Microwave-radiated synthesis of gold nanoparticles/carbon nanotubes composites and its application to voltammetric detection of trace mercury(II)

Gold nanoparticles/carbon nanotubes (Au-NPs/CNTs) composites were rapidly synthesized by microwave radiation, and firstly applied for the determination of trace mercury(II) by anodic stripping voltammetry (ASV). The structure and composition of the synthesized Au-NPs/CNTs nanocomposites were characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), UV–vis absorption spectroscopy and cyclic voltammetry. Au-NPs/CNTs nanocomposites modified glassy carbon electrode (Au-NPs/CNTs/GCE) exhibited excellent performance for Hg(II) analysis. A wide linear range (5 × 10⁻¹⁰–1.25 × 10⁻⁶ mol/L) and good repeatability (relative standard deviation of 1.84%) were obtained for Hg(II) detection. The limit of detection was found to be 3 × 10⁻¹⁰ mol/L (0.06 μg/L) at 2 min accumulation, while the World Health Organization’s guideline value of mercury for drinking water is 1 μg/L, suggesting the proposed method may have practical utility.     

Electrochemiluminescent biosensor based on multi-wall carbon nanotube/nano-Au modified electrode

The electrochemiluminescent (ECL) behavior of lucigenin on a multi-wall carbon nanotube/nano-Au modified glassy carbon electrode (MWNT/nano-Au/GCE) was studied in this paper. Compared with the bare GCE, the ECL intensity of lucigenin can be greatly enhanced at MWNT/nano-Au/GCE. Based on the fact that superoxide dimutase (SOD) could obviously inhibit the ECL of lucigenin at MWNT/nano-Au/GCE, a sensitive ECL biosensor for determination of SOD was developed with a wide linear range of 5.0 × 10⁻⁸–5.0 × 10⁻⁶ mol/L with detection limit of 2.5 × 10⁻⁸ mol/L.     

Microwave-irradiated synthesized platinum nanoparticles/carbon nanotubes for oxidative determination of trace arsenic(III)

Platinum nanoparticles/carbon nanotubes (Pt_nano/CNTs) were rapidly synthesized by microwave radiation, and applied for the oxidative determination of arsenic(III). The transmission electron microscopy (TEM) revealed the size of synthesized Pt nanoparticles with nominal diameter of 15 ± 3 nm. Pt_nano/CNTs modified glassy carbon electrode (Pt_nano/CNTs/GCE) exhibited better performance for arsenic(III) analysis than that of Pt nanoparticles modified GCE (Pt_nano/GCE) by electrochemical deposition or Pt foil electrode. Excellent reproducibility of the Pt_nano/CNTs/GCE was obtained with the relative standard deviation (RSD) of 3.5% at 20 repeated analysis of 40 μM As(III), while the RSD was 9.8% for Pt_nano/GCE under the same conditions. The limit of determination (LOD) of the Pt_nano/CNTs/GCE was 0.12 ppb, which was 1–2 orders of magnitude lower than that of Pt_nano/GCE or Pt foil electrode.     

Ferrocene-modified Fe3O4@SiO2 magnetic nanoparticles as building blocks for construction of reagentless enzyme-based biosensors

A novel amperometric glucose biosensor was developed by entrapping glucose oxidase (GOD) in chitosan (CS) composite doped with ferrocene monocarboxylic acid-modified magnetic core-shell Fe₃O₄@SiO₂ nanoparticles (FMC-AFSNPs). It is shown that the obtained magnetic bio-nanoparticles attached to the surface of a carbon paste electrode (CPE) with the employment of a permanent magnet showed excellent electrochemical characteristics and at the same time acted as mediator to transfer electrons between the enzyme and the electrode. Under optimal conditions, this biosensor was able to detect glucose in the linear range from 1.0 × 10⁻⁵ to 4.0 × 10⁻³ M with a detection limit of 3.2 μM (S/N = 3). This immobilization approach effectively improved the stability of the electron transfer mediator and is promising for construction of biosensor and bioelectronic devices.     

