Sensitive voltammetric determination of baicalein at DNA Langmuir-Blodgett film modified glassy carbon electrode

The present paper describes to modify a double stranded DNA-octadecylamine (ODA) Langmuir-Blodgett film on a glassy carbon electrode (GCE) surface to develop a voltammetric sensor for the detection of trace amounts of baicalein. The electrode was characterized by atomic force microscopy (AFM) and cyclic voltammetry (CV). Electrochemical behaviour of baicalein at the modified electrode had been investigated in pH 2.87 Britton-Robinson buffer solutions by CV and square wave voltammetry (SWV). Compared with bare GCE, the electrode presented an electrocatalytic redox for baicalein. Under the optimum conditions, the modified electrode showed a linear voltammetric response for the baicalein within a concentration range of 1.0 × 10⁻⁸-2.0 × 10⁻⁶ mol L⁻¹, and a value of 6.0 × 10⁻⁹ mol L⁻¹ was calculated for the detection limit. And the modified electrode exhibited an excellent immunity from epinephrine, dopamine, glucose and ascorbic acid interference. The method was also applied successfully to detect baicalein in the medicinal tablets and spiked human blood serum samples with satisfactory results.     

Electrocatalytic reduction of nitrite at polypyrrole nanowire-platinum nanocluster modified glassy carbon electrode

Pt nanoclusters were deposited in polypyrrole (PPy) nanowires by cyclic voltammetry method, fabricating a PPy-Pt nanocomposite on glassy carbon electrode (PPy-Pt/GCE). The electrocatalytic reduction of nitrite at PPy-Pt/GCE has been investigated using 0.5 M H₂SO₄ solution. The sensor exhibited excellent electrocatalytic activity toward nitrite reduction. In acidic medium, the cyclic voltammetry at 20 mV s^− 1 gave a nitrite reduction peak at − 0.124 V with 0.566 μA μM^− 1 current sensitivity in the range of 5.0 × 10^− 7-1.0 × 10^− 3 M. The detection limit was 1.5 × 10^− 7 M (s/n = 3). The proposed method was successfully applied in the detection of nitrite in real water samples and obtained satisfactory results. The PPy-Pt composite modified electrode had good storage stability, reproducibility and anti-interference ability.     

Electrodeposition of gold nanoclusters on overoxidized polypyrrole film modified glassy carbon electrode and its application for the simultaneous determination of epinephrine and uric acid under coexistence of ascorbic acid

A novel biosensor was fabricated by electrochemical deposition of gold nanoclusters on ultrathin overoxidized polypyrrole (PPyox) film, formed a nano-Au/PPyox composite on glassy carbon electrode (nano-Au/PPyox/GCE). The properties of the nanocomposite have been characterized by field emission scanning electron microscope (FE-SEM), X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD) and electrochemical investigations. The nano-Au/PPyox/GCE had strongly catalytic activity toward the oxidation of epinephrine (EP), uric acid (UA) and ascorbic acid (AA), and resolved the overlapping voltammetric response of EP, UA and AA into three well-defined peaks with a large anodic peak difference. The catalytic peak currents obtained from differential pulse voltammetry increased linearly with increasing EP and UA concentrations in the range of 3.0 × 10⁻⁷ to 2.1 × 10⁻⁵ M and 5.0 × 10⁻⁸ to 2.8 × 10⁻⁵ M with a detection limit of 3.0 × 10⁻⁸ and 1.2 × 10⁻⁸ M (s/n = 3), respectively. The results showed that the modified electrode can selectively determine EP and UA in the coexistence of a large amount of AA. In addition, the sensor exhibited excellent sensitivity, selectivity and stability. The nano-Au/PPyox/GCE has been applied to determination of EP in epinephrine hydrochloride injection and UA in urine samples with satisfactory results.     

