The electrochemical determination of phenolic derivates using multiple pulsed amperometry with graphite based electrodes

The electrochemical determinations of 4-chlorophenol (4-CP) and 4-nitrophenol (4-NP) by chronoamperometry (CA) and multiple pulsed amperometry (MPA) using expanded graphite-epoxy composite (EG-Epoxy) and rotating spectral graphite disc (SG) electrodes are reported. The electrochemical behaviours of both electrodes in the presence of organics informed about oxidation peak potential and the electrode fouling with organics concentration increasing. Setting up the oxidation peak potential as detection potential, only SG gave good electroanalytical performance using CA. However, by MPA applying both electrodes exhibited the capability to assess electrochemically and quantitatively the pollutants from aqueous solutions. UV spectrometric method detecting 4-CP and 4-NP at λ = 280 nm and λ = 398 nm wavelength, respectively was used for validation and parallel determinations.     

Thionine-functionalized graphene oxide,new electrocatalyst for determination of nitrite

In this work, thionine (Th) was assembled on the surface of graphene oxide as an electron transfer mediator using diazonium reaction (Th–GO). Then, Th–GO was characterized by different methods such as scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy. Afterward, Th–GO was used for the modification of carbon paste electrode. Several electrochemical methods including cyclic voltammetry, differential pulse voltammetry, and hydrodynamic amperometry were used to investigate the behavior of the modified electrode. Then, the role of the modified electrode for oxidation of nitrite has been studied. For this purpose, the effect of critical experimental parameters including step potential and pulse amplitude (in differential pulse voltammetry technique), applied potential, the rotating speed of the disk (in amperometry technique), and the solution pH was investigated. Under the optimized conditions, the currents were found to be linear with the nitrite concentration in the range 0.05–33.0 and 0.5–800 µmol L^?1 with detection limits of 0.02 and 0.2 µmol L^?1 using differential pulse voltammetry and hydrodynamic amperometry, respectively. The introduced modified electrode showed good repeatability (RSD% = 3.2) and reproducibility (RSD% = 4.7). This electrochemical sensor was exerted successfully for the determination of nitrite and nitrate in real samples including water and wastewater samples.     

Electrocatalytic Nitrite Determination Using Iron Phthalocyanine Modified Gold Nanoparticles

Electrochemical detection of nitrite was achieved via electrodeposition of gold nanoparticles (AuNPs) onto glassy carbon electrodes, followed by 3‐mercaptopropionic acid (MPA) self‐assembly, enabling attachment of an iron(III) monoamino‐phthalocyanine (FeMAPc) catalyst via amide bond formation. The use of scanning electron microscopy, energy dispersive X‐ray spectroscopy and ultraviolet‐visible spectroscopy realised surface characterisation while cyclic voltammetry and electrochemical impedance spectroscopy techniques were applied for electrochemical interrogation. The electrochemical behaviour of nitrite at the bare (GCE), AuNPs/GCE, FeMAPc/GCE and FeMAPc‐MPA/AuNPs/GCE was further scrutinised using differential pulse voltammetry in phosphate buffer solution (0.1 M PBS, pH 5.8). Overall the FeMAPc‐MPA/AuNPs/GCE resulted in sensitivity 14.5 nA/µM, which was double that of AuNPs/GCE, 2.4 times FeMAPc/GCE and 3.5 times the response at a bare GCE, with linear range 1.9 µM–2.04 mM (PBS, pH 5.8) and LOD 0.21 µM. An interference study revealed that the proposed sensor (FeMAPc‐MPA/AuNPs/GCE) exhibited a selective response in the presence of interfering anions and the analytical capability of the sensor was demonstrated via nitrite ion determination in real water samples.     