Electrochemical oxidation behavior of nitrite on a chitosan-carboxylated multiwall carbon nanotube modified electrode

A novel chitosan-carboxylated multiwall carbon nanotube modified glassy carbon electrode (MC/GCE) was developed to investigate the oxidation behavior of nitrite using cyclic voltammetry and differential pulse voltammetry modes. The electrochemical mechanism of the MC/GCE towards nitrite was discussed. The MC/GCE exhibited fast response towards nitrite with a detection limit of 1 × 10⁻⁷ mol l⁻¹ and a linear range of 5 × 10⁻⁷–1 × 10⁻⁴ mol l⁻¹. The possible interference from several common ions was tested. The proposed method was successfully applied in the detection of nitrite in real samples.     

Gelatin-functionalized carbon nanotubes for the bioelectrochemistry of hemoglobin

In this paper, we compared the use of gelatin-functionalized carbon nanotubes (CNTs) as substrates for Hemoglobin (Hb) immobilization and as electrodes for electrochemical reduction of the absorbed Hb. The non-covalently gelatin-functionalized CNTs possessed an improved solubility in aqueous solution and may have an enhanced biocompatibility with Hb. The characteristics of Hb/gelatin-CNTs composite films were studied by using UV–vis spectroscopy, FTIR spectroscopy and electrochemical methods. The immobilized Hb showed a couple of quasi-reversible redox peaks with a formal potential of −0.35 V (vs. SCE) in 0.10 M pH 7.0 phosphate buffer solution (PBS). The surface concentration of electroactive Hb immobilized on gelatin-CNT/GC electrode was about 4.34 × 10⁻¹⁰ mol cm⁻².     

Gold nanoparticles/tetraaminophenyl porphyrin functionalized multiwalled carbon nanotubes nanocomposites modified glassy carbon electrode for the simultaneous determination of p-acetaminophen and p-aminophenol

A novel electrochemical platform was designed and prepared for simultaneous determination of p-acetaminophen (AMP) and p-aminophenol (AP) by combining the excellent conductivity and electrocatalytic activities of tetraaminophenyl porphyrin functionalized multi-walled carbon nanotubes (CNTs-CONH-TAPP) and gold nanoparticles (AuNPs). The as-synthesized CNTs-CONH-TAPP composites were characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscope. The incisive oxidation current responses of AMP and AP at the modified electrode promised a sensitive and selective simultaneous determination of AMP and AP. Under optimized conditions, the peak currents were directly proportional to the concentrations of AMP and AP over the ranges of 4.5–500 μmol L⁻¹ and 0.08–60 μmol L⁻¹, respectively, and the limits of detection were 0.44 μmol L⁻¹ for AMP and 0.025 μmol L⁻¹ for AP(S/N = 3) respectively. The proposed modified electrode showed excellent selectivity, reproducibility and long-term stability and could be applied in simultaneous determination of p-acetaminophen and p-aminophenol in real samples.     

Novel poly (neutral red) nanowires as a sensitive electrochemical biosensing platform for hydrogen peroxide determination

Poly (neutral red) nanowires (PNRNWs) have been synthesized for the first time by the method of cyclic voltammetric electrodeposition using porous anodic aluminum oxide (AAO) template and were examined by scanning electron microscopy (SEM) and transmission electron microscope (TEM). Moreover, horseradish peroxidase (HRP) was encapsulated in situ in PNRNWs (denoted as PNRNWs–HRP) by electrochemical copolymerization for potential biosensor applications. The PNRNWs showed excellent efficiency of electron transfer between the HRP and the glassy carbon (GC) electrode for the reduction of H₂O₂ and the PNRNWs–HRP modified GC electrode showed to be excellent amperometric sensors for H₂O₂ at −0.1 V with a linear response range of 1 μM to 8 mM with a correlation coefficient of 0.996. The detection limit (S/N = 3) and the response time were determined to be 1 μM and <5 s and the high sensitivity is up to 318 μA mM⁻¹ cm⁻².     

