Sensitive voltammetric determination of tyrosine using multi-walled carbon nanotubes/4-aminobenzeresulfonic acid film-coated glassy carbon electrode

A chemically modified electrode is constructed based on the multi-walled carbon nanotubes (MWNTs)/4-aminobenzeresulfonic acid (4-ABSA) film-coated glassy carbon electrode. The electrocatalytic oxidation of tyrosine (Tyr) is investigated on the surface of the MWNTs/4-ABSA-modified electrode using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The prepared modified electrode shows voltammetric responses with high sensitivity and selectivity for Tyr in optimal conditions, which makes it very suitable for sub-micromolar detection of Tyr. A sensitive oxidation peak at +0.64 V is employed to determine Tyr. Good linear relationship between the oxidation peak current and the Tyr concentration in the range of 1 × 10⁻⁷ to 5 × 10⁻⁵ mol/L is obtained in phosphate buffer solution with pH 7.0. By use of modified electrode, the voltammetric detection limit for Tyr in DPV measurements is 8 × 10⁻⁸ mol/L (S/N = 3). Good sensitivity, selectivity and stability of the low-cost modified electrode make it very suitable for the determination of trace amounts of Tyr in pharmaceutical and clinical preparations.     

Electrochemical study of bergenin on a poly(4-(2-pyridylazo)-resorcinol) modified glassy carbon electrode and its determination in tablets and urine

A very sensitive electroanalytical method was employed to determine bergenin in phosphate buffer with a pH of 6.0, bergenin was accumulated at a 4-(2-pyridylazo)-resorcinol (PAR) polymer film modified glassy carbon electrode (GCE) surface under the condition of open-circuit. In the following anodic sweep from −0.4 to 0.8 V, bergenin adsorbed at the PAR polymer film modified electrode surface, was oxidized and yielded a sensitive oxidation peak at 0.595 V. Due to its unique structure and extraordinary properties, the PAR polymer film shows higher accumulation efficiency toward bergenin compared with a bare GCE. Hence, the amount of bergenin at the PAR polymer film modified GCE surface increases significantly, and finally the oxidation peak current improves greatly. The experimental conditions, such as supporting electrolyte, pH value, accumulation time and scan rate, were optimized for the measurement of bergenin, and a sensitive electroanalytical method was proposed for bergenin determination. The oxidation peak current varies linearly with the concentration of bergenin over the range of 2.0 × 10⁻⁷ to 1.2 × 10⁻⁵ mol/L, and the detection limit is 2.0 × 10⁻⁸ mol/L after 3 min open-circuit accumulation. The relative standard deviation of the same electrode in 10 successive scans is 1.8% for 1.0 × 10⁻⁶ mol/L bergenin and 2.1% for interelectrodes, indicating excellent reproducibility. This new method was successfully demonstrated with bergenin tablets and diluted urine.     

Enhancement effect of sodium dodecyl benzene sulfonate (SDBS) and its application into voltammetric determination of telmisartan

A sensitive and rapid electrochemical method was developed for the determination of telmisartan based on the enhancement effect of sodium dodecyl benzene sulfonate (SDBS). In 0.1 mol L⁻¹ HClO₄ and in the presence of 7.5 × 10⁻⁵ mol L⁻¹ SDBS, a well-defined and sensitive oxidation peak was observed for telmisartan at the acetylene black (AB) paste electrode. However, the oxidation peak is poor-shaped and the peak current is very low in the absence of SDBS, suggesting that SDBS shows obvious enhancement effect for the determination of telmisartan. After all the experimental parameters were optimized, a sensitive and simple electrochemical method was developed for determining telmisartan. The oxidation peak current is proportional to the concentration of telmisartan over the range from 2.5 × 10⁻⁷ to 2.0 × 10⁻⁵ mol L⁻¹. The detection limit is 7.5 × 10⁻⁸ mol L⁻¹ after 2 min of accumulation. This new voltammetric method was successfully used to detect telmisartan in drugs.     