Cysteine combined with carbon black as support for electrodeposition of poly (1,8-Diaminonaphthalene): Application as sensing material for efficient determination of nitrite ions

Poly 1,8-Diaminonaphtahlene/cysteine (poly 1,8-DAN/Cys) combined with carbon black (CB) nanoparticles are proposed as an excellent sensor for the detection of nitrite ions. To design the electrocatalyst, a simple approach consisting on drop-casting method was applied to disperse carbon black on the surface of glassy carbon electrode, followed by the immobilization of cysteine on the surface of CB nanoparticles. The electrochemical polymerization of 1,8-Diaminonaphthalene was conducted in acidic medium by using cyclic voltammetry. The prepared hybrid material was denoted poly 1,8-DAN /Cys/CB. Several methods were used to characterize the structural and electrochemical behavior of the reported hybrid material including Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), amperometry and differential pulse voltammetry (DPV). The prepared electrode displayed an outstanding electroactivity towards nitrite ions reflected by an enhancement in the intensity of the current and a decrease of the charge transfer resistance. Poly 1,8-DAN/Cys/CB displayed an excellent sensing performance towards the detection of nitrite with a very low detection limit of 0.25 µM. Two linear ranges of 1–40 µM and 20–210 µM when using amperometry and differential pulse voltammetry (DPV) were obtained respectively. This work highlights the simple preparation of a polymeric film rich in amine and thiol groups for nitrite detection.     

A novel nitrite sensor based on graphene/polypyrrole/chitosan nanocomposite modified glassy carbon electrode

A novel nitrite sensor was fabricated based on a graphene/polypyrrole/chitosan nanocomposite film modified glassy carbon electrode. The nanocomposite film was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and Raman spectroscopy. The electron transfer behaviour of the modified electrodes was investigated in [Fe(CN)(6)](3-)/(4-) redox probe using cyclic voltammetry and electrochemical impedance spectroscopy. Differential pulse voltammetry and amperometry were used to study the electrochemical properties of the proposed sensor. Under optimum conditions, the sensor exhibited good reproducibility and stability for nitrite determination. Linear response was obtained in the range of 0.5-722 μM with a detection limit of 0.1 μM (S/N = 3) for nitrite determination.     

Simultaneous detection of ascorbate and uric acid using a selectively catalytic surface

The direct and selective detection of ascorbate at conventional carbon or metal electrodes is difficult due to its large overpotential and fouling by oxidation products. Electrode modification by electrochemical reduction of diazonium salts of different aryl derivatives is useful for catalytic, analytical and biotechnological applications. A monolayer of o-aminophenol (o-AP) was grafted on a glassy carbon electrode (GCE) via the electrochemical reduction of its in situ prepared diazonium salts in aqueous solution. The o-aminophenol confined surface was characterized by cyclic voltammetry. The grafted film demonstrated an excellent electrocatalytic activity towards the oxidation of ascorbate in phosphate buffer of pH 7.0 shifting the overpotential from +462 to +263 mV versus Ag/AgCl. Cyclic voltammetry and d.c. amperometric measurements were carried out for the quantitative determination of ascorbate and uric acid. The catalytic oxidation peak current was linearly dependent on the ascorbate concentration and a linear calibration curve was obtained using d.c. amperometry in the range of 2-20 μM of ascorbate with a correlation coefficient 0.9998, and limit of detection 0.3 μM. The effect of H₂O₂ on the electrocatalytic oxidation of ascorbate at o-aminophenol modified GC electrode has been studied, the half-life time and rate constant was estimated as 270 s, and 2.57 × 10⁻³ s⁻¹, respectively. The catalytically selective electrode was applied to the simultaneous detection of ascorbate and uric acid, and used for their determination in real urine samples. This o-AP/GCE showed high stability with time, and was used as a simple and precise amperometric sensor for the selective determination of ascorbate.     

