Electrochemical Behavior and Determination of L‐Tyrosine at Single‐walled Carbon Nanotubes Modified Glassy Carbon Electrode

Based on single‐walled carbon nanotubes (SWCNTs) modified glassy carbon electrode (GCE/SWCNTs), a novel method was presented for the determination of L ‐tyrosine. The GCE/SWCNTs exhibited remarkable catalytic and enhanced effects on the oxidation of L ‐tyrosine. In 0.10 mol/L citric acid‐sodium citrate buffer solution, the oxidation potential of L ‐tyrosine shifted negatively from +1.23 V at bare GCE to +0.76 V at GCE/SWCNTs. Under the optimized experimental conditions, the linear range of the modified electrode to the concentration of L ‐tyrosine was 5.0×10^?6–2.0×10^?5 mol/L (R₁=0.9952) and 2.7×10^?5–2.6×10^?4 mol/L (R₂=0.9998) with a detection limit of 9.3×10^?8 mol/L. The kinetic parameters such as α (charge transfer coefficient) and D (diffusion coefficient) were evaluated to be 0.66, 9.82×10^?5 cm² s^?1, respectively. And the electrochemical mechanism of L ‐tyrosine was also discussed.     

Electrochemical Determination of 2‐Nitrophenol in Water Samples Using Mg‐Al‐SDS Hydrotalcite‐Like Clay Modified Glassy Carbon Electrode

A glassy carbon electrode (GCE) modified with Mg‐Al‐SDS hydrotalcite‐like clay (SDS‐HTLC) was used for the sensitive voltammetric determination of 2‐nitrophenol (2‐NP) utilizing the oxidation process. The results indicate the prepared modified electrode has an excellent electrocatalytic activity toward 2‐NP oxidation, lowering the oxidation overpotential and increasing the oxidation current. Under optimal conditions, the oxidation current was proportional to 2‐NP concentration in the range from 1.0×10^?6 to 6.0×10^?4 M with the detection limit of 5.0×10^?7 M by DPV (S/N=3). The fabricated electrode was applied for 2‐NP determination in water samples and the recovery for these samples was from 95.6 to 103.5%.     

Fabrication of Nanocomposite Containing Naphthoquinone and Nanogold Supported on Poly(2,6‐pyridinedicarboxylic acid) Film for Voltammetric Determination of N‐Acetyl‐L‐Cysteine

A modified electrode was fabricated by grafting of poly (2,6‐pyridinedicarboxylic acid) film (PDC) by electropolymerization of 2,6‐pyridinedicarboxylic acid on the glassy carbon electrode (GCE). Then, gold nanoparticles (NG) and 1,2‐naphthoquinone‐4‐sulfonic acid sodium (Nq) were immobilized on the PDC/GCE to prepare Nq/NG/PDC/GCE by immersing electrode into NG and Nq solution, respectively. The Nq species on NG/PDC/GCE could catalyze electrooxidation of N‐acetyl‐L ‐cysteine (NAC) with lowering the over potential by about 600 mV. This method used for detection of NAC in dynamic range from 4.0×10^?6 M to 1.30×10^?4 M with a detection of limit (2σ) 8.0×10^?7 M.     

NADH Electrocatalytic Oxidation on Gold Nanoparticle‐Modified PVC/TTF‐TCNQ Composite Electrode. Application as Amperometric Sensor

We herein report on the electrocatalytic activity towards the oxidation of NADH of a PVC/TTF‐TCNQ composite electrode modified with gold nanoparticles. This electrocatalytic property allows proposing this system as a new alternative for amperometric determination of NADH, without need to add another mediator. The sensor shows a linear response to NADH over a concentration range from 5.0×10^?6 M up to 5.0×10^?4 M, with a sensitivity of 11.22±0.5 mA M^?1 and a detection limit (S/N=3) of 4.0×10^?6 M for measurements in batch and similar data in FIA.     

