Simultaneous Determination of Dihydroxybenzene Isomers at MWCNTs/β‐Cyclodextrin Modified Carbon Ionic Liquid Electrode in the Presence of Cetylpyridinium Bromide

Simultaneous determination of dihydroxybenzene isomers was investigated at a multi‐wall carbon nanotubes (MWCNTs)/β‐cyclodextrin composite modified carbon ionic liquid electrode in phosphate buffer solution (pH 7.0, 1/15 mol/L) in the presence of cationic surfactant cetylpyridinium bromide (CPB). With the great enhancement of surfactant CPB, the voltammetric responses of dihydroxybenzene isomers were more sensitive and selective. The oxidation peak potential of hydroquinone was about 0.024 V, catechol was about 0.140 V and resorcinol 0.520 V in differential pulse voltammetric (DPV) measurements, which indicated that the dihydroxybenzene isomers could be separated entirely. The electrode showed wide linear behaviors in the range of 1.2×10^?7–2.2×10^?3, 7.0×10^?7–1.0×10^?3, 2.6×10^?6–9.0×10^?4 mol/L for hydroquinone, catechol and resorcinol, respectively. And the detection limits of the three dihydroxybenzene isomers were 4.0×10^?8, 8.0×10^?8, 9.0×10^?7 mol/L, respectively. The proposed method could be applied to the determination of dihydroxybenzene isomers in artificial wastewater, and the recovery was from 97.4% to 104.2%.     

Simultaneous Determination of Dihydroxybenzene Isomers Using Preanodized Inlaying Ultrathin Carbon Paste Electrode

In this paper, we described a rapid, sensitive and selective method for simultaneous voltammetric determination of dihydroxybenzene isomers with a preanodized inlaying ultrathin carbon paste electrode (PAIUCPE). Scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS) and voltammetry were employed to characterize the configuration and electrochemical properties of the electrode. The resulting PAIUCPE exhibited excellent recognition ability towards dihydroxybenzene isomers. Three well‐defined oxidation peaks of catechol (CC), resorcinol (RC) and hydroquinone (HQ) can be identified entirely at the electrode. The oxidation peak potential difference between HQ and CC was 120 mV, CC and RC 430 mV, respectively. The peak currents increased linearly with increasing the concentration of dihydroxybenzene isomers. The proposed electrode can be applied to simultaneous determination of dihydroxybenzene isomers without previous chemical or physical separations.     

Simultaneous determination of catechol and hydroquinone based on poly (diallyldimethylammonium chloride) functionalized graphene-modified glassy carbon electrode

Simultaneous determination of catechol (CC) and hydroquinone (HQ) were investigated by voltammetry based on glassy carbon electrode (GCE) modified by poly (diallyldimethylammonium chloride) (PDDA) functionalized graphene (PDDA-G). The modified electrode showed excellent sensitivity and selectivity properties for the two dihydroxybenzene isomers. In 0.1 mol/L phosphate buffer solution (PBS, pH 7.0), the oxidation peak potential difference between CC and HQ was 108 mV, and the peaks on the PDDA-G/GCE were three times as high as the ones on graphene-modified glass carbon electrode. Under optimized conditions, the PDDA-G/GCE showed wide linear behaviors in the range of 1 × 10⁻⁶−4 × 10⁻⁴ mol/L for CC and 1 × 10⁻⁶−5 × 10⁻⁴ mol/L for HQ, with the detection limits 2.0 × 10⁻⁷ mol/L for CC and 2.5 × 10⁻⁷ mol/L for HQ (S/N = 3) in mixture, respectively. Some kinetic parameters, such as the electron transfer number (n), charge transfer coefficient (α), and the apparent heterogeneous electron transfer rate constant (k _s), were calculated. The proposed method was applied to simultaneous determine CC and HQ in real water samples of Yellow River with satisfactory results.     

