A photoelectrochemical wire microelectrode was constructed based on the use of a TiO2 nanotube array with electrochemically deposited CdSe semiconductor. A strongly amplified photocurrent is generated on the sensor surface. The microsensor has a response in the 0.05–20 μM dopamine (DA) concentration range and a 16.7 μM detection limit at a signal-to-noise ratio of 3. Sensitivity, recovery and reproducibility of the sensor were validated by detecting DA in spiked human urine, and satisfactory results were obtained.
Graphical abstract Schematic of a sensitive photoelectrochemical microsensor based on CdSe modified TiO2 nanotube array. The photoelectrochemical microsensor was successfully applied to the determination of dopamine in urine samples.
A novel photoelectrochemical (PEC) aptasensor with graphitic-phase carbon nitride quantum dots (g-C3N4; QDs) and reduced graphene oxide (rGO) was fabricated. The g-C3N4 QDs possess enhanced emission quantum yield (with an emission peak at 450 nm), improved charge separation ability and effective optical absorption, while rGO has excellent electron transfer capability. Altogether, this results in improved PEC performance. The method is making use of an aptamer against sulfadimethoxine (SDM) that was immobilized on electrode through π stacking interaction. Changes of the photocurrent occur because SDM as a photogenerated hole acceptor can further accelerate the separation of photoexcited carriers. Under optimized conditions and at an applied potential of +0.2 V, the aptasensor has a linear response in the 0.5 nM to 80 nM SDM concentration range, with a 0.1 nM detection limit (at S/N =?3). The method was successfully applied to the analysis of SDM in tap, lake and waste water samples.
Graphical abstract Graphitic-phase carbon nitride (g-C3N4) quantum dots (QDs) and reduced graphene oxide (rGO) were used to modify fluorine-doped SnO2 (FTO) electrodes for use in a photoelectrochemical (PEC) aptasensor. SDM oxidized by the hole on valance band (VB) of g-C3N4 QDs promote the separation of electron in the conductive band (CB), which made the changes of photocurrent signal.
Tungsten disulfide (WS2) nanosheets were obtained by exfoliating WS2 bulk crystals in N-methylpyrrolidone by ultrasonication. Gold nanoparticles (GNPs) were synthesized by in-situ ultrasonication of sodium citrate and HAuCl4 while fabricating the WS2 nanosheets. In this way, the GNPs were self-assembled on WS2 nanosheets to form a GNPs/WS2 nanocomposite through interaction between sulfur and gold atoms. The photoelectrochemical response of WS2 nanosheets is significantly enhanced after integration of the GNPs. The GNPs/WS2 nanocomposite was coated onto a glassy carbon electrode (GCE) to construct a sensing interface which then was modified with an antibody against the carcinoembryonic antigen (CEA) to obtain a photoelectrochemical immunosensor for CEA. Under optimized conditions, the decline in relative photocurrent is linearly related to the logarithm of the CEA concentration in the range from 0.001 to 40 ng mL?1. The detection limit is 0.5 pg mL?1 (at S/N =?3). The assay is sensitive, selective, stable and reproducible. It was applied to the determination of CEA in clinical serum samples.
Graphical abstract Schematic presentation of the fabrication of Au/WS2 nanocomposites by in-situ ultrasonication and the procedure for the CEA photoelectrochemical immunosensor preparation, and the photocurrent response towards the carcinoembryonic antigen.
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.
The paper describes a sensitive method for simultaneous sensing of morphine (MOR) and diclofenac (DCF). The surface of a MgFe2O4/graphite paste electrode was modified with multi-walled carbon nanotubes, and the resulting sensor was characterized by cyclic voltammetry, differential pulse voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. The electrode showed an efficient synergistic effect in term of oxidation of DCF and MOR, with sharp oxidation peaks occurring at +0.370 and 0.540 V (vs Ag/AgCl) at pH 7.0. The calibration plot for MOR is linear in the 50 nM to 920 μM concentration range, and the detection limit is 10 nM (at a signal-to-noise ratio of 3). The respective data for DCF are 100 nM to 580 μM, with a 60 nM LOD. The sensor was applied to the determination of MOR and DCF in spiked serum and urine samples, with recoveries ranging between 91.4 and 100.7 %.