An ionic liquid-type carbon paste electrode for electrochemical investigation and determination of calcium dobesilate

An ionic liquid-type carbon paste electrode (IL-CPE) had been fabricated by replacing non-conductive organic binders with a conductive room temperature ionic liquid, 1-pentyl-3-methylimidazolium hexafluorophosphate (PMIMPF₆). The electrochemical responses of calcium dobesilate were investigated at the IL-CPE and the traditional carbon paste electrode (T-CPE) in 0.05 mol L⁻¹ H₂SO₄, respectively. The results showed the superiority of IL-CPE to T-CPE in terms of provision of higher sensitivity, faster electron transfer and better reversibility. A novel method for determination of calcium dobesilate was proposed. The oxidation peak current was rectilinear with calcium dobesilate concentration in the range of 8.0 × 10⁻⁷ to 1.0 × 10⁻⁴ mol L⁻¹, with a detection limit of 4.0 × 10⁻⁷ mol L⁻¹(S/N = 3) by differential pulse voltammetry. The proposed method was applied to directly determine calcium dobesilate in capsule and urine samples.     

Voltammetric determination of glucose based on reduction of copper(II)–glucose complex at lanthanum hydroxide nanowire modified carbon paste electrodes

A novel voltammetric method for the determination of β-d-glucose (GO) is proposed based on the reduction of Cu(II) ion in Cu(II)(NH₃)₄²⁺–GO complex at lanthanum(III) hydroxide nanowires (LNWs) modified carbon paste electrode (LNWs/CPE). In 0.1 mol L⁻¹ NH₃·H₂O–NH₄Cl (pH 9.8) buffer containing 5.0 × 10⁻⁵ mol L⁻¹ Cu(II) ion, the sensitive reduction peak of Cu(II)(NH₃)₄²⁺–GO complex was observed at −0.17 V (versus, SCE), which was mainly ascribed to both the increase of efficient electrode surface and the selective coordination of La(III) in LNW to GO. The increment of peak current obtained by deducting the reduction peak current of the Cu(II) ion from that of the Cu(II)(NH₃)₄²⁺–GO complex was rectilinear with GO concentration in the range of 8.0 × 10⁻⁷ to 2.0 × 10⁻⁵ mol L⁻¹, with a detection limit of 3.5 × 10⁻⁷ mol L⁻¹. A 500-fold of sucrose and amylam, 100-fold of ascorbic acid, 120-fold of uric acid as well as gluconic acid did not interfere with 1.0 × 10⁻⁵ mol L⁻¹ GO determination.     

Sensitive determination of phenylephrine and chlorprothixene at poly(4-aminobenzene sulfonic acid) modified glassy carbon electrode

Phenylephrine (i.e. PHE) and chlorprothixene (i.e. CPT), two effective and important antipsychotic drugs with low redox activity, were found generating an irreversible anodic peak at about +0.89 V (vs. SCE) and +1.04 V in 0.05 M HAc–NaAc (pH 5.0) or NH₂CH₂COOH–HCl (pH 2.4) buffer solution at poly(4-aminobenzene sulfonic acid) modified glassy carbon electrode (i.e. poly(4-ABSA)/GC), respectively. Sensitive and quantitative measurement for them based on the anodic peaks was established under the optimum conditions. The anodic peak current was linear to PHE and CPT concentrations from 1 × 10⁻⁷ to 1.5 × 10⁻⁵ M and 2 × 10⁻⁶ to 4.5 × 10⁻⁵ M, the detection limits obtained were 1 × 10⁻⁸ and 1 × 10⁻⁷ M, separately. The modified electrode exhibited some excellent characteristics including easy regeneration, high stability, good reproducibility and selectivity. The method proposed was successfully applied to the determination of PHE and CPT in drug injections or tablets and proved to be reliable compared with ultraviolet spectrophotometry. The modified electrode was characterized by electrochemical methods.     

Selective determination of dopamine in the presence of high concentration of ascorbic acid using nano-Au self-assembly glassy carbon electrode

The cysteamine (CA) was bound onto surface of the pretreated glassy carbon electrode (GC) with cyclic voltammetry (CV). Gold nanoparticles were self-assembled to the electrode binding with cysteamine via strong AuS covalent bond to fabricate the nano-Au self-assembled modified electrode (nano-Au/CA/GC). The modified electrode was characterized with cyclic voltammetric and ac impedance methods. The electrochemical behavior of dopamine (DA) on the modified electrode was investigated with cyclic voltammetry and differential pulse voltammetry (DPV). A well-defined redox peaks of DA on the nano-Au/CA/GC electrode were obtained at E_pa = 0.175 V and E_pc = 0.146 V (vs. SCE), respectively. The peak current of DA is linear with the concentration of DA in the range of 1.0 × 10⁻⁸ mol L⁻¹ to 2.5 × 10⁻⁵ mol L⁻¹, with the correlation coefficient of 0.998. The detection limit is 4.0 × 10⁻⁹ mol L⁻¹ (S/N = 3). The modified electrode exhibited an excellent reproducibility, sensibility and stability for determination of DA in the presence of high concentration AA, and can be applied to determinate dopamine injection, with satisfied result.     