Voltammetric Determination of L‐Dopa Using a Carbon Nanotubes‐Nafion Modified Glassy Carbon Electrode

Abstract

A method for determination of L‐dopa by the adsorption stripping voltammetry (ASV) using a multiwalled carbon nanotubes (MWNTs)–Nafion modified glassy carbon electrode (GMGCE) was proposed. This chemically modified electrode (CME) shows a better stability. A sensitive oxidation peak was observed and the anodic peak potential is ca. 0.374V (vs. SCE). The influences of various experimental parameters on the current peak were completely studied. Under the optimized condition, the method has been applied to the determination of L‐dopa in samples. There is a good linear relationship between the peak current (i_p) and L‐dopa concentration in the range of 3.5×10^?7～1.5×10^?5 mol/L, with the limit of detection 5.0×10^?8 mol/L.     

Electrochemical solid-phase nanoextraction of copper(II) on a magnesium oxinate-modified carbon paste electrode by cyclic voltammetry

Solid-phase nanoextraction is a sample preparation technique, which combines nanotechnology with analytical chemistry, and brings analytical chemistry to a higher level, particularly for complex system analysis. This paper describes a typical example of electrochemical solid-phase nanoextraction and electrochemical detection. Trace amounts of copper (5.0?×?10^?13?mol/L) were extracted by electrochemical solid-phase nanoextraction on to the magnesium oxinate nanoparticle-modified carbon paste electrode surface in a pH?7.2 phosphate buffer system at ?0.50 V for 100 s. The extraction is achieved by the cation exchange between copper(II) in the aqueous solution and magnesium(II) from the magnesium oxinate nanoparticles on the electrode surface. The extracted copper shows an irreversible anodic peak at about 0.2 V (vs. saturated calomel electrode). The peak current is proportional to the scan rate, which shows this to be a surface-controlled process. The oxidation peak current is proportional to the logarithm of the copper concentration in the range 5.0?×?10^?13?～?5.0?×?10^?7?M with a slope of 2.215. This powerful method uses the carbon paste electrode to combine extraction with electrochemical analysis.     

Study on the Electrochemical Behavior of Dopamine and Uric Acid at a 2‐Amino‐5‐mercapto‐[1,3,4] Triazole Self‐Assembled Monolayers Electrode

Selected from a series of structurally related heteroaromatic thiols, a newly synthesized reagent 2‐amino‐5‐mercapto‐[1,3,4] triazole (MATZ) was used to fabricate self‐assembled monolayers (SAMs) on gold electrode for the first time. The MATZ/Au SAMs was characterized by electrochemical methods and scanning electronic microscopy (SEM). In 0.04 mol/L Britton–Robinson buffer solution (pH 5), the electrochemical behavior of dopamine showed a quasireversible process at the MATZ/Au SAMs with an electrode kinetic constant 0.1049 cm/s. However, the electrochemical reaction of uric acid at the SAMs electrode showed an irreversible oxidation process, the charge‐transfer kinetics of uric acid was promoted by the SAMs. By Osteryoung square‐wave voltammetry (OSWV), the simultaneous determination of dopamine and uric acid can be accomplished with an oxidation peak separation of 0.24 V, the peak current of dopamine and uric acid were linearly to its concentration in the range of 2.5×10^?6–5.0×10^?4 mol/L for dopamine and 1×10^?6–1×10^?4 mol/L for uric acid with a detection limit of 8.0×10^?7 mol/L for dopamine and 7.0×10^?7 mol/L for uric acid. The MATZ/Au SAMs electrode was used to detect the content of uric acid in real urine and serum sample with satisfactory results.     

Selective determination of hydroquinone in the presence of catechol based on over-oxidized poly(hydroquinone)

Selective determination of hydroquinone (HQ) in the presence of catechol (CC) was developed at an over-oxidized poly(hydroquinone) (PHQ) electrode. The electrochemical polymerization of HQ was carried out by potentiostatic method on a glassy carbon electrode. The resulting PHQ was over-oxidized in 0.10?mol/L NaOH solution and thus poly(p-benzoquinone) was obtained. Two dihydroxybenzene isomers, HQ and CC, show different voltammetric behavior at the over-oxidized PHQ electrode. The peak current of HQ is much larger than that of CC with the same concentration, which is attributed to the different position of the hydroxyl groups in benzene ring of the two isomers. The results from electrochemical impedance spectroscopy also demonstrates that the over-oxidized PHQ electrode has a stronger affinity for HQ over CC.     