Simultaneous determination of uric acid,xanthine, hypoxanthine and caffeine in human blood serum and urine samples using electrochemically reduced graphene oxide modified electrode

This paper describes the fabrication of graphene on glassy carbon electrode (GCE) by electrochemical reduction of graphene oxide (GO) attached through 1,6-hexadiamine on GCE and the simultaneous determination of structurally similar four purine derivatives using the resultant electrochemically reduced GO (ERGO) modified electrode. The electrocatalytic activity of ERGO was investigated toward the oxidation of four important purine derivatives, uric acid (UA), xanthine (XN), hypoxanthine (HXN) and caffeine (CAF) at physiological pH. The modified electrode not only enhanced the oxidation currents of the four purine derivatives but also shifted their oxidation potentials toward less positive potentials in contrast to bare GCE. Further, it successfully separates the voltammetric signals of the four purine derivatives in a mixture and hence used for the simultaneous determination of them. Selective determination of one purine derivative in the presence of low concentrations other three purine derivatives was also realized at the present modified electrode. Using differential pulse voltammetry, detection limits of 8.8 × 10⁻⁸ M, 1.1 × 10⁻⁷ M, 3.2 × 10⁻⁷ M and 4.3 × 10⁻⁷ M were obtained for UA, XN, HXN and CAF, respectively. The practical application of the modified electrode was demonstrated by simultaneously determining the concentrations of UA, XN, HXN and CAF in human blood plasma and urine samples.     

Mercury-free simultaneous determination of cadmium and lead at a glassy carbon electrode modified with multi-wall carbon nanotubes

A multi-wall carbon nanotube (MWNT) modified glassy carbon electrode (GCE) was described for the simultaneous determination of trace levels of cadmium and lead by anodic stripping voltammetry (ASV). In pH 4.5 NaAc-HAc buffer containing 0.02 mol/l KI, Cd²⁺ and Pb²⁺ first adsorb onto the surface of a MWNT film coated GCE and then reduce at −1.20 V. During the positive potential sweep, reduced cadmium and lead were oxidized, and two well-defined stripping peaks appeared at −0.88 and −0.62 V. Compared with a bare GCE, a MWNT film coated GCE greatly improves the sensitivity of determining cadmium and lead. Low concentration of I⁻ significantly enhances the stripping peak currents since it induces Cd²⁺ and Pb²⁺ to adsorb at the electrode surface. The striping peak currents change linearly with the concentration of Cd²⁺ from 2.5×10⁻⁸ to 1×10⁻⁵ mol/l and with that of Pb²⁺ from 2×10⁻⁸ to 1×10⁻⁵ mol/l. The lowest detectable concentrations of Cd²⁺ and Pb²⁺ are estimated to be 6×10⁻⁹ and 4×10⁻⁹ mol/l, respectively. The high sensitivity, selectivity, and stability of this MWNT film coated electrode demonstrated its practical application for a simple, rapid and economical determination of trace levels of Cd²⁺ and Pb²⁺ in water samples.     

Electrochemical deoxyribonucleic acid biosensor based on carboxyl functionalized graphene oxide and poly-l-lysine modified electrode for the detection of tlh gene sequence related to vibrio parahaemolyticus

A carboxyl functionalized graphene oxide (GO-COOH) and electropolymerized ploy-l-lysine (PLLy) modified glassy carbon electrode (GCE) was fabricated and used for the construction of an electrochemical deoxyribonucleic acid (DNA) biosensor. The NH₂ modified probe ssDNA sequences were immobilized on the surface of GO-COOH/PLLy/GCE by covalent linking with the formation of amide bonds, which was stable and furthur hybridized with the target ssDNA sequence. Differential pulse voltammetry (DPV) was used to monitor the hybridization events with methylene blue as electrochemical indicator, which gave a sensitive reduction peak at −0.287 V (vs. SCE). Under the optimal conditions the reduction peak current was proportional to the concentration of tlh gene sequence in the range from 1.0 × 10⁻¹² to 1.0 × 10⁻⁶ mol L⁻¹ with a detection limit as 1.69 × 10⁻¹³ mol L⁻¹ (3σ). The polymerase chain reaction products of tlh gene from oyster samples were detected with satisfactory results, indicating the potential application of this electrochemical DNA sensor.     