Simultaneous electrochemical sensing of ascorbic acid,dopamine and uric acid at anodized nanocrystalline graphite-like pyrolytic carbon film electrode

Nanocrystalline graphite-like pyrolytic carbon film (PCF) electrode fabricated by a non-catalytic chemical vapor deposition (CVD) process was used for the simultaneous electrochemical sensing of ascorbic acid (AA), dopamine (DA), and uric acid (UA). The electrode was studied with respect to changes in electrocatalytic activity caused by a simple and fast electrochemical pretreatment. The anodized electrode exhibited excellent performance compared to many chemically modified electrodes in terms of detection limit, linear dynamic range, and sensitivity. Differential pulse voltammetry (DPV) was used for the simultaneous determination of ternary mixtures of DA, AA, and UA. Under optimum conditions, the detection limits were 2.9 μM for AA, 0.04 μM for DA, and 0.03 μM for UA with sensitivities of 0.078, 5.345, and 6.192 A M⁻¹, respectively. The peak separation was 219 mV between AA and DA and 150 mV between DA and UA. No electrode fouling was observed and good reproducibility was obtained in all the experiments. The sensor was successfully applied for the assay of DA in an injectable drug and UA in human urine by using standard addition method.     

Nitrite sensor based on multilayer film of Dawson-type tungstophosphate α-K7[H4PW18O62]·18H2O immobilized on glassy carbon

A nitrite sensor based on immobilized Dawson-type tungstophosphate α-K₇[H₄PW₁₈O₆₂]·18H₂O (PW₁₈) in multilayers of charged polyelectrolyte poly(allylamine hydrochloride) (PAH) on a glassy carbon electrode is described. A nitrite sensor manufactured with 10 layers has a sensitivity of ∼4 nA/μM nitrite, fast response time (<6 s), low detection limit (∼0.1 μM), high selectivity towards endogenous interferences such as nitrate and molecular oxygen, a linear range from 0.1 μM to at least 20 mM nitrite and was stable for at least 2 months. In addition, such nitrite sensors can operate in a pH range from 1 to 9, and the sensitivity can be increased by increasing the number of layers at the expense of increasing the response time.     

Highly accessible Pt nanodots homogeneously decorated on Au nanorods surface for sensing

Some nanostructures are reported to possess enzyme-mimetic activities similar to those of natural enzymes. Herein, highly-dispersed Pt nanodots on Au nanorods (HD- PtNDs@AuNRs) with mimetic peroxidase activity were designed as an active electrode modifier for fabrication of a hydrogen peroxide (H₂O₂) electrochemical sensor. The HD-PtNDs@AuNRs were synthesized by a seed-mediated growth approach and confirmed by scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, and UV–vis spectroscopy. The electrochemical and catalytical performances of HD-PtNDs@AuNRs towards H₂O₂ reduction were investigated in detail by cyclic voltammetry and amperometry. The HD-PtNDs@AuNRs modified electrode displayed a high catalytic activity to H₂O₂ at −0.10 V (versus SCE), a rapid response within 5 s, a wide linear range of 2.0–3800.0 μM, a detection limit of 1.2 μM (S/N = 3), and a high sensitivity of 181 μA mM⁻¹ cm⁻². These results suggested a promising potential of fabricating H₂O₂ electrochemical sensor using HD- PtNDs@AuNRs.     

Facile hydrothermal growth graphene/ZnO nanocomposite for development of enhanced biosensor