Electrocatalytic Oxidation of Acyclovir on Poly(p‐Aminobenzene Sulfonic Acid) Film Modified Glassy Carbon Electrode

Acyclovir is an antiviral effective drug active compound. A glassy carbon electrode (GCE) was modified with an electropolymerized film of p‐aminobenzene sulfonic acid (p‐ABSA) in phosphate buffer solution (PBS). The polymer film‐modified electrode was used to electrochemically detect acyclovir. Polymer film showed excellent electrocatalytic activity for the oxidation of acyclovir. The anodic peak potential value of the acyclovir at the poly(p‐ABSA) modified glassy carbon electrode was 950 mV obtained by DPV. A linear calibration curve for DPV analysis was constructed in the acyclovir concentration range 2×10^?7–9×10^?6 mol L^?1. Limit of detection (LOD) and limit of quantification (LOQ) were obtained as 5.57×10^?8 and 1.85×10^?7 mol L^?1 respectively. The proposed method exhibits good recovery and reproducibility.     

Simultaneous Determination of Dopamine and Ascorbic Acid Using the Nano‐Gold Self‐Assembled Glassy Carbon Electrode

Electrochemical behavior of dopamine (DA) was investigated at the gold nanoparticles self‐assembled glassy carbon electrode (GNP/LC/GCE), which was fabricated by self‐assembling gold nanoparticles on the surface of L ‐cysteine (LC) modified glassy carbon electrode (GCE) via successive cyclic voltammetry (CV). A pair of well‐defined redox peaks of DA on the GNP/LC/GCE was obtained at E_pa=0.197 V and E_pc=0.146 V, respectively. And the peak separation between DA and AA is about 0.2 V, which is enough for simultaneous determination of DA and AA. The peak currents of DA and AA were proportional with their concentrations in the range of 6.0×10^?8–8.5×10^?5 mol L^?1 and 1.0×10^?6–2.5×10^?3 mol L^?1, with the detection limit of 2.0×10^?8 mol L^?1 and 3.0×10^?7 mol L^?1 (S/N=3), respectively. The modified electrode exhibits an excellent reproducibility, sensibility and stability for simultaneous determination of DA and AA in human serum with satisfactory result.     

Direct Electrochemistry of Glucose Oxidase Immobilized on Titanium Carbide‐Au Nanoparticles‐Fullerene C60 Composite Film and Its Biosensing for Glucose

The direct electrochemistry of glucose oxidase (GOD) immobilized on the designed titanium carbide‐Au nanoparticles‐fullerene C₆₀ composite film modified glassy carbon electrode (TiC‐AuNPs‐C₆₀/GCE) and its biosensing for glucose were investigated. UV‐visible and Fourier‐transform infrared spectra of the resulting GOD/TiC‐AuNPs‐C₆₀ composite film suggested that the immobilized GOD retained its original structure. The direct electron transfer behaviors of immobilized GOD at the GOD/TiC‐AuNPs‐C₆₀/GCE were investigated by cyclic voltammetry in which a pair of well‐defined, quasi‐reversible redox peaks with the formal potential (E^0′) of ‐0.484 V (vs. SCE) in phosphate buffer solution (0.05 M, pH 7.0) at the scan rate of 100 mV·s^?1 were obtained. The proposed GOD modified electrode exhibited an excellent electrocatalytic activity to the reduction of glucose, and the currents of glucose reduction peak were linearly related to glucose concentration in a wider linearity range from 5.0 × 10^?6 to 1.6 × 10^?4 M with a correlation coefficient of 0.9965 and a detection limit of 2.0 × 10^?6 M (S/N = 3). The sensitivity and the apparent Michaelis‐Menten constant (K_M^app) were determined to be 149.3 μA·mM^?1·cm^?2 and 6.2 × 10^?5 M, respectively. Thus, the protocol will have potential application in studying the electron transfer of enzyme and the design of novel electrochemical biosensors.     

Selective Electroanalysis of Ascorbic Acid Using a Nickel Hexacyanoferrate and Poly(3,4‐ethylenedioxythiophene) Hybrid Film Modified Electrode