The electrochemical oxidation of pentachlorophenol and its sensitive determination at chitosan modified carbon paste electrode

We report on a novel electrochemical method to detect trace pentachlorophenol (PCP) by using a chitosan (CS) modified carbon paste electrode (CS/CPE). Compared with that at a bare carbon paste electrode (CPE), the current response was greatly improved at the CS/CPE due to the enhancement effect of CS. Under optimal working conditions, the oxidation peak current of PCP was proportional to its concentration in the range of 1.0 × 10^?7 to 5.0 × 10^?6 and 5.0 × 10^?6 to 1.0 × 10^?4 mol/L, with an extremely low detection limit of 4.0 × 10^?8 mol/L. Our method was successfully used to detect the PCP concentration in vegetable samples.     

Electrochemical behavior of dihydroxybenzene isomers at MWCNTs modified electrode and simultaneous determination in neutral condition

Simultaneous determination of dihydroxybenzene isomers in neutral condition was successfully realized by a simple and easy prepared modified electrode without previous chemical or physical separations. The multi-walled carbon nanotubes modified glassy carbon electrode (MWCNTs/GCE), which was prepared by the drop-coating method, was characterized by FE-SEM and TEM. Then, the electrochemical behavior of dihydroxybenzene isomers at MWCNTs/GCE was systematically studied at different temperature and pH conditions. The oxidation peak potentials were separated in neutral condition with 105 mV to hydroquinone (HQ) and catechol (CC) and 390 mV to CC and resorcinol (RS). And in neutral condition, the amperometric current were found to be linear with concentration of HQ, CC, and RS (20–140 μM) with the presence of 100 μM other isomers. Furthermore, excellent anti-interference, stability, and reproducibility were also presented by this modified electrode.     

Preparation of a Novel COOH Ion Implantation Sensor and Its Application

A novel ion implantation sensor (DNA/COOH/ITO) based on DNA immobilization in COOH/ITO probe was manufactured for the first time. The surface morphologies of the electrodes were characterized by X‐ray photoelectron spectroscopy (XPS), field‐emission‐scanning electron microscopy (FSEM) and electrochemical methods. In a 0.5 mol/L PBS solution, a sensitive oxidation peak of DNA on the COOH/ITO electrode was obtained by voltammetry. The electrochemical behavior of DNA was studied. And the oxidative peak potential of DNA was +0.400 V (vs. Ag/AgCl). Its peak current was proportional to the concentration of DNA over the range of 1.0×10^?8?1.0×10^?6 mol/L with a detection limit of 5.0×10^?9 mol/L (about 0.5 ng/mL). This sensor was applied to the direct detection of DNA samples.     

Covalent modification of a glassy carbon electrode with penicillamine for simultaneous determination of hydroquinone and catechol

A simple and highly selective electrochemical method has been developed for the simultaneous determination of hydroquinone (HQ) and catechol (CC) at a glassy carbon electrode covalently modified with penicillamine (Pen). The electrode is used for the simultaneous electrochemical determination of HQ and CC and shows an excellent electrocatalytical effect on the oxidation of HQ and CC upon cyclic voltammetry in acetate buffer solution of pH 5.0. In differential pulse voltammetric measurements, the modified electrode was able to separate the oxidation peak potentials of HQ and CC present in binary mixtures by about 103 mV although the bare electrode gave a single broad response. The determination limit of HQ in the presence of 0.1 mmol L⁻¹ CC was 1.0 × 10⁻⁶ mol L⁻¹, and the determination limit of CC in the presence of 0.1 mmol L⁻¹ HQ was 6.0 × 10⁻⁷ mol L⁻¹. The method was applied to the simultaneous determination of HQ and CC in a water sample. It is simple and highly selective.     

A Novel Sensor Based on Manganese azo‐Macrocycle/Carbon Nanotubes to Perform the Oxidation and Reduction Processes of Two Diphenol Isomers

