Iridium nanoparticles (IrNPs) with intrinsic oxidase-like activity were synthesized by using sodium citrate as the stabilizer and NaBH4 as the reducing agent. The IrNPs have an average diameter of 2.5 ± 0.5 nm and exhibit excellent oxidase-like property. Under the catalytic action of the IrNPs, 3,3′,5,5′-tetramethylbenzidine (TMB) is oxidized by dissolved oxygen (DO) to form a blue product with an absorption maximum at 652 nm. The catalytic activity is ascribed to the production of superoxide anion radical (O2ˉ?). The chromogenic reaction is exploited for the determination of DO. The method exhibits a wide calibration range from 12.5 to 257.5 μM of DO and a limit of detection as low as 4.7 μM. Compared to other methods, this method presented here shows improved precision and faster response time.
Graphic abstract Iridium nanoparticles (IrNPs) stabilized by sodium citrate exhibit oxidase-like activity and can effectively catalyze dissolved oxygen (DO) by oxidizing 3,3′,5,5′-tetramethylbenzidine (TMB) to form a blue product.
Core-shell Au@Ag nanorods (Ag@GNRs) were synthesized and utilized to construct a voltammetric biosensor for trichloroacetic acid (TCA). The biosensor was prepared by immobilizing hemoglobin (Hb) on a glassy carbon electrode (GCE) that was modified with the Ag@GNRs. Cyclic voltammetry revealed a pair of symmetric redox peaks, indicating that direct electron transfer occurs at the Hb on the Ag@GNR-film. The electron transfer rate constant is as high as 2.32 s?1. The good electrocatalytic capability and large surface area of the Ag@GNR-film is beneficial in terms of electron transfer between Hb and the underlying electrode. The modified GCE, best operated at ?0.4 V (vs. SCE), exhibits electrocatalytic activity toward TCA in the 0.16 μM to 1.7 μM concentration range, with a 0.12 μM detection limit (at an S/N ratio of 3).
Graphical abstract Core-shell Au@Ag nanorods (Ag@GNRs) were synthesized and used to immobilize hemoglobin to construct an effective biosensor for trichloroacetic acid.
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.
The authors report that the peroxidase-like activity of Au@Pt core-shell nanohybrids (Au@PtNHs) is selectively inhibited by cysteine. This finding has led to a highly sensitive colorimetric assay for cysteine that is based on the nanohybrid-catalyzed oxidation of TMB by H2O2 to form a blue product. The method has a detection limit of 5.0 nM and a linear range from 10 nM to 20 μM. The assay is highly selective over other amino acids. It was successfully applied to the determination of cysteine in an injection containing a mixture of amino acids.
Graphical abstract The peroxidase-like activity of Au@Pt core-shell nanohybrids (Au@PtNHs) is selectively inhibited by cysteine, enabling the determination of cysteine.
Carbon polymer dots (CPDs) were prepared by a one-pot aqueous synthetic route from ascorbic acid and diethylenetriamine at room-temperature. The CPDs under 350-nm excitation exhibit blue fluorescence peaking at 430 nm with a quantum yield of 47%. Other features include an average diameter of 5 nm, a fluorescence that is independent of the excitation wavelength, good water dispersibility and photostability, and excellent biocompatibility. The CPDs are shown to be viable fluorescent probes for ferric ion which acts as a strong quencher. The response to Fe(III) is linear in the 0.2 to 10 μM concentration range, and the detection limit is 0.1 μM. The probe was applied to the determination of Fe(III) in environmental waters and to intracellular imaging of ferric ions in HeLa cells.
Graphical abstract Carbon polymer dots (CPDs) are prepared from ascorbic acid and diethylenetriamine (DETA) at room-temperature (RT). The RT-CPDs exhibit excellent optical performance, biocompatibility and selectivity of quenching by ferric ions. This can be applied for determination and intracellular imaging of ferric ion.