Simultaneous determination of ascorbic acid,epinephrine, and uric acid by differential pulse voltammetry using poly(p-xylenolsulfonephthalein) modified glassy carbon electrode

A novel poly(p-xylenolsulfonephthalein) modified glassy carbon electrode was prepared for the simultaneous determination of ascorbic acid (AA), epinephrine (EP) and uric acid (UA). Cyclic voltammetric, chronoamperometric, and differential pulse voltammetric methods were used to investigate the modified electrode for the electrocatalytic oxidation of EP, AA, and UA in aqueous solutions. The separation of the oxidation peak potentials for AA–EP and EP–UA was about 200 and 130 mV, respectively. The calibration curves obtained for AA, EP, and UA were in the ranges of 10–1343, 2–390, and 0.1–560 μmol L⁻¹, respectively. The detection limits (S/N = 3) were 4, 0.1, and 0.08 μmol L⁻¹ for AA, EP and UA, respectively. The diffusion coefficient and the catalytic rate constant for the oxidation of EP at the modified electrode were calculated as 1.40(±0.10) × 10⁻⁴ cm² s⁻¹ and 1.06 × 10³ mol⁻¹ L s⁻¹, respectively. The present method was applied to the determination of EP in pharmaceutical and urine samples, AA in commercially available vitamin C tablet, and EP plus UA in urine samples.     

Layer-by-layer assembled DNA functionalized single-walled carbon nanotube hybrids for arsenic(III) detection

Based on layer-by-layer assembled DNA functionalized single-walled carbon nanotube hybrids, a DNA biosensor for the detection of arsenic(III) in a nearly physiological pH environment was developed. The redox process between arsenic(III) and arsenic(0) on the biosensor was proved. The growth of those hybrids on glassy carbon electrode was monitored by detecting arsenic(III). The arsenic(III) current on the biosensor was similar over a broad pH range (3.0–8.0) and the limit of detection (S/N = 3) was 0.05 μg L⁻¹ at pH 7.0. The biosensor can be reused up to 16 times.     

Amperometric biosensing of glutamate using carbon nanotube based electrode

Amperometric biosensing of glutamate using nanobiocomposite derived from multiwall carbon nanotube (CNT), biopolymer chitosan (CHIT), redox mediator meldola’s blue (MDB) and glutamate dehydrogenase (GlDH) is described. The CNT composite electrode shows a reversible voltammetric response for the redox reaction of MDB at −0.15 V; the composite electrode efficiently mediates the oxidation of NADH at −0.07 V, which is 630 mV less positive than that on an unmodified glassy carbon (GC) electrode. The CNTs in the composite electrode facilitates the mediated electron transfer for the oxidation of NADH. The CNT composite electrode is highly sensitive (5.9 ± 1.52 nA/μM) towards NADH and it could detect as low as 0.5 μM of NADH in neutral pH. The CNT composite electrode is highly stable and does not undergo deactivation by the oxidation products. The electrode does not suffer from the interference due to other anionic electroactive compounds such as ascorbate (AA) and urate (UA). Separate voltammetric peaks have been observed for NADH, AA and UA, allowing the individual or simultaneous determination of these bioanalytes. The glutamate biosensor was developed by combining the electrocatalytic activity of the composite film and GlDH. The enzymatically generated NADH was electrocatalytically detected using the biocomposite electrode. Glutamate has been successfully detected at −0.1 V without any interference. The biosensor is highly sensitive, stable and shows linear response. The sensitivity and the limit of detection of the biosensor was 0.71 ± 0.08 nA/μM and 2 μM, respectively.     

Effective bioelectrocatalysis of bilirubin oxidase on electrochemically reduced graphene oxide

Graphene oxide (GO) was applied for construction of an effective biocathode based on bilirubin oxidase (BOD). Separation of small-sized GO sheets together with the BOD immobilisation protocol has detrimental effects on the bioelectrocatalytic reduction of oxygen. When BOD was deposited on electrochemically reduced GO (ErGO) only a negligible current density j = 2.6 μA cm^− 2 was observed. Current density dramatically increased to a value of 46 μA cm^− 2 once BOD was in-situ mixed with as-received GO directly on a glassy carbon electrode (GCE) with subsequent electrochemical reduction of the BOD/GO composite. When this protocol was tested with small-sized GO flakes separated simply using centrifugation, the fabricated biocathode exhibited j = 120 μA cm^− 2. A current density further increased to j = 280 μA cm^− 2 when BOD and purified GO were incubated ex-situ for 4 h, followed by the BOD/GO composite collection by centrifugation, its deposition on the GCE and electrochemical reduction. Moreover, oxygen reduction current increased steeply with a steady-state current density achieved at high potential (≈ 500 mV), close to the onset potential of oxygen reduction (≈ 580 mV).     