The present work describes the development of a selective and sensitive voltammetric sensor for simultaneous determination of catechol (CC) and hydroquinone (HQ), based on a glassy carbon (GC) electrode modified with manganese phthalocyanine azo‐macrocycle (MnPc) adsorbed on multiwalled carbon nanotubes (MWCNT). Scanning electron microscopy and scanning electrochemical microscopy were used to characterize the composite material (MnPc/MWCNT) on the glassy carbon electrode surface. The modified electrode showed excellent electrochemical activity towards the simultaneous oxidation and reduction of CC and HQ. On the MnPc/MWCNT/GC electrode, both CC and HQ can generate a pair of quasi‐reversible and well‐defined redox peaks. Under optimized experimental and operational conditions, the cathodic peak currents were linear over the range 1–600 µmol L^?1 for both CC and HQ, with limits of detection of 0.095 and 0.041 µmol L^?1, respectively. The anodic peak currents were also linear over the range 1–600 µmol L^?1 for both CC and HQ, with limits of detection of 0.096 and 0.048 µmol L^?1, respectively. The proposed method was effectively applied for the simultaneous detection of hydroquinone and catechol in water samples and the results were in agreement with those obtained by a comparative method described in the literature.     

Simple sensor for simultaneous determination of dihydroxybenzene isomers

A simple sensor based on bare carbon ionic liquid electrode was fabricated for simultaneous determination of dihydroxybenzene isomers in 0.1 mol L⁻¹ phosphate buffer solution (pH 6.0). The oxidation peak potential of hydroquinone was about 0.136 V, catechol was about 0.240 V, and resorcinol 0.632 V by differential pulse voltammetric measurements, which indicated that the dihydroxybenzene isomers could be separated absolutely. The sensor showed wide linear behaviors in the range of 5.0 × 10⁻⁷–2.0 × 10⁻⁴ mol L⁻¹ for hydroquinone and catechol, 3.5 × 10⁻⁶–1.535 × 10⁻⁴ mol L⁻¹ for resorcinol, respectively. And the detection limits of the three dihydroxybenzene isomers were 5.0 × 10⁻⁸, 2.0 × 10⁻⁷, 5.0 × 10⁻⁷ mol L⁻¹, respectively (S/N = 3). The proposed method could be applied to the determination of dihydroxybenzene isomers in artificial wastewater and the recovery was from 93.9% to 104.6%.     

Adsorptive Voltammetric Measurement of Trace Level of Iron(III) with 4–(2–Pyridylazo) Resorcin

Abstract

The polarographic behavior of the complex of iron–4– (2–pyridylazo) resorcin(PAR) was studied. In HAc– NaAc– EDTA buffer solution, the complex can be adsorped on a hanging mercury drop electrode giving a sensitive adsorptive complex reduction peak with a peak potential at -0.36V(vs. SCE). Optimum experimental conditions were found by the use of 0.08mol/L HAc, 0.06mol/L NaAc, 5.0 × 10^?3mol/L EDTA and 1.0 × 10^?5mol/L PAR. With preconcentration for 60s, the derivative peak height of the complex compound is linearly proportional to the concentration for Fe in the range from 1.0 × 10^?9mol/L to 1.0 × 10^?7mol/L. For a 2–min pre–concentration time, the detection limit found was 2.0 × 10^?10mol/L. This method has high sensitivity and selectivity. It has been applied to the determination of trace iron in food and water samples without any pre–separation step.     

Direct Electrochemistry of Hemoglobin Entrapped in Composite Electrodeposited Chitosan‐Multiwall Carbon Nanotubes and Nanogold Particles Membrane and Its Electrocatalytic Application

Hemoglobin was entrapped in composite electrodeposited chitosan‐multiwall carbon nanotubes (MCNTs) film by assembling gold nanoparticles and hemoglobin step by step. In phosphate buffer solution (pH 7), a pair of well‐defined and quasireversible redox peaks appeared with formal potential at ?0.289 V and peak separation of 100 mV. The redox peaks respected for the direct electrochemistry of hemoglobin at the surface of chitosan‐MCNTs‐gold nanoparticles modified electrode. The parameters of experiments have also been optimized. The composite electrode showed excellent electrocatalysis to peroxide hydrogen and oxygen, the peak current was linearly proportional to H₂O₂ concentration in the range from 1×10^?6 mol/L to 4.7×10^?4 mol/L with a detection limit of 5.0×10^?7 mol/L, and this biosensor exhibited high stability, good reproducibility and better selectivity. The biosensor showed a Michaelis–Menten kinetic response as H₂O₂ concentration is larger than 5.0×10^?4 mol/L, the apparent Michaelis–Menten constant for hydrogen peroxide was calculated to be 1.61 μmol/L.     