Three-dimensional structures comprising polypyrrole nanowires (PPyNWs) and molecularly imprinted polymer (MIP) were prepared by electropolymerization on the surfaces of a glassy carbon electrode (GCE). The modified GCE possesses both large surface area and good electrocatalytic activity for oxidizing dopamine (DA), and this leads to high sensitivity. The electropolymerized MIP has a large number of accessible surface imprints, and this makes the GCE more selective. Under optimal conditions and at a working voltage of typically 0.23 V (vs. SCE), the calibration plot is linear in the 50 nM to 100 μM DA concentration range, and the limit of detection is 33 nM. The sensor has been successfully applied to the analysis of DA in injections.
Graphical abstract Schematic of a three-dimensional nanocomposite based dopamine sensing platform based on the use of a molecularly imprinted polymer and poly(pyrrole) nanowires. The modified polypyrrole nanowires and molecularly imprinted polymer endowed high electrocatalytic capacity and good selectivity for dopamine recognition, respectively.
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.
A glassy carbon electrode (GCE) was modified with gold nanoparticles (AuNPs) coated on monolayer graphene (AuNP/MG) by direct in situ sputtering of AuNPs on CVD-generated graphene. This process avoids complicated polymer transfer and polymer cleaning processes and affords AuNPs with a clean surface. The monolayer graphene is ductile and well dispersed. The clean surface of the AuNPs renders this sensor superior to GCEs modified with AuNPs on reduced graphene oxide in terms of the amperometric non-enzymatic determination of hydrogen peroxide. The detection limit is 10 nM (S/N = 3) at 0.55 V (vs. SCE), which is lower than that for similar methods, and the response time is as short as 2 s. Another attractive feature of the sensor is its feasibility for large-scale production via CVD and sputtering.
Graphical abstract Gold nanoparticles deposited onto monolayered graphene generated by chemical vapor deposition (CVD) are used for electrochemical sensing of H2O2, with the detection limit of 10 nM (S/N = 3) and response time of less than 2 s.
A conducting polymer composite was prepared from nano-sized hydroxyaptite (nHAp) doped into poly(3,4-ethylenedioxythiophene) (PEDOT) and then electrodeposited on a glassy carbon electrode (GCE). The nHAp carries carboxy groups and therefore is negatively charged at moderate pH value. When doped into PEDOT (PEDOT-nHAp), it forms a uniform and stable film that exhibits low electrochemical impedance, a large specific surface, and high activity toward the electrochemical oxidation of nitrite. Under optimized conditions and at a relatively low working potential of 0.78 V (vs. SCE), the modified GCE exhibited a linear amperometric response in the 0.25 μM to 1.05 mM nitrite concentration range, and the limit of detection is as low as 83 nM.
Graphical abstract A highly sensitive nitrite sensor was developed based on conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) doped with carboxyl group functionalized hydroxyapatite nanoparticles, which exhibited a large surface area and good conductivity and stability.
The authors describe the fabrication of an interconnected edge-exposed graphene nanostructure via chemical vapor deposition (CVD) of foliated graphene onto a network of alumina nanofibers. The fibers such obtained are shown to enable ultra-sensitive voltammetric determination of dopamine (DA), uric acid (UA) and ascorbic acid (AA). The electrode displays powerful and persistent electro oxidative behavior and excellent electron transport properties. Cyclic voltammetry and differential pulse voltammetry demonstrate excellent selectively and sensitivity for AA, DA and UA, with typical peaks at ?0.08 V, +0.19 V, and +0.34 V (vs. SCE), respectively. Under optimum conditions, the calibration plots are linear in the 1–80 μM range for DA, in the 1–60 μM range for UA, and in the 0.5–60 μM range for UA, with detection limits of 0.47 μM, 0.28 μM and 0.59 μM, respectively. The sensor was successfully applied to the simultaneous determination of DA and UA in the presence of AA in spiked urine sample.
Graphical abstract Material with high density of graphene foliates grown over highly aligned nano-dimensional ceramic fibers is used as electrode for simultaneous highly sensitive electrochemical determination of DA in the presence of UA and AA with a considerably low limit of detection.