Preparation of monodisperse carbon nanospheres for electrochemical capacitors

The efficiently hydrothermal route using sucrose without any catalysts is employed to prepare the uniform carbon spheres. The monodisperse 100–150 nm carbon spheres are obtained with the activation treatment in molten KOH. The carbon spheres are characterized by transmission electron microscope, X-ray diffraction, N₂ adsorption, Raman spectroscopy and electrochemical techniques. The relationships of specific capacitance and surface properties of carbon spheres are investigated. A single electrode of carbon nanosphere materials performs excellent specific capacitance (328 F g⁻¹), area capacitance (19.2 μF cm⁻²) and volumetric capacitance (383 F cm⁻³).     

Gold nanoparticles integrated in a nanotube array for electrochemical detection of glucose

An enzyme-free amperometric glucose sensor of gold nanoparticle-constituted nanotube array electrode is presented. The resulted gold nanotube array electrode with significantly enhanced surface roughness shows prominent catalytic activity toward the electrooxidation of glucose in a pH 7.4 phosphate buffer (PBS) solution and thus can be used to individually or simultaneously determine glucose and the common interfering molecule of ascorbic acid (AA). In the case of glucose detection, the amperometric responses show a linear relationship to glucose concentration in the range of 1 mM–42.5 mM with a detection limit down to 10 μM. The present non-enzymatic glucose electrochemical biosensor shows a good stability and reproducibility.     

Simultaneous determination of acetaminophen,dopamine and ascorbic acid using a PbS nanoparticles Schiff base-modified carbon paste electrode

A highly sensitive method was investigated for the simultaneous determination of acetaminophen (AC), dopamine (DA), and ascorbic acid (AA) using a PbS nanoparticles Schiff base-modified carbon paste electrode (PSNSB/CPE). Differential pulse voltammetry peak currents of AC, DA and AA increased linearly with their concentrations within the ranges of 3.30 × 10⁻⁸–1.58 × 10⁻⁴ M, 5.0 × 10⁻⁸–1.2 × 10⁻⁴ M and 2.50 × 10⁻⁶–1.05 × 10⁻³ M, respectively, and the detection limits for AC, DA and AA were 5.36 × 10⁻⁹, 2.45 × 10⁻⁹ and 1.86 × 10⁻⁸ M, respectively. The peak potentials recorded in a phosphate buffer solution (PBS) of pH 4.6 were 0.672, 0.390, and 0.168 V (vs Ag/AgCl) for AC, DA and AA, respectively. The modified electrode was used for the determination of AC, DA, and AA simultaneously in real and synthetic samples.     

Dual-signal anodic stripping voltammetric determination of trace arsenic(III) at a glassy carbon electrode modified with internal-electrolysis deposited gold nanoparticles

A glassy carbon electrode (GCE) modified with internal-electrolysis deposited gold nanoparticles (AuNPs_ied) was applied to sensitively and selectively detect As(III) by anodic stripping linear sweep voltammetry (ASLSV). The AuNPs_ied/GCE was prepared based on the redox replacement reaction between a supporting-electrolyte-free aqueous HAuCl₄ and a copper sheet in saturated KCl separated by a salt bridge. Under optimum conditions (0.5 M aqueous H₂SO₄, 300-s preconcentration at − 0.4 V), the ASLSV peak current for the As(0)–As(III) oxidation responded linearly to As(III) concentration from 0.02 to 3 μM with a limit of detection (LOD) of 0.9 nM (0.07 μg L^− 1) (S/N = 3), while that for the As(III)–As(V) oxidation was linear with As(III) concentration from 0.02 to 1 μM with a LOD of 4 nM (0.3 μg L^− 1) (S/N = 3). An appropriate high-scan-rate for ASLSV can enhance both the sensitivity and signal-to-noise ratio. This method was applied for analyses of As(III) in real water samples.     