The mixed‐valent nickel hexacyanoferrate (NiHCF) and poly(3,4‐ethylenedioxythiophene) (PEDOT) hybrid film (NiHCF‐PEDOT) was prepared on a glassy carbon electrode (GCE) by multiple scan cyclic voltammetry. The films were characterized using atomic force microscopy, field emission scanning electron microscopy, energy dispersive spectroscopy, X‐ray diffraction, and electrochemical impedance spectroscopy (AC impedance). The advantages of these films were demonstrated for the detection of ascorbic acid (AA) using cyclic voltammetry and amperometric techniques. The electrocatalytic oxidation of AA at different electrode surfaces, such as the bare GCE, the NiHCF/GCE, and the NiHCF‐PEDOT/GCE modified electrodes, was determined in phosphate buffer solution (pH 7). The AA electrochemical sensor exhibited a linear response from 5×10⁻⁶ to 1.5×10⁻⁴ M (R²=0.9973) and from 1.55×10⁻⁴ to 3×10⁻⁴ M (R²=0.9983), detection limit=1×10⁻⁶ M, with a fast response time (3 s) for AA determination. In addition, the NiHCF‐PEDOT/GCE was advantageous in terms of its simple preparation, specificity, stability and reproducibility.     

Selective Electrochemical Epinephrine Sensor Using Self‐Assembled Monomolecular Film of 1,8,15,22‐Tetraaminophthalocyanatonickel(II) on Gold Electrode

This article describes the highly sensitive and selective determination of epinephrine (EP) using self‐assembled monomolecular film (SAMF) of 1,8,15,22‐tetraamino‐phthalocyanatonickel(II) (4α‐Ni^IITAPc) on Au electrode. The 4α‐Ni^IITAPc SAMF modified electrode was prepared by spontaneous adsorption of 4α‐Ni^IITAPc from dimethylformamide solution. The modified electrode oxidizes EP at less over potential with enhanced current response in contrast to the bare Au electrode. The standard heterogeneous rate constant (k°) for the oxidation of EP at 4α‐Ni^IITAPc SAMF modified electrode was found to be 1.94×10^?2 cm s^?1 which was much higher than that at the bare Au electrode. Further, it was found that 4α‐Ni^IITAPc SAMF modified electrode separates the voltammetric signals of ascorbic acid (AA) and EP with a peak separation of 250 mV. Using amperometric method the lowest detection limit of 50 nM of EP was achieved at SAMF modified electrode. Simultaneous amperometric determination of AA and EP was also achieved at the SAMF modified electrode. Common physiological interferents such as uric acid, glucose, urea and NaCl do not interfere within the potential window of EP oxidation. The present 4α‐Ni^IITAPc SAMF modified electrode was also successfully applied to determine the concentration of EP in commercially available injection.     

Highly Sensitive Electrochemical Sensor for Nitric Oxide Using the Self‐Assembled Monolayer of 1,8,15,22‐Tetraaminophthalocyanatocobalt(II) on Glassy Carbon Electrode

Glassy carbon (GC) electrode modified with a self‐assembled monolayer (SAM) of 1,8,15,22‐tetraaminophthalocyanatocobalt(II) (4α‐Co^IITAPc) was used for the selective and highly sensitive determination of nitric oxide (NO). The SAM of 4α‐Co^IITAPc was formed on GC electrode by spontaneous adsorption from DMF containing 1 mM 4α‐Co^IITAPc. The SAM showed two pairs of well‐defined redox peaks corresponding to Co^III/Co^II and Co^IIIPc^?1/Co^IIIPc^?2 in 0.2 M phosphate buffer (PB) solution (pH 2.5). The SAM modified electrode showed excellent electrocatalytic activity towards the oxidation of nitric oxide (NO) by enhancing its oxidation current with 310 mV less positive potential shift when compared to bare GC electrode. In amperometric measurements, the current response for NO oxidation was linearly increased in the concentration range of 3×10^?9 to 30×10^?9 M with a detection limit of 1.4×10^?10 M (S/N=3). The proposed method showed a better recovery for NO in human blood serum samples.     

Direct Voltammetry of Copper,Zinc‐Superoxide Dismutase Immobilized onto Electrodeposited Nickel Oxide Nanoparticles: Fabrication of Amperometric Superoxide Biosensor

Direct electron transfer of immobilized copper, zinc‐superoxide dismutase (SOD) onto electrodeposited nickel‐oxide (NiOx) nanoparticle modified glassy carbon (GC) electrode displays a well defined redox process with formal potential of ?0.03 V in pH 7.4. Cyclic voltammetry was used for deposition of (NiOx) nanoparticles and immobilization of SOD onto GC electrode. The surface coverage (Γ) and heterogeneous electron transfer rate constant (k_s) of immobilized SOD are 1.75×10^?11 mol cm^?2 and 7.5±0.5 s^?1, respectively. The biosensor shows a fast amperometric response (3 s) toward superoxide at a wide concentration range from 10 µM to 0.25 mM with sensitivity of 13.40 nA µM^?1 cm^?2 and 12.40 nA µM^?1 cm^?2, detection limit of 2.66 and 3.1 µM based on anodically and cathodically detection. This biosensor exhibits excellent stability, reproducibility and long life time.     