Graphical abstract A sensitive method for simultaneous sensing of morphine (MOR) and diclofenac (DCF) is described. The surface of MgFe2O4/graphite paste electrode was modified with multi-walled carbon nanotubes, and the resulting sensor showed an efficient synergistic effect in terms of oxidation of DCF and MOR. The calibration plot for MOR is linear in the 50 nM to 920 μM concentration range, and the detection limit is 10 nM. The respective data for DCF are 100 nM to 580 μM, with a 60 nM LOD.
The authors describe a dye-sensitized photoelectrochemical immunoassay for the tumor marker carcinoembryonic antigen (CEA). The method employs the rhodamine dye Rh123 with red color and absorption maximum at 500 nm for spectral sensitization, and a 3D nanocomposite prepared from graphene oxide and MoS2 acting as the photoelectric conversion layer. The nanocomposite with flower-like 3D architectures was characterized by transmission electron microscopy, scanning electron microscopy, X-ray powder diffraction, and UV-vis diffuse reflectometry. A photoelectrochemical sandwich immunoassay was developed that is based on the use of the nanocomposite and based on the specific binding of antibody and antigen, and by using a secondary antibody labeled with Rh123 and CdS (Ab2-Rh123@CdS). Under optimal conditions and at a typical working voltage of 0 V (vs. Hg/HgCl2), the photocurrent increases linearly 10 pg mL?1 to 80 ng mL?1 CEA concentration range, with a 3.2 pg mL?1 detection limit.
Graphical abstract Flower-like GO-MoS2 complex with high efficiency of electron transport was synthesized to construct photoelectrochemical platform. The sandwich-type immunoassay was built on this platform based on specific binding of antigen and antibody. Carcinoembryonic antigen in sample was detected sensitively by using sensitization of rhodamine dye Rh123 as signal amplification strategy.
The authors describe a highly efficient photoelectrochemical (PEC) scheme for the determination of hydrogen peroxide (H2O2). BiVO4 microrods were hydrothermally synthesized and deposited on fluorine - doped tin oxide (FTO) glass which acts as the working electrode. Scanning electron microscopy, X-ray powder diffraction and Raman spectroscopy were utilized for the characterization of the microrods. On irradiation with visible light, the holes generated in the microrods are capturing electrons from H2O2 to produce a photocurrent at an operating potential of 0 V vs. Ag/AgCl. Under optimal conditions, the photocurrent increases with the concentration of H2O2 in the range from 50 μmol·L?1 to 1.5 mmol·L?1, and the limit of detection is 8.5 μmol·L?1 (at 3σ). A repeatability and intermediate precision of ≤6.6% was accomplished at H2O2 levels of 0.1, 0.5 and 1.0 mmol·L?1. The method was applied to the determination of H2O2 in spiked sterilized milk samples and gave satisfactory results. As the method works at zero potential, the photocurrent can be measured with simple instrumentation such as digital multimeters, and this will enable expensive electrochemical workstations to be replaced in future.
Graphical abstract An enzyme-free photoelectrochemical sensing strategy is described for sensitive determination of hydrogen peroxide in foodstuff using fluorine-doped tin oxide electrode modified with BiVO4 microrods.
The authors report on the fabrication of Co(OH)2-enfolded Cu2O nanocubes on reduced graphene oxide (rGO), and the use of this material in an electrochemical caffeine sensor. The rGO/Cu2O/Co(OH)2 composite was characterized by X-ray powder diffraction pattern analysis, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy and Raman spectroscopy. A rotating disc glassy carbon electrode covered with the nanocomposite displays enhanced electrocatalytic activity towards the electro-oxidation of caffeine. The peak oxidation potential is at 1.4 V (vs. Ag/AgCl) and hence is strongly shifted to the negative side when compared to other modified electrodes. The calibration plot is linear in the 0.83 to 1200 μM concentration range, with a 0.4 μM detection limit (at a signal-to-noise ratio of 3). The modified electrode is sensitive, selective and stable. It was successfully applied to the determination of caffeine in (spiked) caffeine-containing beverages and coffee powder and gave recoveries that ranged from 95.7 to 98.3 %.