Determination of chromium(III) and total chromium using dual channels on glass chip with chemiluminescence detection

A simple, rapid and sensitive method for the determination of chromium(III) and total chromium using the simple dual T channels on glass chip with negative pressure pumping system and chemiluminescence (CL) detection is presented. The CL reaction was based on luminol oxidation by hydrogen peroxide in basic aqueous solution catalyzed by chromium(III). Total chromium in form of chromium(III) was achieved after chromium(VI) was completely reduced by acidic sodium hydrogen sulfite. Total chromium could then be determined with the same strategy as the chromium(III). The CL reagent was composed of 1.0 × 10⁻⁴ mol/L luminol, 1.0 × 10⁻² mol/L hydrogen peroxide and 0.10 mol/L sodium bromide in 0.050 mol/L carbonate buffer (pH 11.00). The 1.0 × 10⁻² mol/L ethylenediaminetetraacetic acid was added into the sample solution in order to improve the selectivity. Chromium(III) could be detected at a notably concentration of 1.6 × 10⁻¹⁶ mol/L and a linear calibration curve was obtained from 1.0 × 10⁻¹⁵ to 1.0 × 10⁻¹³ mol/L. The sample and CL reagent consumption were only 15 and 20 μL, respectively. The analysis time was less than 1 min per sample with the precision (%R.S.D.) was 4.7%. The proposed method has been applied successfully to the analysis of river water, mineral waters, drinking waters and tap water. Its performance was verified by the analysis of certified total chromium-reference materials and by recovery measurement on spiked synthetic seawater sample.     

Iodide-selective carbon paste electrodes based on recently synthesized Schiff base complexes of Fe(III)

A new modified carbon paste electrode (CPE) based on a recently synthesized Schiff base complex of Fe(III) as a suitable carrier for I⁻ ion is described. The electrode exhibits a super Nernstian slope of 71.0±0.3 mV per decade for I⁻ ion over a wide concentration range from 1.0×10⁻⁶ to 5.0×10⁻¹ M, with a low detection limit of 6.5×10⁻⁷ M. It has a relatively fast response time, a satisfactory reproducibility and relatively long life time. The proposed sensor shows a fairly good selectivity toward I⁻ ion in comparison to other common anions. The potentiometric response is independent of the pH of the test solution in the pH range 3.5–10.0. Spectrophotometric studies confirmed the redox-type response mechanism of the electrode toward iodide ion. The proposed electrode was used as an indicator electrode in potentiometric titration of iodide ion.     

Square wave adsorptive stripping voltammetric determination of famotidine in urine

Electrochemical studies of famotidine were carried out using voltammetric techniques: cyclic voltammetry, linear sweep and square wave adsorptive stripping voltammetry. The dependence of the current on pH, buffer concentration, nature of the buffer, and scan rate was investigated. The best results for the determination of famotidine were obtained in MOPS buffer solution at pH 6.7. This electroanalytical procedure enabled to determine famotidine in the concentration range 1 × 10⁻⁹–4 × 10⁻⁸ mol L⁻¹ by linear sweep adsorptive stripping voltammetry (LS AdSV) and 5 × 10⁻¹⁰–6 × 10⁻⁸ mol L⁻¹ by square wave adsorptive stripping voltammetry (SW AdSV). Repeatability, precision and accuracy of the developed methods were checked. The detection and quantification limits were found to be 1.8 × 10⁻¹⁰ and 6.2 × 10⁻¹⁰ mol L⁻¹ for LS AdSV and 4.9 × 10⁻¹¹ and 1.6 × 10⁻¹⁰ mol L⁻¹ for SW AdSV, respectively. The method was applied for the determination of famotidine in urine.     