Amperometric detection of dopamine based on tyrosinase-SWNTs-Ppy composite electrode

A novel 3-dimensional single wall carbon nanotubes (SWNTs)-polypyrrole (Ppy) composite was prepared as an electrode by chemically polymerizing polypyrrole onto SWNTs using a LiClO₄ oxidant. This composite electrode was characterized by scanning electron microscopy (SEM) and cyclic voltammetry with 1 mM [Fe(CN)₆]⁻³/[Fe(CN)₆]⁻⁴. The SWNTs were thickly coated with chemically polymerized polypyrrole and the composite had many surface pores and crevices which could enhance mass transfer. The SWNTs-Ppy composite electrode showed a large specific surface area (30 m²/g) and a good reproducible current response, at about 100 times the peak current of a glassy carbon electrode (GCE). The diffusion coefficient was calculated to be 4.81 × 10⁻⁶ cm²/s. As a biosensor application, tyrosinase was immobilized on the functionalized SWNTs and tyrosinase-SWNTs-Ppy composite was prepared in the same manner. This tyrosinase-SWNT-Ppy composite electrode was used for amperometric detection of dopamine in the presence of ascorbic acid and showed high sensitivity (467 mA/M cm²) and lower detection limit (5 μM) compared to previous reports.     

Simultaneous determination of N-acetyl-p-aminophenol and p-aminophenol with poly(3,4-ethylenedioxythiophene) modified glassy carbon electrode

A sensitive and selective method was developed for the determination of N-acetyl-p-aminophenol (APAP) and p-aminophenol (PAP) using poly(3,4-ethylenedioxythiophene) (PEDOT)-modified glassy carbon electrode (GCE). Cyclic voltammetry and differential pulse voltammetry were used to investigate the electrochemical reaction of APAP and PAP at the modified electrode. Both APAP and PAP showed quasireversible redox reactions with formal potentials of 367 mV and 101 mV (vs. Ag/AgCl), respectively, in phosphate buffer solution of pH 7.0. The significant peak potential difference (266 mV) between APAP and PAP enabled the simultaneous determination both species based on differential pulse voltammetry. The voltammetric responses gave linear ranges of 1.0 × 10⁻⁶-1.0 × 10⁻⁴ mol L⁻¹ and 4.0 × 10⁻⁶-3.2 × 10⁻⁴ mol L⁻¹, with detection limits of 4.0 × 10⁻⁷ mol L⁻¹ and 1.2 × 10⁻⁶ mol L⁻¹ for APAP and PAP, respectively. The method was successfully applied for the determination of APAP and PAP in pharmaceutical formulations and biological samples.     

Electrochemical reduction and voltammetric determination of metronidazole at a nanomaterial thin film coated glassy carbon electrode

Simple and sensitive electrochemical method for the determination of metronidazole, based on a nanostructured film coated glassy carbon electrode (GCE), is described. Multi-walled carbon nanotubes (MWNT) was dispersed into water in the presence of a hydrophobic surfactant to give very stable and homogeneous MWNT suspension, and a MWNT-film coated GCE was achieved via evaporating solvent. Metronidazole yields a well-defined reduction peak whose potential is −0.71 V at the MWNT-film coated GCE in pH 9.0 Britton-Robinson buffer. Compared with bare GCE, the MWNT-film modified GCE significantly enhances the reduction peak current of metronidazole. All the experimental parameters were optimized for the determination of metronidazole. The detection limit is 6×10⁻⁹ mol/l at 2 min accumulation. This method has been successfully used to determine metronidazole in the drugs. Furthermore, results obtained by the proposed method have been compared with spectrophotometric method.     

Voltammetric performance and application of a sensor for sodium ions constructed with layered birnessite-type manganese oxide

The preparation and electrochemical characterization of a carbon paste electrode modified with layered birnessite-type manganese oxide for use as a sodium sensor is described. The effects of powder synthesis process (sol-gel and redox precipitation) for birnessite on the electrochemical activity of the sensor was investigated by cyclic voltammetry. The carbon paste electrode modified with birnessite-type manganese oxide that was synthesized by the sol-gel method showed a best electrochemical for sodium ions. The detection is based on the measurement of anodic current generated by oxidation of Mn(III) to Mn(IV) at the surface of the electrode and consequently the sodium ions extraction into the birnessite structure. The best voltammetric response was obtained for an electrode composition of 15% (w/w) birnessite oxide in the paste, a TRIS buffer solution of pH 8.0 and a scan rate of 50 mV s⁻¹. A sensitive linear voltammetric response for sodium ions was obtained in the concentration range of 7.89 × 10⁻⁵ to 3.49 × 10⁻⁴ mol L⁻¹ with a slope of 37.5 μA L mmol⁻¹ and a detection limit (3σ/slope) of 3.43 × 10⁻⁵ mol L⁻¹ using cyclic voltammetry. Under the working conditions, the proposed method was successfully applied to determination of sodium ions in urine samples.     