Sodium dodecyl sulfate modified carbon nanotubes paste electrode as a novel sensor for the simultaneous determination of dopamine,ascorbic acid,and uric acid

A novel modified multiwall carbon nanotubes paste electrode with sodium dodecyl sulfate as a surfactant (SDS) has been fabricated through an electrochemical oxidation procedure and was used to electrochemically detect dopamine (DA), ascorbic acid (AA), uric acid (UA), and their mixture by cyclic voltammetry (CV) and differential voltammetry (DPV) methods. Several factors affecting the electrocatalytic activity of the hybrid material, such as the effect of pH, of the scan rate and of the concentration were studied. The bare carbon nanotubes paste electrode (BCNTPE) and SDS-modified carbon nanotubes paste electrode (SDSMCNTPE) were characterized using Field Emission Scanning Electron Microscopy (FESEM) and Energy-Dispersive X-ray spectroscopy (EDX). Using the CV procedure, a linear analytical curve was observed in the 1 × 10⁻⁶–2.8 × 10⁻⁵ M range with a detection limit at 3.3 × 10⁻⁷ M in pH 6.5, 0.2 M phosphate buffer solutions (PBS).     

MgO polyhedral nanocages and nanocrystals based glucose biosensor

MgO polyhedral nanocages and nanocrystals, synthesized by non-catalytic simple thermal evaporation process, were used to fabricate high-sensitive amperometric glucose biosensor which showed a high and reproducible sensitivity of 31.6 μA μM^?1 cm^?2 with a response time less than 5 s, linear dynamic range from 1.0 to 9.0 μM and correlation coefficient of R = 0.9993. The detection limit of fabricated biosensor (based on S/N ratio = 3) was estimated to be 68.3 ± 0.02 nM. To the best of our knowledge, this is the first report which demonstrates the use of MgO nanostructures for the fabrication of glucose biosensor; hence, this work opens a new way to utilize MgO nanostructures as an efficient electron mediator to fabricate efficient glucose biosensors.     

Development of urease based amperometric biosensors for the inhibitive determination of Hg (II)

Enzymatic amperometric procedures for measurement of Hg (II), based on the inhibitive action of this metal on urease enzyme activity, were developed. Screen-printed carbon electrodes (SPCEs) and gold nanoparticles modified screen-printed carbon electrodes (AuNPs/SPCEs) were used as supports for the cross-linking inmobilization of the enzyme urease. The amperometric response of urea was affected by the presence of Hg (II) ions which caused a decreasing in the current intensity. The optimum working conditions were found using experimental design methodology. Under these conditions, repeatability and reproducibility for both types of biosensors were determined, reaching values below 6% in terms of residual standard deviation. The detection limit obtained for Hg (II) was 4.2 × 10^?6 M for urease/SPCE biosensor and 5.6 × 10^?8 M for urease/AuNPs/SPCE biosensor. Analysis of the possible effect of the presence of foreign ions in the solution was performed. The method was applied to determine levels of Hg (II) in spiked human plasma samples.     

Direct electrochemistry and electrocatalysis of hemoglobin entrapped in composite matrix based on chitosan and CaCO3 nanoparticles

The direct electron transfer between hemoglobin (Hb) and the underlying glassy carbon electrode (GCE) can be readily achieved via a high biocompatible composite system based on biopolymer chitosan (CHT) and inorganic CaCO₃ nanoparticles (nano-CaCO₃). Cyclic voltammetry of Hb-CHT/nano-CaCO₃/GCE showed a pair of stable and quasi-reversible peaks for HbFe(III)/Fe(II) redox couple in pH 7.0 buffer. The electrochemical reaction of Hb immobilized in CHT/nano-CaCO₃ composite matrix exhibited a surface-controlled process accompanied by electron and proton transfer. The electron transfer rate constant was estimated to be 1.8 s⁻¹. This modified electrode showed a high thermal stability up to 60 °C. The apparent Michaelis–Menten constant was calculated to be 7.5 × 10⁻⁴ M, indicating a high catalytic activity of the immobilized Hb toward H₂O₂. The interaction between Hb and this nano-hybrid material was also investigated using FT-IR and UV–vis spectroscopy, indicating that Hb retained its native structure in this hybrid matrix.