A nanocomposite consisting of cetyltrimethylammonium bromide (CTAB), Fe3O4 nanoparticles and reduced graphene oxide (CTAB-Fe3O4-rGO) was prepared, characterized, and used to modify the surface of a glassy carbon electrode (GCE). The voltammetric response of the modified GCE to 4-nonylphenol (NPh) was investigated by cyclic voltammetry and revealed a strong peak at around 0.57 V (vs. SCE). Under optimum conditions, the calibration plot is linear in the ranges from 0.03 to 7.0 μM and from 7.0 to 15.0 μM, with a 8 nM detection limit which is lower that that of many other methods. The modified electrode has excellent fabrication reproducibility and was applied to the determination of NPh in spiked real water samples to give recoveries (at a spiking level of 1 μM) between 102.1 and 99.1%.
Graphical abstract A nanocomposite consisting of cetyltrimethylammonium bromide (CTAB), Fe3O4 nanoparticles and reduced graphene oxide (CTAB-Fe3O4-rGO) was prepared and used to modify the surface of a glassy carbon electrode (GCE) for the differential pulse voltammetric (DPV) determination of 4-nonylphenol (NPh).
Thin films of La2O3 were deposited onto glass substrates by ultrasonic spray pyrolysis. Their structural and morphological properties were characterized by X-ray diffraction, Fourier transform Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photo-electron spectroscopy, Brunauer-Emmett-Teller and optical absorption techniques. The sensor displays superior CO2 gas sensing performance at a low operating temperature of 498 K. The signal change on exposure to 300 ppm of CO2 is about 75%, and the signal only drops to 91% after 30 days of operation.
Graphical abstract Schematic diagram of the CO2 gas sensing mechanism of an interconnected web-like La2O3 nanostructure in presence of 300 ppm of CO2 gas and at an operating temperature of 498 K.
A voltammetric sensor is described for the quantitation of propyl gallate (PG). A screen-printed carbon electrode (SPCE) was modified with reduced graphene sheets that were decorated with cobalt diselenide nanoparticles (CoSe2@rGO). The material was hydrothermally prepared and characterized by several spectroscopic techniques. The modified SPCE displays excellent electrocatalytic ability towards PG. Differential pulse voltammetry, with a peak voltage at 0.34 V (vs. Ag/AgCl) has a sensitivity of 12.84 μA·μM?1·cm?2 and a detection limit as low as 16 nM. The method is reproducible, selective, and practical. This method was applied to the determination of PG in spiked meat samples, and the result showed an adequate recovery.
A composite material obtained by ultrasonication of graphene oxide (GO) and multi-walled carbon nanotubes (MWCNTs) was loaded with manganese dioxide (MnO2), poly(diallyldimethylammonium chloride) and gold nanoparticles (AuNPs), and the resulting multilayer hybrid films were deposited on a glassy carbon electrode (GCE). The microstructure, composition and electrochemical behavior of the composite and the modified GCE were characterized by transmission electron microscopy, Raman spectra, energy-dispersive X-ray spectroscopy, electrochemical impedance spectroscopy and cyclic voltammetry. The electrode induces efficient electrocatalytic oxidation of dopamine at a rather low working voltage of 0.22 V (vs. SCE) at neutral pH values. The response is linear in the 0.5 μM to 2.5 mM concentration range, the sensitivity is 233.4 μA·mM￣1·cm￣2, and the detection limit is 0.17 μM at an SNR of 3. The sensor is well reproducible and stable. It displays high selectivity over ascorbic acid, uric acid and glucose even if these are present in comparable concentrations.
Graphical abstract Gold nanoparticles were self-assembled onto the surface of the MnO2 decorated graphene oxide-carbon nanotubes composites with poly(diallyldimethylammonium chloride) (PDDA) as a coupling agent. Further, a sensitive electrochemical sensor of dopamine was developed via immobilizing this nanocomposite on a glassy carbon electrode (GCE).
This study describes an amperometric sensor for hydrogen peroxide (H2O2) that uses an ITO glass electrode which was modified with a nanocomposite consisting of electrochemically reduced graphene oxide and gold nanoclusters (AuNCs). The sensor was used to quantify extracellular H2O2 released from human neuroblastoma cells of type SH-SY5Y. The calibration plot, established best at a working voltage of ?0.4 V (vs. Ag/AgCl) is linear in the 40 nmol?L?1 to 2 μmol?L?1 concentration range, and the detection limit is 20 nmol?L?1 (at a signal-to-noise ratio of 3). The method was further applied to study bupivacaine-induced cell damage and the protective effects of α-lipoic acid. The study indicated that pretreatment of the cells with lipoic acid retards cell damage induced by bupivacaine. The sensor can be easily fabricated, is disposable and highly sensitive. The sensor is perceived to represent an alternative for studying the interactions of drugs with cells, and as an effective tool to quantify cell-secreted H2O2.