CdSe:Eu nanocrystals were successfully synthesized and characterized by transmission electron microscopy, X-ray powder diffraction, and X-ray photoelectric spectroscopy. The CdSe:Eu nanocrystals showed enhanced green electrochemiluminescence (ECL) intensity when compared to pure CdSe nanocrystals. Further, the nanocrystals were used to design an ECL immunosensor for the detection of carcinoembryonic antigen (CEA) that has a linear response over the 1.0 fg·mL?1 to 100 ng·mL?1 CEA concentration range with a 0.4 fg·mL?1 detection limit. The assay was applied to the determination of CEA in human serum samples.
Graphical abstract Schematic of the assay: GCE-glassy-carbon electrode, Ab- Antibody, BSA- Bovine serum albumin, Ag- Antigen. CdSe:Eu nanocrystals were used to design an ECL immunosensor for the detection of carcinoembryonic antigen.
The authors describe a voltammetric sensor for simultaneous determination of dopamine (DA), uric acid (UA), L-tyrosine (Tyr), and the diuretic drug hydrochlorothiazide (HCTZ). The assay is based on the use of graphene nanowalls deposited on a tantalum substrate. The nanowalls are characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, electrochemical impedance spectroscopy, and cyclic voltammetry. The nanowalls are vertically grown on the substrate by direct-current arc plasma jet chemical vapor deposition. The modified electrode is shown to enable simultaneous differential pulse voltammetric determination of DA, UA, Tyr, and HCTZ. The graphene nanowalls display a large specific surface, high conductivity, and a large number of catalytically active sites for oxidation of analytes. Simultaneous detection is performed best at a pH value of 7.0 and at peak potentials of 0.124 V (vs. SCE) for DA, 0.256 V for UA, 0.536 V for Tyr and 0.708 V for HCTZ. The respective detection limits are 0.04 μM, 0.1 μM, 0.6 μM and 0.4 μM. The results show that this graphene wall modified electrode is a promising tool for the design of sensitive, selective, and stable sensors.
Graphical abstract The graphene-based differential pulse voltammetric sensor for simultaneous determination of dopamine, uric acid, L-tyrosine, and hydrochlorothiazide exhibits high selectivity, sensitivity, and stability.
The authors describe a method for DNA target recognition and signal amplification that is based on the target-induced formation of a three way junction. The subsequent assembly of two DNA probes releases the inhibitory strand and triggers a downstream strand displacement amplification. This causes the formation of a G-rich single sequence that binds to a hemin monomer with its peroxidase-mimicking properties. The resulting peroxidase (POx) activity is quantified by using H2O2 and TMB as the substrate. In the presence of an inhibitor, in contrast, the POx-like activity is strongly reduced. This forms the basis for a highly sensitive DNA assay. It has a 0.8 pM detection limit when operated at a wavelength of 450 nm and was applied to the isothermal determination of target DNA with high selectivity.
Graphical abstract Schematic of the assay: Introduction of target results in the formation of a three way junction. The subsequent assembly of two probes releases the inhibitory strand and triggers a downstream strand displacement amplification, generating amount of G-rich single sequence which causes peroxidase-mimicking activity on binding to a hemin monomer.
The authors report on a new approach for the determination of the breast cancer biomarker microRNA-155 (miRNA-155). It is based on the measurement of the fluorescence shift of oligonucleotide-templated copper nanoclusters (DNA-CuNC). A probe DNA was designed that acts as a template for the preparation of CuNC which, under 400 nm excitation, exhibit strong fluorescence enhancement at 490 nm and a 90 nm Stokes shift after binding to target miRNA-155 and formation of a DNA-RNA heteroduplex. Under the optimal conditions, the fluorescence of the DNA-CuNC increases with increasing concentration of miRNA-155 in the range from 50 pM to 10 nM, with a 11 pM detection limit. The assay has excellent selectivity over noncomplementary RNA. The method was applied to the determination of miRNA-155 in the presence of human plasma and saliva.
Graphical abstract Schematic of the detection strategy that relies on the fluorescence shift of DNA-CuNCs resulting from the specific binding of DNA-CuNCs with target miRNA-155. Fluorescence intensities are linearly proportional to the concentrations of target RNA from 50 pM to 10 nM.
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.