Electrocatalytic Determination of Ascorbic Acid at the Surface of 2,7‐Bis(ferrocenyl ethyl)fluoren‐9‐one Modified Carbon Paste Electrode

A chemically modified carbon paste electrode with 2,7‐bis(ferrocenyl ethyl)fluoren‐9‐one (2,7‐BFEFMCPE) was employed to study the electrocatalytic oxidation of ascorbic acid in aqueous solution using cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The diffusion coefficient (D=1.89×10^?5 cm² s^?1), and the kinetic parameter such as the electron transfer coefficient, α (=0.42) of ascorbic acid oxidation at the surface of 2,7‐BFEFMCPE was determined using electrochemical approaches. It has been found that under an optimum condition (pH 7.00), the oxidation of ascorbic acid at the surface of such an electrode occurs at a potential about 300 mV less positive than that of an unmodified carbon paste electrode. The catalytic oxidation peak currents show a linear dependence on the ascorbic acid concentration and linear analytical curves were obtained in the ranges of 8.0×10^?5 M–2.0×10^?3 M and 3.1×10^?5 M–3.3×10^?3 M of ascorbic acid with correlation coefficients of 0.9980 and 0.9976 in cyclic voltammetry and differential pulse voltammetry, respectively. The detection limits (2δ) were determined to be 2.9×10^?5 M and 9.0×10^?6 M with cyclic voltammetry and differential pulse voltammetry, respectively. This method was also examined for determination of ascorbic acid in pharmaceutical preparations.     

Electrocatalytic Oxidation and Determination of Dopamine in the Presence of Ascorbic Acid and Uric Acid at a Poly (4‐(2‐Pyridylazo)‐Resorcinol) Modified Glassy Carbon Electrode

A sensitive and selective electrochemical method for the determination of dopamine (DA) was developed using a 4‐(2‐Pyridylazo)‐Resorcinol (PAR) polymer film modified glassy carbon electrode (GCE). The PAR polymer film modified electrode shows excellent electrocatalytic activity toward the oxidation of DA in a phosphate buffer solution (PBS) (pH 4.0). The linear range of 5.0×10^?6–3.0×10^?5 M and detection limit of 2.0×10^?7 M were observed. Simultaneous detection of AA, DA and UA has also been demonstrated on the modified electrode. This work provides a simple and easy approach to selective detection of DA in the presence of AA and UA.     

Electrocatalytic Oxidation and Determination of Cysteamine by Poly‐N,N‐dimethylaniline/Ferrocyanide Film Modified Carbon Paste Electrode

Functionalized poly‐N,N‐dimethylaniline film was prepared by adsorption of ferrocyanide onto the polymer forming at the surface of carbon paste electrode (CPE) in aqueous solution by using potentiostatic method. The electrocatalytic ability of poly‐N,N‐dimethylaniline/ferrocyanide film modified carbon paste electrode (PDMA/FMCPE) was demonstrated by oxidation of cysteamine. Cyclic voltammetry and chronoamperometry techniques were used to investigate this ability. Results showed that pH 7.00 is the most suitable for this purpose. It is found that the catalytic reaction rate constant, (k_h), is equal to 2.142×10³ M^?1 s^?1 by the data of chronoamperometry. The catalytic reduction peak current was linearly dependent on the cysteamine concentration and the linearity range obtained was 8.00×10^?5 M–1.14×10^?2 M. Detection limit was determined 7.97×10^?5 M (2σ). This method has been successfully employed for quantification of cysteamine in real sample.     

