Simultaneous Determination of Dopamine and Uric Acid by Electrocatalytic Oxidation on a Carbon Paste Electrode Using Pyrogallol Red as a Mediator

A sensitive and selective electrochemical method for the simultaneous determination of dopamine (DA) and uric acid (UA) was developed using a pyrogallol red modified carbon paste electrode. Under the optimized conditions, the peak current was linearly dependent on 1.0–700.0 μmol L^?1 DA and 50.0–1000.0 μmol L^?1 UA. The detection limits for DA and UA were 0.78 μmol L^?1 and 35 μmol L^?1, respectively. Finally, this method was also examined for the determination of DA and uric acid in real samples such as drugs and urine.     

Sensitive detection of sulfanilamide by redox process electroanalysis of oxidation products formed in situ on glassy carbon electrode

This paper reported a simple method for sulfanilamide determination by redox process electroanalysis of oxidation products (SFDox) formed in situ on glassy carbon electrode. The CV experiments showed a reversible process after applied E _acc = + 1.06 V and t _acc = 1 s, in 0.1 mol L^?1 BRBS (pH = 2.0) at 50 mV s^?1. Different voltammetric scan rates (from 10 to 450 mV s^?1) suggested that the redox peaks of SFDox on the glassy carbon electrode (GCE) is an adsorption-controlled process. Square-wave voltammetry (SWV) method optimized conditions showed a linear response to SFD from 3.00 to 250.0 μmol L^?1 (R = 0.998) with a limit of detection of 0.638 μmol L^?1 and limit of quantification of 2.0 μmol L^?1. The developed the SWV method was successfully used in the determination of SFD pharmaceutical formulation and human serum. The SFD quantification results in pharmaceutical obtained by SWV-GCE were comparable to those found by official analytical protocols.     

Highly sensitive electrocatalytic determination of pyrazinamide using a modified poly(glycine) glassy carbon electrode by square-wave voltammetry

A new voltammetric sensor based on electropolymerization of glycine at glassy carbon electrode (GCE) was developed and applied to determine of pyrazinamide (PZA) by square-wave voltammetry (SWV). The initial cyclic voltammetric studies showed an electrocatalytic activity of poly(Gly)/GCE on redox system of pyrazinamide in 0.1 mol L^?1 phosphate buffer solution pH 7.5, with E _Pc and E _Pa in ?0.85 and ?0.8 V (versus E _Ag/AgCl), respectively. Studies at different scan rates suggest that the redox system of pyrazinamide at poly(Gly)/GCE is a process controlled by diffusion in the interval from 10 to 100 mV s^?1. Square-wave voltammetry-optimized conditions showed a linear response of PZA concentrations in the range from 0.47 to 6.15 μmol L^?1 (R?=?0.998) with a limit of detection (LOD) of 0.035 μmol L^?1 and a limit of quantification (LOQ) of 0.12 μmol L^?1. The developed SWV-poly(Gly)/GCE method provided a good intra-day (RSD?=?3.75 %) and inter-day repeatability (RSD?=?4.96 %) at 4.06 μmol L^?1 PZA (n?=?10). No interference of matrix of real samples was observed in the voltammetric response of PZA, and the method was considered to be highly selective for the compound. In the accuracy test, the recovery was found in the range of 98.2 and 104.0 % for human urine samples and pharmaceutical formulation (tablets). The PZA quantification results in pharmaceutical tablets obtained by the proposed SWV-poly(Gly)/GCE method were comparable to those found by official analytical protocols.     

Flow injection amperometric determination of hydrogen peroxide in household commercial products with a ruthenium oxide hexacyanoferrate modified electrode

Hydrogen peroxide was determined in oral antiseptic and bleach samples using a flow-injection system with amperometric detection. A glassy carbon electrode modified by electrochemical deposition of ruthenium oxide hexacyanoferrate was used as working electrode and a homemade Ag/AgCl (saturated KCl) electrode and a platinum wire were used as reference and counter electrodes, respectively. The electrocatalytic reduction process allowed the determination of hydrogen peroxide at 0.0 V. A linear relationship between the cathodic peak current and concentration of hydrogen peroxide was obtained in the range 10–5000 μmol L^?1 with detection and quantification limits of 1.7 (S/N?=?3) and 5.9 (S/N?=?10) μmol L^?1, respectively. The repeatability of the method was evaluated using a 500 μmol L^?1 hydrogen peroxide solution, the value obtained being 1.6% (n?=?14). A sampling rate of 112 samples h^?1 was achieved at optimised conditions. The method was employed for the quantification of hydrogen peroxide in two commercial samples and the results were in agreement with those obtained by using a recommended procedure.     