Determination of Ag(I) with chemically modified carbon paste electrode based on 2,3-dicyano 1,4-naphthoquinone

The utility of carbon paste modified with 2,3-dicyano 1,4-naphthoquinone (CYNQ) for the voltammetric determination of Ag(I) is demonstrated. The method is based on the formation of Ag(I) complex with CYNQ by accumulation from the aqueous solution to the electrode surface without an applied potential. Using the medium exchange technique, the electrode was transferred to another media followed by linear-scan voltammetric measurements. The reduction peak of the Ag(I)-CYNQ complex was observed at +0.22 V (vs. SCE). The silver response is studied with respect to paste composition, pH of the measurement solution, reproducibility, interference and other variables. A detection limit of 5 × 10⁻⁸M was obtained and the calibration curve was linear over the range 1 × 10⁻⁶−8 × 10⁻⁵M.     

The nano-Au self-assembled glassy carbon electrode for selective determination of epinephrine in the presence of ascorbic acid

Gold nanoparticles were self-assembled to the modified glassy carbon electrode (GC) with cysteamine (CA) to prepare the nano-Au/CA/GC modified electrode. The electrochemical behavior of epinephrine (EP) on the modified electrode was explored with cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Epinephrine gave a pair of redox peaks at E_pa = 0.190 mV and E_pc = −0.224 mV (versus SCE), respectively. The nano-Au/CA/GC modified electrode shows an excellent electrocatalytic activity for the oxidation of EP. The modified electrode could be used to determine EP in the presence of ascorbic acid (AA). The response of catalytic current with EP concentration shows a linear relation in the range of 1.0 × 10⁻⁷ to 5.0 × 10⁻⁴ mol L⁻¹ with the correlation coefficient of 0.998. The detection limit is 4.0 × 10⁻⁸ mol L⁻¹. The modified electrode exhibited a good reproducibility, sensitivity and stability for the determination of EP injection.     

Application of lead film electrode for simultaneous adsorptive stripping voltammetric determination of Ni(II) and Co(II) as their nioxime complexes

An adsorptive stripping voltammetric (AdSV) procedure for simultaneous determination of Ni(II) and Co(II) in the presence of nioxime as a complexing agent at an in situ plated lead film electrode was described. The Co(II) signal was enhanced by exploitation of the catalytic process in the presence of nitrite. Ni(II) and Co(II) signals are better separated than in the case of bismuth film electrodes. Calibration graphs for an accumulation time of 120 s are linear from 1 × 10⁻⁹ to 1 × 10⁻⁷ mol L⁻¹ and from 1 × 10⁻¹⁰ to 5 × 10⁻⁹ mol L⁻¹ for Ni(II) and Co(II), respectively. The proposed procedure was applied for Ni(II) and Co(II) determination in water certified reference materials.     

Development of an anodic stripping voltammetric assay, using a disposable mercury-free screen-printed carbon electrode, for the determination of zinc in human sweat

This paper reports on the development of a novel electrochemical assay for Zn²⁺ in human sweat, which involves the use of disposable screen-printed carbon electrodes (SPCEs). Initially, SPCEs were used in conjunction with cyclic voltammetry to study the redox characteristics of Zn²⁺ in a selection of supporting electrolytes. The best defined cathodic and anodic peaks were obtained with 0.1 M NaCl/0.1 M acetate buffer pH 6.0. The anodic peak was sharp and symmetrical which is typical for the oxidation of a thin metal film on the electrode surface. This behaviour was exploited in the development of a differential pulse anodic stripping voltammetric (DPASV) assay for zinc. It was shown that a deposition potential of −1.6 V versus Ag/AgCl and deposition time of 60 s with stirring (10 s equilibration) produced a well-defined stripping peak with E_pa = −1.2 V versus Ag/AgCl. Using these conditions, the calibration plot was linear over the range 1 × 10⁻⁸ to 5 × 10⁻⁶ M Zn²⁺. The precision was examined by carrying out six replicate measurements at a concentration of 2 × 10⁻⁶ M; the coefficient of variation was calculated to be 5.6%. The method was applied to the determination of the analyte in sweat from 10 human volunteers. The concentrations were between 0.39 and 1.56 μg/mL, which agrees well with previously reported values. This simple, low-cost sensitive assay should have application in biomedical studies and for stress and fatigue in sports studies.     