Graphene/zinc oxide nanocomposite was synthesised via a facile, green and efficient approach consisted of novel liquid phase exfoliation and solvothermal growth for sensing application. Highly pristine graphene was synthesised through mild sonication treatment of graphite in a mixture of ethanol and water at an optimum ratio. The X-ray diffractometry (XRD) affirmed the hydrothermal growth of pure zinc oxide nanoparticles from zinc nitrate hexahydrate precursor. The as-prepared graphene/zinc oxide (G/ZnO) nanocomposite was characterised comprehensively to evaluate its morphology, crystallinity, composition and purity. All results clearly indicate that zinc oxide particles were homogenously distributed on graphene sheets, without any severe aggregation. The electrochemical performance of graphene/zinc oxide nanocomposite-modified screen-printed carbon electrode (SPCE) was evaluated using cyclic voltammetry (CV) and amperometry analysis. The resulting electrode exhibited excellent electrocatalytic activity towards the reduction of hydrogen peroxide (H₂O₂) in a linear range of 1–15 mM with a correlation coefficient of 0.9977. The sensitivity of the graphene/zinc oxide nanocomposite-modified hydrogen peroxide sensor was 3.2580 μAmM⁻¹ with a limit of detection of 7.4357 μM. An electrochemical DNA sensor platform was then fabricated for the detection of Avian Influenza H5 gene based on graphene/zinc oxide nanocomposite. The results obtained from amperometry study indicate that the graphene/zinc oxide nanocomposite-enhanced electrochemical DNA biosensor is significantly more sensitive (P < 0.05) and efficient than the conventional agarose gel electrophoresis.     

Voltammetric Study of Diethyltin Dichloride and the Electrocatalytic Reduction of Nitrate and Nitrite

The electrochemical characteristics of diethyltin dichloride on a platinum electrode were studied by cyclic voltammetry, rotating disk electrode and other methods. The results show that Et₂SnCl₂ can catalyze the reduction of nitrate and nitrite. The over-potential for the reduction of nitrate and nitrite on the modified electrode dropped significantly. The catalytic kinetics of the electrode were also studied. The proposed method can be used to determine nitrate and nitrite simultaneously in waste water.Received July 27, 2002; accepted March 10, 2003 Published online July 16, 2003     

Amperometric sulfite sensor based on multiwalled carbon nanotubes/ferrocene-branched chitosan composites

A novel amperometric sensor for the determination of sulfite was fabricated based on multiwalled carbon nanotubes (MWCNTs)/ferrocene-branched chitosan (CHIT-Fc) composites-covered glassy carbon electrode (GCE). The electrochemical behavior of the sensor was investigated in detail by cyclic voltammetry. The apparent surface electron transfer rate constant (K_s) and charge transfer coefficient (α) of the CHIT-Fc/MWCNTs/GCE were also determined by cyclic voltammetry, which were about 1.93 cm s⁻¹ and 0.42, respectively. The sensor displayed good electrocatalytic activity towards the oxidation of sulfite. The peak potential for the oxidation of sulfite was lowered by at least 330 mV compared with that obtained at CHIT/MWCNTs/GCE. In optimal conditions, linear range spans the concentration of sulfite from 5 μM to 1.5 mM and the detection limit was 2.8 μM at a signal-to-noise ratio of 3. The proposed method was used for the determination of sulfite in boiler water. In addition, the sensor has good stability and reproducibility.     

Electrochemical preparation of composite of poly brilliant cresyl blue (PBCB)–poly 5-amino-2-napthalenesulfonic acid electrode and electrocatalytic application

Poly brilliant cresyl blue (PBCB) and poly 5-amino-2-napthalenesulfonic (PANS) polymer composite modified electrode was fabricated by the electrochemical polymerization of brilliant cresyl blue and 5-amino-2-napthalenesulfonic acid. When compared polymer composite electrodes with PBCB and PANS electrode, it showed enhanced electrochemical property. The morphology of the resulting composite electrode was characterized by AFM, and the electrochemical properties of the modified electrode were characterized by cyclic voltammetry and amperometry. The composite electrode showed surface-confined and pH-dependent electrochemical property. The composite electrode exhibited high catalytic behavior toward the reduction of hydrogen peroxide at low overpotential. The detection limit and sensitivity of the electrode toward H₂O₂ detection was 5 μM and 1 μA/mM, respectively, and response time was less than 10 s for hydrogen peroxide.     