Enhanced Oxidation of Simvastatin at a Multi‐Walled Carbon Nanotubes‐Dihexadecyl Hydrogen Phosphate Composite Modified Glassy Carbon Electrode and the Application in Determining Simvastatin in Pharmaceutical Dosage Forms

A sensitive electrochemical method for the determination of simvastatin (SV) was established, based on the enhanced oxidation of SV at a multi‐walled carbon nanotubes‐dihexadecyl hydrogen phosphate composite modified glassy carbon electrode (MWNTs‐DHP/GCE). The voltammetric studies showed that MWNTs instead of DHP or GCE could effectively catalyze the oxidation of SV. The dependence of oxidation current on SV concentration was explored under optimal conditions, which exhibited a good linear relationship in the range of 1.0×10^?7–7.5×10^?6 M. The detection limit of SV was also examined and a low value of 5.0×10^?8 M was obtained for 5 min accumulation (σ=3). This electrode was applied to the detection of SV in drug forms and the results were in accordance with those obtained by UV spectroscopy.     

Sensitive Voltammetric Response of p‐Nitroaniline on Single‐Wall Carbon Nanotube‐Ionic Liquid Gel Modified Glassy Carbon Electrodes

An ionic liquid (i.e., 1‐butyl‐3‐methylimidazolium hexafluorophosphate, BMIMPF₆)‐single‐walled carbon nanotube (SWNT) gel modified glassy carbon electrode (BMIMPF₆‐SWNT/GCE) is fabricated. At it the voltammetric behavior and determination of p‐nitroaniline (PNA) is explored. PNA can exhibit a sensitive cathodic peak at ?0.70 V (vs. SCE) in pH 7.0 phosphate buffer solution on the electrode, resulting from the irreversible reduction of PNA. Under the optimized conditions, the peak current is linear to PNA concentration over the range of 1.0×10^?8–7.0×10^?6 M, and the detection limit is 8.0×10^?9 M. The electrode can be regenerated by successive potential scan in a blank solution for about 5 times and exhibits good reproducibility. Meanwhile, the feasibility to determine other nitroaromatic compounds (NACs) with the modified electrode is also tested. It is found that the NACs studied (i.e., p‐nitroaniline, p‐nitrophenol, o‐nitrophenol, m‐nitrophenol, p‐nitrobenzoic acid, and nitrobenzene) can all cause sensitive cathodic peaks under the conditions, but their peak potentials and peak currents are different to some extent. Their peak currents and concentrations show linear relationships in concentration ranges with about 3 orders of magnitude. The detection limits are 8.0×10^?9 M for p‐nitroaniline, 2.0×10^?9 M for p‐nitrophenol, 5.0×10^?9 M for o‐nitrophenol, 5.0×10^?9 M for m‐nitrophenol, 2.0×10^?8 M for p‐nitrobenzoic acid and 8.0×10^?9 M for nitrobenzene respectively. The BMIMPF₆‐SWNT/GCE is applied to the determination of NACs in lake water.     

Electrocatalysis and Voltammetric Determination of Dopamine at a Calix[4]arene Crown‐4 Ether Modified Glassy Carbon Electrode

A sensitive and selective electrochemical method for the determination of dopamine (DA) was developed using a calix[4]arene crown‐4 ether (CACE) film modified glassy carbon electrode (GCE).The modified electrode exhibited good electrocatalytic activity for electrochemical oxidation of DA in the pH 6.00 Britton–Robinson buffer solution, and ascorbic acid (AA) did not interfere with it. The diffusion coefficient (D=2.7×10^?5 cm² s^?1), and the kinetic parameter such as the electron transfer coefficient (α=0.54) of DA at the surface of CACE were determined using electrochemical approaches. The catalytic oxidation peak currents showed a linear dependence on the DA concentration and a linear analytical curve was obtained in the range of 2.0×10^?5–1.0×10^?3 M of DA with a correlation coefficient of 0.9990. The detection limit (S/N=3) was estimated to be 3.4×10^?6 M. This method was also examined for the determination of DA in an injection sample. In addition, effects of possible interferences were investigated. The present work shows the potential of the proposed method for the fabrication of a modified electrode, as it can be effectively used for voltammetric detection of DA.     