Electroanalytical investigation and determination of pefloxacin in pharmaceuticals and serum at boron-doped diamond and glassy carbon electrodes

The anodic behavior and determination of pefloxacin on boron-doped diamond and glassy carbon electrodes were investigated using cyclic, linear sweep, differential pulse and square wave voltammetric techniques. In cyclic voltammetry, pefloxacin shows one main irreversible oxidation peak and additional one irreversible ill-defined wave depending on pH values for both electrodes. The results indicate that the process of pefloxacin is irreversible and diffusion controlled on boron-doped diamond electrode and irreversible but adsorption controlled on glassy carbon electrode. The peak current is found to be linear over the range of concentration 2 × 10⁻⁶ to 2 × 10⁻⁴ M in 0.5 M H₂SO₄ at about +1.20 V (versus Ag/AgCl) for differential pulse and square wave voltammetric technique using boron-doped diamond electrode. The repeatability, reproducibility, precision and accuracy of the methods in all media were investigated. Selectivity, precision and accuracy of the developed methods were also checked by recovery studies. The procedures were successfully applied to the determination of the drug in pharmaceutical dosage forms and humans serum samples with good recovery results. No electroactive interferences from the excipients and endogenous substances were found in the pharmaceutical dosage forms and biological samples, respectively.     

A peroxidase-tetrathiafulvalene biosensor based on self-assembled monolayer modified Au electrodes for the flow-injection determination of hydrogen peroxide

The construction and performance under flow-injection conditions of an integrated amperometric biosensor for hydrogen peroxide is reported. The design of the bioelectrode is based on a mercaptopropionic acid (MPA) self-assembled monolayer (SAM) modified gold disk electrode on which horseradish peroxidase (HRP, 24.3 U) was immobilized by cross-linking with glutaraldehyde together with the mediator tetrathiafulvalene (TTF, 1 μmol), which was entrapped in the three-dimensional aggregate formed.

The amperometric biosensor allows the obtention of reproducible flow injection amperometric responses at an applied potential of 0.00 V in 0.05 mol L⁻¹ phosphate buffer, pH 7.0 (flow rate: 1.40 mL min⁻¹, injection volume: 150 μL), with a range of linearity for hydrogen peroxide within the 2.0 × 10⁻⁷–1.0 × 10⁻⁴ mol L⁻¹ concentration range (slope: (2.33 ± 0.02) × 10⁻² A mol⁻¹ L, r = 0.999). A detection limit of 6.9 × 10⁻⁸ mol L⁻¹ was obtained together with a R.S.D. (n = 50) of 2.7% for a hydrogen peroxide concentration level of 5.0 × 10⁻⁵ mol L⁻¹. The immobilization method showed a good reproducibility with a R.S.D. of 5.3% for five different electrodes. Moreover, the useful lifetime of one single biosensor was estimated in 13 days.

The SAM-based biosensor was applied for the determination of hydrogen peroxide in rainwater and in a hair dye. The results obtained were validated by comparison with those obtained with a spectrophotometric reference method. In addition, the recovery of hydrogen peroxide in sterilised milk was tested.     

Voltammetric study of the interaction of ciprofloxacin-copper with nucleic acids and the determination of nucleic acids

The behavior of the ciprofloxacin (CPFX) complex with copper, Cu(II)L₂, at a mercury electrode has been investigated in borax–boric acid buffer. The adsorption phenomena were observed by linear sweep voltammetry. The mechanism of the electrode reaction was found to be reduction of Cu(II)L₂ adsorbed on the surface of the electrode by an irreversible charge transfer to metal amalgam, Cu(0)(Hg). In the presence of DNA, the formation of the electrochemically non-active complexes Cu(II)L₂–DNA results in the decrease of the equilibrium concentration of Cu(II)L₂ and its peak current. Under the optimum conditions, the decrease of the peak current is proportional to DNA concentration. The linear ranges are 6.67×10⁻⁸ to 1.20×10⁻⁵ g ml⁻¹ for calf thymus DNA (ctDNA), 3.30×10⁻⁸ to 2.33×10⁻⁶ g ml⁻¹ for fish sperm DNA (fsDNA) and 1.0×10⁻⁸ to 1.2×10⁻⁶ g ml⁻¹ for yeast RNA. The detection limits are 5.00×10⁻⁹, 3.00×10⁻⁹ and 2.50×10⁻⁹ g ml⁻¹, respectively. This method exhibits good recovery and high sensitivity.     