Adsorptive stripping voltammetric determination of trace concentrations of molybdenum at an in situ plated lead film electrode

An in situ plated lead film electrode has been applied for adsorptive stripping voltammetric determination of trace concentrations of molybdenum in the presence of Alizarin S. The procedure is based on the preconcentration of the molybdenum-Alizarin S complex at an in situ plated lead film electrode held at −0.6 V (versus Ag/AgCl), followed by a negatively sweeping square wave voltammetric scan. The peak current is proportional to the concentration of molybdenum over the range 2 × 10⁻⁹ to 5 × 10⁻⁸ mol L⁻¹, with a 3σ detection limit of 9 × 10⁻¹⁰ mol L⁻¹ with an accumulation time of 60 s. The measurements were carried out from underaerated solutions. The proposed procedure was validated in the course of Mo(VI) determination in water certified reference materials.     

Determination of trace thiocyanate with nano-silver coated multi-walled carbon nanotubes modified glassy carbon electrode

Novel nano-silver coated multi-walled carbon nanotube composites were prepared and used to fabricate a modified electrode. The application of the nano-silver coated multi-walled carbon nanotube composites modified electrode for determination of trace thiocyanate is demonstrated for the first time. The influence of substrate, pH and interference of coexisting substances was investigated for response properties of the electrode. There was a linear relationship at the range 2.5 × 10⁻⁹ to 5 × 10⁻⁸ mol L⁻¹ and 5 × 10⁻⁸ to 1 × 10⁻⁶ mol L⁻¹ of thiocyanate with the decrement of anodic DPV peak currents. The limit of detection was 1 × 10⁻⁹ mol L⁻¹(S/N = 3). The constructed electrode showed excellent reproducibility and stability. Actual urine and saliva samples of smoker and non-smoker were analyzed and satisfactory results were obtained. This method provides a new way to construct any electrode for biological and environmental analysis.     

Direct electrocatalytic oxidation of nitric oxide and reduction of hydrogen peroxide based on α-Fe2O3 nanoparticles-chitosan composite

α-Fe₂O₃ nanoparticles prepared using a simple solution-combusting method have been dispersed in chitosan (CH) solution to fabricate nanocomposite film on glass carbon electrode (GCE). The as-prepared α-Fe₂O₃ nanoparticles were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM). The nanocomposite film exhibits high electrocatalytic oxidation for nitric oxide (NO) and reduction for hydrogen peroxide (H₂O₂). The electrocatalytic oxidation peak is observed at +0.82 V (vs. Ag/AgCl) and controlled by diffusion process. The electrocatalytic reduction peak is observed at −0.45 V (vs. Ag/AgCl) and controlled by diffusion process. This α-Fe₂O₃-CH/GCE nanocomposite bioelectrode has response time of 5 s, linearity as 5.0 × 10⁻⁷ to 15.0 × 10⁻⁶ M of NO with a detection limit of 8.0 × 10⁻⁸ M and a sensitivity of −283.6 μA/mM. This α-Fe₂O₃-CH/GCE nanocomposite bioelectrode was further utilized in detection of H₂O₂ with a detection limit of 4.0 × 10⁻⁷ M, linearity as 1.0 × 10⁻⁶ to 44.0 × 10⁻⁶ M and with a sensitivity of 21.62 μA/mM. The shelf life of this bioelectrode is about 6 weeks under room temperature conditions.     