Graphical abstract One-step electrochemical synthesis of graphene oxide and gold nanoclusters on an ITO electrode for studying the release of H2O2 from SH-SY5Y cells and for evaluation of drug-induced cell damage
The authors describe an amperometric sensor for dopamine (DA) by employing olive-like Fe2O3 microspheres (OFMs) as the electrocatalyst for DA oxidization. The OFMs were prepared by using a protein templated method. The structure and properties of the OFMs were characterized by scanning electron microscopy, X-ray powder diffraction, energy dispersive x-ray spectroscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The OFMs possess excellent catalytic activity towards DA oxidization due to their unique morphology. The sensor responds to DA within less than 5 s. The sensor, best operated at a voltage of +0.2 V (vs. SCE) responds linearly in the 0.2 to 115 μM DA concentration range and has a 30 nM detection limit. The selectivity, reproducibility and long-term stability of the sensor are acceptable. It performs well when applied to spiked human urine samples.
Graphical abstract Olive-like Fe2O3 microspheres (OFMs), synthesized using egg white as template, display excellent catalytic activity towards dopamine (DA) oxidization due to their unique morphology. They were applied for DA detection using the amperometric technique. The electrochemical sensor exhibited a high sensitivity and a 30 nM detection limit. DAQ: dopaquinone.
We describe a chemical exfoliation method for the preparation of MoS2 nanosheets. The nanosheets were incorporated into poly(3,4-ethylenedioxythiophene) (PEDOT) by electrodeposition on a glassy carbon electrode (GCE) to form a nanocomposite. The modified GCE is shown to enable simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA). Due to the synergistic effect of MoS2 and PEDOT, this electrode displays better properties in terms of electrocatalytic oxidation of AA, DA and UA than pure PEDOT, which is illustrated by cyclic voltammetry and differential pulse voltammetry (DPV). Under optimum conditions and at pH 7.4, the respective sensitivities and best working potentials are as follows: AA: 1.20 A?mM?1?m?2, 30 mV; DA: 36.40 A?mM?1?m?2, 210 mV; UA: 105.17 A?mM?1?m?2, 350 mV. The calculated detection limits for AA, DA and UA are 5.83 μM, 0.52 μM and 0.95 μM, respectively. The modified electrode was applied to the detection of the three species in human urine samples and gave satisfactory results.
Graphical abstract MoS2 nanosheets were prepared by a facile chemical exfoliation method. MoS2 and poly(3,4-ethylenedioxythiophene) nanocomposite modified glassy carbon electrodes were fabricated, which are shown to enable simultaneous determination of ascorbic acid, dopamine and uric acid with high sensitivity and selectivity.
Ionic liquid coated nanoparticles (IL-NPs) consisting of zero-valent iron are shown to display intrinsic peroxidase-like activity with enhanced potential to catalyze the oxidation of the chromogenic substrate 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide. This results in the formation of a blue green colored product that can be detected with bare eyes and quantified by photometry at 652 nm. The IL-NPs were further doped with bismuth to enhance its catalytic properties. The Bi-doped IL-NPs were characterized by FTIR, X-ray diffraction and scanning electron microscopy. A colorimetric assay was worked out for hydrogen peroxide that is simple, sensitive and selective. Response is linear in the 30–300 μM H2O2 concentration range, and the detection limit is 0.15 μM.
Graphical abstract Schematic of ionic liquid coated iron nanoparticles that display intrinsic peroxidase-like activity. They are capable of oxidizing the chromogenic substrate 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide. This catalytic oxidation generated blue-green color can be measured by colorimetry. Response is linear in the range of 30–300 μM H2O2 concentration, and the detection limit is 0.15 μM.
A nanocomposite consisting of a few layers of graphene (FLG) and tin dioxide (SnO2) was prepared by ultrasound-assisted synthesis. The uniform SnO2 nanoparticles (NPs) on the FLG were characterized by X-ray diffraction in terms of lattice and phase structure. The functional groups present in the composite were analyzed by FTIR. Electron microscopy (HR-TEM and FE-SEM) was used to study the morphology. The effect of the fraction of FLG present in the nanocomposite was investigated. Sensitivity, selectivity and reproducibility towards resistive sensing of liquid propane gas (LPG) was characterized by the I-V method. The sensor with 1% of FLG on SnO2 operated at a typical voltage of 1 V performs best in giving a rapid and sensitive response even at 27 °C. This proves that the operating temperature of such sensors can be drastically decreased which is in contrast to conventional metal oxide LPG sensors.