Cathodic adsorptive stripping voltammetric behaviour of guanine in the presence of copper at the static mercury drop electrode

The cathodic adsorptive electrochemical behavior of guanine in the presence of some metal ions at the static mercury drop electrode was investigated. A 1.0×10⁻³ mol l⁻¹ NaOH or a 2.0×10⁻² mol l⁻¹ Hepes buffer at pH 8.0 solutions were used as supporting electrolytes. The reduction peak potential for guanine was found to be around −0.15 V, which is very close to the mercury reduction wave. A new peak appears at −0.60 V in the presence of copper or at −1.05 V in the presence of zinc. A square wave voltammetric procedure for electroanalytical determination of guanine in 2.0×10⁻² mol l⁻¹ Hepes buffer at pH 8.0 containing 1.6×10⁻⁵ mol l⁻¹of copper ions, was developed. An accumulation potential of −0.15 V during 270 s for the prior adsorption of guanine at the electrode surface was used. The response of the system was found to be linear in the range of guanine concentration from 6.62×10⁻⁸ to 1.32×10⁻⁷ mol l⁻¹ and the detection limit was 7.0×10⁻⁹ mol l⁻¹. The influence of DNA bases such as adenine, cytosine and thymine was also examined. Cyclic voltammetry was used to characterize the interfacial and redox mechanism.     

A novel electrogenerated chemiluminescence sensor for pyrogallol with core-shell luminol-doped silica nanoparticles modified electrode by the self-assembled technique

The core-shell luminol-doped SiO₂ nanoparticles were synthesized and immobilized on the surface of chitosan film coating graphite electrode by the self-assembled technique. Then, a novel electrogenerated chemiluminescence (ECL) sensor for pyrogallol was developed based on its ECL enhancing effect for the core-shell luminol-doped silica nanoparticles. The ECL analytical performances and the sensing mechanism of this ECL sensor for pyrogallol were investigated in detail. The corresponding results showed that: compared with the conventional ECL reaction procedures by luminol ECL reaction system, the electrochemical (EC) reaction of pyrogallol and its subsequent chemiluminescence (CL) reaction occurred in the different spatial region whilst offering a high efficiency to couple the EC with the CL reaction to form the ECL procedures. In this case, this new sensing scheme offered more potential to improve the analytical performances of the ECL reaction. Under the optimum experimental conditions, this ECL sensor showed less than 5% decrease in continuums over 100 times ECL measurements, the detection limit was 1.0 × 1.0⁻⁹ mol/L for pyrogallol. The linear range extended from 3.0 × 10⁻⁹ mol/L to 2.0 × 10⁻⁵ mol/L for pyrogallol.     

Flow-injection chemiluminescence determination of tetracyclines with in situ electrogenerated bromine as the oxidant

By designing a novel flow-through electrolytic cell (FEC), bromine was produced near to the surface of the platinum electrode by electrochemical oxidation of acidic KBr. The fast and weak chemiluminescence signal produced by the chemical reaction of the electrogenerated bromine with H₂O₂ was greatly enhanced by tetracyclines Based on these observations, a new, sensitive and simple electrogenerated chemiluminescence (ECL) method for the determination of tetracyclines was developed. Under the optimum experimental conditions, the calibration graphs are linear over the range 3.0×10⁻⁸ to 5.0×10⁻⁵ g ml⁻¹ for tetracycline, 2.0×10⁻⁷ to 2.4×10⁻⁵ g ml⁻¹ for oxytetracycline and 1.0×10⁻⁷ to 5.0×10⁻⁵ g ml⁻¹ for chlortetracycline. The limits of detection (S/N=3) are 1.0×10⁻⁸ g ml⁻¹ for tetracycline, 7.0×10⁻⁸ g ml⁻¹ for oxytetracycline and 1.5×10⁻⁷ g ml⁻¹ for chlortetracycline. For the determination 5.0×10⁻⁷ g ml⁻¹ tetracycline, the relative standard deviation was <5%. The proposed method was used to determine tetracyclines in pharmaceutical formulations.