Electrochemiluminescent behaviors of alkaloids and tris(2,2'-bipyridine) ruthenium in organically modified silicate film

Electrogenerated chemiluminescences (ECLs) of alkaloids, such as berberine, trigonelline, allantoin and betaine, were studied in an aqueous alkaline buffer solution (pH 9.5), based on tris(2,2′-bipyridine)ruthenium(II) [Ru(bpy)₃²⁺] immobilized in organically modified silicates (ORMOSILs) film on a glassy carbon electrode (GCE). The immobilized Ru(bpy)₃²⁺ showed good electrochemical and photochemical activities. In a flow system, the eluted alkaloids were oxidized on the modified GCE, and reacted with immobilized Ru(bpy)₃²⁺ at the potential of +1.50 V (versus Ag/AgCl). The luminescence with λ_max 610 nm was caused by a reaction of electrolytically formed Ru(bpy)₃³⁺ with an oxidized amine group to generate Ru(bpy)₃^2+*. The determination limit was 5 × 10⁻⁶ mol L⁻¹, 8 × 10⁻⁶ mol L⁻¹, 2.0 × 10⁻⁵ mol L⁻¹ and 5.0 × 10⁻⁵ mol L⁻¹ for berberine, trigonelline, allantoin and betaine at S/N 3, respectively. In addition, the factors affecting the determination of the four alkaloids were also studied.     

An electrochemiluminescent biosensor for glucose based on the electrochemiluminescence of luminol on the nafion/glucose oxidase/poly(nickel(II)tetrasulfophthalocyanine)/multi-walled carbon nanotubes modified electrode

A poly(nickel(II) tetrasulfophthalocyanine)/multi-walled carbon nanotubes composite modified electrode (polyNiTSPc/MWNTs) was fabricated by electropolymerization of NiTSPc on MWNTs-modified glassy carbon electrode (GCE). The modified electrode was found to be able to greatly improve the emission of luminol electrochemiluminescence (ECL) in a solution containing hydrogen peroxide. Glucose oxidase (GOD) was immobilized on the surface of polyNiTSPc/MWNTs modified GC electrode by Nafion to establish an ECL glucose sensor. Under the optimum conditions, the linear response range of glucose was 1.0 × 10⁻⁶ to 1.0 × 10⁻⁴ mol L⁻¹ with a detection limit of 8.0 × 10⁻⁸ mol L⁻¹ (defined as the concentration that could be detected at the signal-to-noise ratio of 3). The ECL sensor showed an outstanding well reproducibility and long-term stability. The established method has been applied to determine the glucose concentrations in real serum samples with satisfactory results.     

Quantitative determination of zinc in milkvetch by anodic stripping voltammetry with bismuth film electrodes

Bismuth film electrode (BiFE) was shown to be an attractive alternative to common mercury film electrode (MFE) for anodic stripping voltammetric measurements. In this study, bismuth film, that was in situ deposited onto glassy carbon electrode, was used to detect zinc content of milkvetch, used in traditional Chinese medicine. Variables affecting the response have been evaluated and optimized. Experimental results showed a high response, with a good linearity (between 0.5 × 10⁻⁶ mol L⁻¹ and 3 × 10⁻⁶ mol L⁻¹) a good precision (R.S.D. = 3.58%) and a low detection limit (9.6 × 10⁻⁹ mol L⁻¹ with a 120 s anodic). The anodic stripping performance makes the bismuth film electrode very desirable for measurements of trace nutritive element zinc in milkvetch and should impart possible restrictions on the use of mercury electrode.     

Langmuir-Blodgett film of p-tert-butylthiacalix[4]arene modified glassy carbon electrode as voltammetric sensor for the determination of Hg(II)

The π-A isotherms and UV-vis spectra of the transferred films suggested that the monolayer of p-tert-butylthiacalix[4]arene can coordinate with Hg²⁺ at the air-water surface. From these observations, a glassy carbon electrode coated with Langmuir-Blodgett film of p-tert-butylthiacalix[4] arene as a new voltammetric sensor is designed for the determination of trace amounts of Hg²⁺. Compared with bare glassy carbon electrode and modified glassy carbon electrode using direct coating method, the Langmuir-Blodgett film-modified electrode can greatly improve the measuring sensitivity of Hg²⁺. Under the selected conditions, the Langmuir-Blodgett film-modified electrode in 0.1 mol L⁻¹ H₂SO₄ + 0.01 mol L⁻¹ KCl solution shows a linear voltammetric response for Hg²⁺ in the range of 5.0 × 10⁻¹⁰ to 1.5 × 10⁻⁷ mol L⁻¹, with a detection limit of 2.0 × 10⁻¹⁰ mol L⁻¹. The proposed method was also applied to determine Hg²⁺ in water samples (tap, lake and river water). In addition, the fabricated electrode exhibited a distinct advantage of simple preparation, non-toxicity, good reproducibility and good stability.     