Graphical abstract Schematic of a room temperature gas sensor for liquefied petroleum gas (LPG). It is based on the use of a few-layered graphene (1 wt%)/SnO2 nanocomposite that was deposited on an interdigitated electrode (IDEs). A sensing mechanism for LPG detection has been established.
The authors describe an electrochemical sensor for hydrogen peroxide (H2O2). It was constructed by consecutive, selective modification of a glassy carbon electrode (GCE) with Prussian Blue (PB), layered molybdenum disulfide (MoS2), and reduced graphene oxide (rGO). The properties of the modified GCE were characterized via high-resolution transmission electron microscopy, UV-vis spectroscopy and X-ray diffraction. The electrochemical properties of the electrode were studied using cyclic voltammetry and electrochemical impedance spectroscopy. The sensor exhibits excellent electrocatalytic activity for the reduction of hydrogen peroxide in comparison to GCEs modified with MoS2-rGO or PB only. Response is linear in the 0.3 μM to 1.15 mM H2O2 concentration range at a working analytical voltage of 0.1 V, with a 0.14 μM detection limit. The electrochemical sensitivity is 2883.5 μA·μM?1·cm?2, and response is fast (<10 s). The sensor is selective, stable and reproducible. This is attributed to the efficient electron transport properties of the MoS2-rGO composite and the high loading with PB.
Graphic abstract Prussian Blue nanoparticles were deposited on MoS2-rGO modified glassy carbon electrode by electrochemical method. This sensor was used for the detection of H2O2 in tap water and river water.
An electrochemical microsensor for chloramphenicol (CAP) was fabricated by introducing magnetic Fe3O4 nanoparticles (NPs) onto the surface of activated carbon fibers. This microsensor exhibited increased electrochemical response toward CAP because of the synergetic effect of the Fe3O4 NPs and the carbon fibers. Cyclic voltammograms were acquired and displayed three stable and irreversible redox peaks in pH 7.0 solution. Under optimized conditions, the cathodic current peaks at ?0.67 V (vs. Ag/AgCl). The calibration plot is linear in the 40 pM to 1 μM CAP concentration range, with a 17 pM detection limit (at a signal-to-noise ratio of 3). The sensor was applied to the determination of CAP in spiked sediment samples. In our perception, this electrocatalytic platform provided a useful tool for fast, portable, and sensitive analysis of chloramphenicol.
Graphical abstract A sensitive carbon fiber microsensor modified with Fe3O4 nanoparticles is found to display two cathodic peaks when detecting chloramphenicol at 100 mV·s?1 and at pH 7.0. The sensor was applied to the determination of chloramphenicol in sediment samples.
The authors report on a low temperature method for large-scale fabrication of cuprous oxide nanocubes deposited on nitrogen-doped reduced graphene oxide (Cu2O/N-RGO). The material was deposited in a glassy carbon electrode (GCE) where it is found to display enhanced electrocatalytic activity for oxidation of diethylstilbestrol (DES). The morphology and composition of Cu2O/N-RGO were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and energy-dispersive spectroscopy. The results demonstrate that the RGO is doped with 3.5% of nitrogen (atomic ratio), and that nanostructured Cu2O particles with controlled cubical morphology and an average size of about 450 nm have been homogeneously deposited on the surface of N-RGO sheets. The oxidation peak of DES was recorded at 0.315 V (vs. saturated calomel electrode) using differential pulse voltammetry. Under the optimal conditions, the modified GCE displays a linear response in the 0.3 to 150 μM DES concentration range, and the limit of detection is 10 nM. The method was applied to the determination of DES in spiked milk, meat and urine samples and gave excellent selectivity, stability and reproducibility.
Graphic abstract A nanocomposite consisting of Cu2O nanocubes/N-doped reduced graphene oxide (Cu2O/N-RGO) for the electrochemical determination of diethylstilbestrol (DES). The Cu2O/N-RGO modified electrode displays a linear response in the 0.3 to 150 μM DES concentration range. The method was applied to the determination of DES in spiked milk, meat and urine samples