Electrocatalytic Oxidation and Voltammetric Determination of Hydrazine on the Tetrabromo‐p‐Benzoquinone Modified Carbon Paste Electrode

The electrochemical properties of hydrazine studied at the surface of a carbon paste electrode spiked with p‐bromanil (tetrabromo‐p‐benzoquinone) using cyclic voltammetry (CV), double potential‐step chronoamperometry and differential pulse voltammetry (DPV) in aqueous media. The results show this quinone derivative modified carbon paste electrode, can catalyze the hydrazine oxidation in an aqueous buffered solution. It has been found that under the optimum conditions (pH 10.00), the oxidation of hydrazine at the surface of this carbon paste modified electrode occurs at a potential of about 550 mV less positive than that of a bar carbon paste electrode. The electrocatalytic oxidation peak current of hydrazine showed a linear dependent on the hydrazine concentrations and linear analytical curves were obtained in the ranges of 6.00×10^?5 M–8.00×10^?3 M and 7.00×10^?6 M–8.00×10^?4 M of hydrazine concentration with CV and differential pulse voltammetry (DPV) methods, respectively. The detection limits (3σ) were determined as 3.6×10^?5 M and 5.2×10^?6 M by CV and DPV methods. This method was also used for the determination of hydrazine in the real sample (waste water of the Mazandaran wood and paper factory) by standard addition method.     

Efficient Electrocatalytic Detection of Epinephrine at Gold Electrodes Modified with Self‐Assembled Metallo‐Octacarboxyphthalocyanine Complexes

Electrocatalysis of epinephrine at gold electrode pre‐modified with the self‐assembled monolayer of cysteamine and subsequently integrated with novel metallo‐octacarboxyphthalocyanine (MOCPc where M=Fe, Co and Mn) complexes (Au‐Cys‐MOCPc) was investigated. The electrodes showed response to the presence of epinephrine. The oxidation peak potential (E_p/V vs. Ag|AgCl, sat'd KCl) and charge transfer resistance (R_ct (kΩ)) in epinephrine solution depend markedly on the central metal of the phthalocyanine cores: Au‐Cys‐FeOCPck_ch=4.1×10⁷ M^?1 s^?1) which is higher than that of the Au‐cys‐CoOCPc or Au‐cys‐MnOCPc electrode. Mechanism, recognizing the mediation of the electrocatalytic process by the central M(II)/M(III) redox processes was proposed. Epinephrine electro‐oxidation at the Au‐cys‐FeOCPc electrode was studied in more details for the response characteristics. The diffusion coefficient of epinephrine was evaluated as (2.62±0.23)×10^?9 cm² s^?1. It was established that Au‐Cys‐FeOCPc is suitable for sensitive determination of epinephrine in physiological pH (7.40) conditions showing linear concentration range of up to 300 nM, with excellent sensitivity (0.53±0.01 nA nM^?1), and very low limits of detection (13.8 nM) and quantification (45.8 nM). The peak separation between ascorbic acid and epinephrine is large enough (190 mV) to permit simultaneous determination of both epinephrine and ascorbic acid in physiological pH 7.4 conditions using the Au‐cys‐FeOCPc electrode. Au‐cys‐FeOCPc electrode was successfully used for the determination of epinephrine in epinephrine hydrochloric acid injection with recovery of ca. 98.4%.     

Electrochemical Behaviors of Adenosine‐5′‐triphosphate on Molecular Wire Modified Carbon Paste Electrode and Its Sensitive Detection

A new electrochemical method was proposed for the determination of adenosine‐5′‐triphosphate (ATP) based on the electrooxidation at a molecular wire (MW) modified carbon paste electrode (CPE), which was fabricated with diphenylacetylene (DPA) as the binder. A single well‐defined irreversible oxidation peak of ATP appeared on MW‐CPE with adsorption‐controlled process and enhanced electrochemical response in a pH 3.0 Britton‐Robinson buffer solution, which was due to the presence of high conductive DPA in the electrode. The electrochemical parameters of ATP were calculated with the electron transfer coefficient (α) as 0.54, the electron transfer number (n) as 1.9, the apparent heterogeneous electron transfer rate constant (k_s) as 2.67 × 10^?5 s^?1 and the surface coverage (Γ_T) as 4.15 × 10^?10 mol cm^?2. Under the selected conditions the oxidation peak current was proportional to ATP concentration in the range from 1.0 × 10^?7 mol L^?1 to 2.0 × 10^?3 mol L^?1 with the detection limit as 1.28 × 10^?8 mol L^?1 (3σ) by sensitive differential pulse voltammetry. The proposed method showed good selectivity without the interferences of coexisting substances and was successful applied to the ATP injection samples detection.