Reduced graphene oxide hollow microspheres (rGO HMS) were encapsulated with gold nanoparticles (AuNPs) by spray drying. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction and Raman spectroscopy were used to characterize the AuNP/rGO HMS. When placed on a glassy carbon electrode (GCE), it exhibits excellent electrochemical catalytic properties towards the oxidation of nitrite. The electrocatalytic properties were studied using various electrochemical techniques. Compared to AuNP-decorated graphene sheet based electrodes documented in the literature, the one presented here provides a larger surface area. This enhances the catalytic activity towards nitrite. The electrode, typically operated at a working potential of 0.82 V (vs. SCE), has a linear response in the 5.0 μM to 2.6 mM nitrate concentration range, and a detection limit as low as 0.5 μM (at an S/N ratio of 3).
Graphical abstract Schematic presentation of the synthesis of graphene hollow microspheres encapsulated with of gold nanoparticles (AuNP/rGO HMS) through a spray drying technique. The material was applied to the electrochemical determination of nitrite.
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 voltammetric analytical assay for the selective quantification of vanillin is described. It is based on the use of a gold nanoparticle-modified screen-printed carbon electrode (SPCE) modified with graphene quantum dots (GQD) in a Nafion matrix. The GQD were synthesized by an acidic thermal method and characterized by UV-Vis, photoluminescence, and FTIR spectroscopy. The modified SPCE displays a strongly enhanced response to vanillin. Linear sweep voltammetry (LSV) and differential pulse voltammetry (DPV) were applied to optimize the methods. The analytical assay has linear responses in the 13 to 660 μM and 0.66 to 33 μM vanillin concentration ranges. The detection limits are 3.9 μM and 0.32 μM when using LSV and DPV, respectively. The analytical assay is selective and stable. It was applied to the determination of vanillin in several food samples with satisfactory results. Recoveries from spiked samples ranged between 92.1 and 113.0%.
Graphical abstract The selective and sensitive quantification of vanillin is carried out by the use of a gold nanoparticle-modified screen-printed carbon electrode modified with graphene quantum dots in a Nafion matrix.
The authors report that sulfide ions are capable of inhibiting the peroxidase-like activity of copper nanoclusters (CuNCs). The catalytic activity of CuNCs toward the oxidation of the chromogenic substrate 3,3′,5,5′-tetramethylbenzidine by H2O2 is remarkably decreased in the presence of sulfide. Based on this finding, a colorimetric assay was developed for the rapid determination of sulfide. Best operated at a wavelength of 652 nm, it has a 0.5 μM detection limit. The method is highly selective and has been successfully applied to the quantification of sulfide in environmental water samples.
Graphical abstract The catalytic activity of CuNCs toward the oxidation of 3,3′,5,5′-tetramethylbenzidine by H2O2 is remarkably decreased in the presence of sulfide ions. This finding has been applied to design a method for colorimetric quantification of sulfide ions in environmental samples.
Near-infrared photoluminescence is intrinsic only to a minority of carbonaceous nanomaterials. Longwave fluorescence is, however, well suited for bio-sensing and bio-imaging owing to the low autofluorescence and low absorbance by biomatter. The authors describe here sulfur doped carbon quantum dots (S-CQDs) and their derivatives (referred to as 3D carbon nanoflowers; S-CNFs). Their average diameters are 2 and 28.5 nm, respectively. They display two emission peaks, one being purple and peaking at 407 nm, the other in the near-infrared and peaking at 780 nm. Quantum yields are 4% for S-CQDs and 6.4% for S-CNFs. The nanoparticles are shown to be viable fluorescent probes for hydrogen peroxide which acts as a quencher. The 3D structure of the S-CNFs and near-infrared detection result in a better linear relationship and lower detection limits. The detection limits for H2O2 are 1.1 μM for S-CQDs, and 0.6 μM for S-CNFs. The results presented here contribute to an improved understanding on how the nanostructure and selection of wavelengths affect the sensitivity and detection limits of such probes.
Graphical abstract “Button-up” - synthesized sulfur-doped carbon quantum dots and carbon nanoflowers display two emission peaks, one being purple, the other in the near-infrared. The nanoparticles are shown to be viable fluorescent probes for hydrogen peroxide which acts as a quencher.