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 oxidation determination and voltammetric behaviour of 4-nitrophenol based on Cu2O nanoparticles modified glassy carbon electrode

Cu₂O nanoparticles (nano-Cu₂O) modified glassy carbon electrode (GCE) was fabricated and used to investigate the electrochemical behaviour of 4-nitrophenol (4-NP) by cyclic voltammetry (CV), chronoamperometry (CA), chronocoulometry (CC) and differential pulse voltammetry (DPV). Compared with GCE, a remarkable increase in oxidation peak current was observed. It indicates that nano-Cu₂O exhibits remarkable enhancement effect on the electrochemical oxidation of 4-NP. Under the optimised experimental conditions, the oxidation peak currents were propotional to 4-NP concentration in the range from 1.0?×?10^?6 to 4.0?×?10^?4?mol?L^?1 with a detection limit of 5.0?×?10^?7?mol?L^?1 (S/N?=?3). The fabricated electrode presented good repeatability, stability and anti-interference. Finally, the proposed method was applied to determine 4-NP in water samples. The recoveries for these samples were from 94.60% to 105.5%.     

Electrochemical Oxidation of Tryptophan and Its Analysis in Pharmaceutical Formulations at a Poly(Methyl Red) Film-Modified Electrode

A poly(methyl red) film-modified glassy carbon electrode was fabricated and the oxidation behavior of tryptophan at the modified electrode was investigated by cyclic and linear sweep voltammetry. The oxidation peak current of tryptophan at the modified electrode increased significantly, and the oxidation process was irreversible and adsorption-controlled. An analytical method was developed for the determination of tryptophan in a phosphate buffer solution at pH 3.5. The anodic peak current varied linearly with a tryptophan concentration in the range 1.0 × 10^?7 to 1.0 × 10^?4 mol/L with a limit of detection of 4.0 × 10^?8 mol/L. The proposed method was successfully applied to determine tryptophan in composite amino acid injections.     

Covalent modification of glassy carbon electrode with aspartic acid for simultaneous determination of hydroquinone and catechol

Glassy carbon electrode (GCE) is covalently modified with aspartic acid (Asp). The modified electrode is used for the simultaneous electrochemical determination of hydroquinone (HQ) and catechol (CC) and shows an excellent electrocatalytical effect on the oxidation of HQ and CC by cyclic voltammetry (CV) in 0.1 mol/L acetate buffer solution (pH 4.5). In differential pulse voltammetric (DPV) measurements, the modified electrode could separate the oxidation peak potentials of HQ and CC present in binary mixtures by about 101 mV though the bare electrode gave a single broad response. A successful elimination of the fouling effect by the oxidized product of HQ on the response of CC has been achieved at the modified electrode. The determination limit of HQ in the presence of 0.1 mmol/L CC was 9.0 x 10(-7) mol/L and the determination limit of CC in the presence of 0.1 mmol/L HQ was 5.0 x 10(-7) mol/L. The proposed method has been applied to the simultaneous determination of HQ and CC in a water sample with simplicity and high selectivity.     

Catalytic Adsorptive Stripping Voltammetry of Germanium(IV) in the Presence of Gallic Acid and Vanadium(IV)‐EDTA

A highly sensitive and selective catalytic adsorptive cathodic striping procedure for the determination of trace germanium is presented. The method is based on adsorptive accumulation of the Ge(IV)‐gallic acid (GA) complex onto a hanging mercury drop electrode, followed by reduction of the adsorbed species. The reduction current is enhanced catalytically by addition of vanadium(IV)‐EDTA. The optimal experimental conditions include the use of 0.03 mol/L HClO₄ (pH1.6), 6.0×10^?3 mol/L GA, 3.0×10^?3 mol/L V(IV), 4.0×10^?3 mol/L EDTA, an accumulation potential of ?0.10 V(vs. Ag/AgCl), an accumulation time of 120 s and a differential pulse potential scan mode. The peak current is proportional to the concentration of Ge(IV) over the range of 3.0×10^?11 to 1.0×10^?8 mol/L and the detection limit is 2×10^?11 mol/L for a 120 s adsorption time. The relative standard deviation at 5.0×10^?10 mol/L level is 3.1%. No serious interferences were found. The method was applied to the determination of germanium in ore, mineral water and vegetable samples with satisfactory results.