A novel non-enzymatic glucose sensor based on Cu nanoparticle modified graphene sheets electrode

A novel, stable and sensitive non-enzymatic glucose sensor was developed by potentiostatically electrodepositing metallic Cu nanoparticles on graphene sheets. The electrochemical performance of the Cu-graphene sheets electrode for detection of glucose was investigated by cyclic voltammetry and chronamperometry. The Cu-graphene sheets electrode displayed a synergistic effect of copper nanoparticles and graphene sheets towards the oxidation of glucose in alkaline solution, showing higher oxidation current and negative shift in peak potential. At detection potential of 500 mV, the Cu-graphene electrode sensor presented a wide linear range up to 4.5 mM glucose with a detection limit of 0.5 μM (signal/noise = 3). In addition, the sensor responds very quickly (<2 s) with addition of glucose. Furthermore, the Cu-graphene sheets electrode exhibits high stability and selectivity to glucose, and the poisoning by chloride ion as well as interference from the oxidation of common interfering species (ascorbic, dopamine, uric acid and carbohydrate) are effectively avoided. The Cu-graphene sheets electrode allows highly selective and sensitive, stable and fast amperometric sensing of glucose, which is promising for the development of non-enzymatic glucose sensor.     

A highly sensitive electrochemical sensor for simultaneous determination of hydroquinone and bisphenol A based on the ultrafine Pd nanoparticle@TiO2 functionalized SiC

A titanium dioxide–silicon carbide nanohybrid (TiO₂–SiC) with enhanced electrochemical performance was successfully prepared through a facile generic in situ growth strategy. Monodispersed ultrafine palladium nanoparticles (Pd NPs) with a uniform size of ∼2.3 nm were successfully obtained on the TiO₂–SiC surface via a chemical reduction method. The Pd-loaded TiO₂–SiC nanohybrid (Pd@TiO₂–SiC) was characterized by transmission electron microscopy and X-ray diffractometry. A method for the simultaneous electrochemical determination of hydroquinone (HQ) and bisphenol A (BPA) using a Pd@TiO₂–SiC nanocomposite-modified glassy carbon electrode was established. Utilizing the favorable properties of Pd NPs, the Pd@TiO₂–SiC nanohybrid-modified glassy carbon electrode exhibited electrochemical performance superior to those of TiO₂–SiC and SiC. Differential pulse voltammetry was successfully used to simultaneously quantify HQ and BPA within the concentration range of 0.01–200 μM under optimal conditions. The detection limits (S/N = 3) of the Pd@TiO₂–SiC nanohybrid electrode for HQ and BPA were 5.5 and 4.3 nM, respectively. The selectivity of the electrochemical sensor was improved by introducing 10% ethanol to the buffer medium. The practical application of the modified electrode was demonstrated by the simultaneous detection of HQ and BPA in tap water and wastewater samples. The simple and straightforward strategy presented in this paper are important for the facile fabrication of ultrafine metal NPs@metal oxide–SiC hybrids with high electrochemical performance and catalytic activity.     

Nitrite electrochemical sensor for food analysis based on direct immobilization of hemoglobin on multi-walled carbon nanotube ionic liquid electrode

A novel nitrite biosensor was constructed by simultaneous immobilization of hemoglobin (Hb) and a room temperature ionic liquid, octylpyridinium chloride ([OcPy][Cl]), on multi-walled carbon ionic liquid electrode (MWILE). The direct electron transfer of Hb showed a pair of redox peaks with a formal potential of ?0.187 V vs. Ag/AgCl in pH 5.0 acetate buffer solution. Nitrite (NO₂ ^?) catalysis on the modified electrode was investigated by cyclic voltammetry and amperometry. The biosensor exhibited a wide linear range for NO₂ ^? detection from 0.01 to 15 mM, with a detection limit (3σ) of 1.46 μM. MWILE provided an excellent matrix for protein immobilization and biosensor fabrication which could be used for the determination of NO₂ ^? with a low detection limit, fast response, long linearity, and excellent sensitivity.     