Anodic voltammetric behavior and determination of cefixime in pharmaceutical dosage forms and biological fluids

The voltammetric behavior of cefixime was studied using cyclic, linear sweep, differential pulse and square wave voltammetric techniques. The oxidation of cefixime was irreversible and exhibited diffusion controlled process depending on pH. The oxidation mechanism was proposed and discussed. Different parameters were tested to optimize the conditions for the determination of cefixime. The dependence of current intensities and potentials on pH, concentration, scan rate, nature of the buffer was investigated. According to the linear relationship between the peak current and the concentration, differential pulse (DPV) and square wave (SWV) voltammetric methods for cefixime assay in pharmaceutical dosage forms and biological fluids were developed. For the determination of cefixime were proposed in acetate buffer at pH 4.5, which allows quantitation over the 6 × 10⁻⁶-2 × 10⁻⁴ M range in supporting electrolyte and spiked serum sample; 8 × 10⁻⁶-2 × 10⁻⁴ M range in urine sample; 6 × 10⁻⁶-1 × 10⁻⁴ M range in breast milk samples for both techniques. The repeatability, reproducibility, precision and accuracy of the methods in all media were investigated. No electroactive interferences from the excipients and endogenous substances were found in the pharmaceutical dosage forms and in the biological samples, respectively.     

Glassy carbon electrodes sequentially modified by cysteamine-capped gold nanoparticles and poly(amidoamine) dendrimers generation 4.5 for detecting uric acid in human serum without ascorbic acid interference

Glassy carbon electrodes (GCE) were sequentially modified by cysteamine-capped gold nanoparticles (AuNp@cysteamine) and PAMAM dendrimers generation 4.5 bearing 128-COOH peripheral groups (GCE/AuNp@cysteamine/PAMAM), in order to explore their capabilities as electrochemical detectors of uric acid (UA) in human serum samples at pH 2. The results showed that concentrations of UA detected by cyclic voltammetry with GCE/AuNp@cysteamine/PAMAM were comparable (deviation <±10%; limits of detection (LOD) and quantification (LOQ) were 1.7 × 10⁻⁴ and 5.8 × 10⁻⁴ mg dL⁻¹, respectively) to those concentrations obtained using the uricase-based enzymatic-colorimetric method. It was also observed that the presence of dendrimers in the GCE/AuNp@cysteamine/PAMAM system minimizes ascorbic acid (AA) interference during UA oxidation, thus improving the electrocatalytic activity of the gold nanoparticles.     

Simultaneous determination of copper and lead in seawater using optimised thin-mercury film electrodes in situ plated in thiocyanate media

In the present work the anodic stripping voltammetric (ASV) methodology using a thin mercury film electrode in situ plated in thiocyanate media was re-assessed in order to allow the simultaneous determination of copper and lead in seawater. Under previously suggested conditions [6], i.e. using a concentration of thiocyanate of 5 mM, the ASV peaks of copper and lead overlapped due to the formation of a stable copper(I)-thiocyanate species, limiting the analytical determinations. Therefore, the best value for the thiocyanate concentration was re-evaluated: for 0.05 mM a trade-off between good resolution of the copper and lead peaks and high reproducibility of the mercury film formation/removing processes was achieved. In this media, the ASV peaks for Pb and Cu occurred, separated by 140 mV. Also, the in situ thin mercury film electrode was produced and removed with good repeatability, which was confirmed by the relative standard deviation values for the ASV determinations: 0.5% for Pb and 2.0% for Cu (10 replicate determinations in a solution with metal concentrations 1.5×10⁻⁸ M for lead and 2.2×10⁻⁸ M for copper). The optimised methodology was successfully applied to the determination of copper in the presence of lead, in certified seawater (NASS-5).