 μM concentration range, with a 34 nM limit of detection.