Amperometric sensor for nitrite using a glassy carbon electrode modified with alternating layers of iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin and cobalt(II) tetrasulfonated phthalocyanine

The development of a highly sensitive amperometric sensor for nitrite using a glassy carbon electrode modified with alternated layers of iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and cobalt(II) tetrasulfonated phthalocyanine (CoTSPc) is described. The modified electrode showed an excellent catalytic activity and stability for the nitrite oxidation decreasing the peak potentials about 200 mV toward less positive values and presenting much higher peak currents than those obtained on the bare GC electrode. A linear response range of 0.2-8.6 μmol l⁻¹, with a sensitivity of 0.37 μA l μmol⁻¹ and detection limit of 0.04 μmol l⁻¹ were obtained with this sensor. The repeatability of the proposed sensor, evaluated in term of relative standard deviation, was verified to be 1.4% for 10 measurements of 0.2 μmol l⁻¹ nitrite solution. Interference caused by common ions has been investigated in simulated mixtures containing high concentration level of interfering ions and the sensor was found to be tolerant against these ions. The developed sensor was applied for the nitrite determination in water samples and the results were in agreement with those obtained by a comparative method described in the literature. The average recovery for these samples was 100.1 (±0.7)%.     

Electrochemical determination of iodide on a vanadium oxide-polypropylene carbonate coated glassy carbon electrode

A vanadium oxide-modified glassy carbon electrode was simply and conveniently fabricated by casting vanadium tri(isoproxide) oxide (VO(OC₃H₇)₃) and poly(propylene carbonate) (PPC) onto the glassy carbon electrode surface. The electrochemical properties of iodide at the VO(OC₃H₇)₃-PPC film-modified glassy carbon electrode were investigated by cyclic voltammetry, and an anodic peak was observed at approximately +0.71 V (vs. SCE). Based on this, a sensitive and convenient electrochemical method was proposed for the determination of iodide. Flow injection amperometry (FIA) exhibited a good linear relationship with the concentration of iodide in the range of 5 × 10⁻⁷ mol L⁻¹ and 1 × 10⁻³ mol L⁻¹, and the detection limit was 1 × 10⁻⁷ mol L⁻¹. Quantitative recovery of iodide in synthetic samples has been obtained and the interferences from different cations and anions have been studied. The method has been successfully applied to the determination of iodide in dry edible seaweed. The concentrations of iodide measured by this method are in good agreement with those obtained by spectrophotometric method.     

Nano composite system based on coumarin derivative–titanium dioxide nanoparticles and ionic liquid: Determination of levodopa and carbidopa in human serum and pharmaceutical formulations

The combination of coumarin derivative (7-(1,3-dithiolan-2-yl)-9,10-dihydroxy-6H-benzofuro[3,2-c]chromen-6-on), (DC)–titanium dioxide nanoparticles (TiO₂) and ionic liquid (IL) yields nanostructured electrochemical sensor, formed a novel kind of structurally uniform and electrocatalytic activity material. This new ionic liquid–TiO₂ nanoparticles modified carbon paste electrode (IL–CTP) due to its enhanced conductivity presented very large current response from electroactive substrates. The modified electrode was characterized by different methods including a scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS) and voltammetry. A pair of well-defined quasi reversible redox peaks of coumarin derivative was obtained at the modified carbon paste electrode (DC/IL–CTP) by direct electron transfer between the coumarin derivative and the CP electrode. Dramatically enhanced electrocatalytic activity was exemplified at the DC/IL–CTP electrode, as an electrochemical sensor to study the electro oxidation of levodopa (LD) and carbidopa (CD). Based on differential pulse voltammetry (DPV), the oxidation of LD and CD exhibited the dynamic range between 0.10– 900.0 μM and 20.0–900.0 μM respectively, and the detection limit (3σ) for LD and CD were 41 nM and 0.38 μM, respectively. DPV was used for simultaneous determination of LD and CD at the DC/IL–CTP electrode, and quantitation of LD and CD in some real samples (such as tablets of Parkin-C Fort and Madopar, Sinemet, water, urine, and human blood serum) by the standard addition method.