On-line Micro Solid-Phase Extraction of Clodinafop Propargyl from Water,Soil and Wheat Samples Using Electrospun Polyamide Nanofibers

An on-line extraction/determination set up was designed for micro solid-phase extraction of clodinafop propargyl from water, soil and wheat samples using electrospun polyamide nanofiber mats. The prepared mats were packed in a stainless steel tube which conveniently acted as a high-performance liquid chromatography injection loop. Influential parameters affecting the extraction efficiency were optimized using a distilled water sample fortified with 25 μg L^?1 of clodinafop propargyl. An enrichment factor of 440 was achieved for clodinafop propargyl indicating the ability of the whole procedure. Under the optimum conditions, the linearity for the analyte was in the range of 6–700 μg L^?1, while a limit of detection and limit of quantification of 2 and 6 μg L^?1 were achieved, respectively. The intra-day and inter-day RSD% at the concentration level of 25 μg L^?1 were 4.6 and 9.3 %, respectively. To investigate the matrix effect, the developed method was applied to the analysis of real water samples including paddy and river waters as well as the wheat and soil samples. The relative recovery percentages for the spiked samples were in the range of 63–95 %.     

Trace determination of manganese(II) by temperature-controlled/assisted ionic liquid-based dispersive liquid-phase microextraction and electrothermal atomic absorption spectrometry

A microextraction method, namely temperature-controlled/assisted ionic liquid-based dispersive liquid-phase microextraction (DLPME) for manganese(II) determination in environmental water samples is presented. Manganese(II) was extracted from aqueous solution into an ionic liquid (IL) after complexation with 1-(2-thiazolylazo)-2-naphthol (TAN) and directly introduced for electrothermal atomic absorption spectrometry (ETAAS) determination. Several factors that might affect ETAAS signal and extraction efficiency, such as pyrolysis and atomization temperature; and pH adjustment, concentration of TAN, extraction time, volume of IL and stirring rate were studied. Within optimal experimental conditions, the detection limit (3σ), the quantification limit (10σ), the enrichment factor and the relative standard deviation for five replicate determinations at 0.5 μg L^?1 of manganese(II) were calculated as 0.023 μg L^?1, 0.076 μg L^?1, 58.7 and 6.3 %, respectively. The presented method was also successfully applied to the determination of manganese(II) in real samples. The main benefits of the method are simplicity, low cost, rapidity, high recovery, powerful extraction efficiency and the proposed approach is free of volatile organic solvents.     

An immediate luminescence enhancement method for determination of vitamin B1 using long-wavelength emitting water-soluble CdTe nanorods

A method for determination of vitamin B₁ has been developed that is based on the enhancement effect of vitamin B₁ on the luminescence of water-soluble CdTe nanorods modified with thioglycolic acid and cysteine. The effect of variables including the size of the nanorods on the enhancement of luminescence have been investigated. A preliminary mechanistic study showed that the passivating action of vitamin B₁ on the surface of the CdTe nanorods is likely to be responsible for the enhancement. Interferences by shortwave fluorescence are effectively eliminated because measurements are performed in the near-infrared. Due to the near-infrared measurement character, the fluorescence interference of vitamin B₂ can be effectively eliminated. Under the optimum conditions, the extent of luminescence enhancement is proportional to the concentration of vitamin B₁ in the range from 0.1 to 3.0 μmol L^?1 and the detection limit is 0.03 μmol L^?1. The relative standard deviation for 2.0 μmol L^?1 vitamin B₁ is 1.3% (n?=?6). The method is highly sensitive and selective, avoids the sample treatment needed in other procedures, and can be applied to the determination of vitamin B₁ in real samples with satisfactory results.     

Development of sequential injection spectrophotometric method for determination of mercury (II) using pyrogallol red

A sequential injection analysis (SIA) spectrophotometric method for the determination of trace amount of mercury (II) with pyrogallol red (PGR) was described. The method was based on the measurement of absorbance of the mercury (II)–PGR complex, yielding a light yellow-coloured product at pH 9.0 with absorption maximum at 370 nm. The SIA parameters affecting the signal response were optimised in order to obtain the better sensitivity and minimum reagent consumption. The linear range for determination of mercury (II) was over the range of 0.1–2.0 mg L^?1. The limit of detection and limit of quantification, calculated following IUPAC were 0.06 and 0.10 mg L^?1, respectively. The repeatability was 1.25% (n = 10) for 0.5 mg L^?1 of mercury (II). The proposed method was successfully applied to determine the mercury (II) in commercial cosmetics, local Thai traditional medicines and water samples with a sampling rate of 40 h^?1. Results obtained were in justifiable agreement with those obtained by the official ICP-MS method at the 95% confidence level.     

A novel biosensor based on ZnO nanoparticle/1,3-dipropylimidazolium bromide ionic liquid-modified carbon paste electrode for square-wave voltammetric determination of epinephrine

The direct electrochemistry of epinephrine (EP) on a modified carbon paste electrode (CPE) was described. The electrode was modified with Zinc oxide (ZnO) nanoparticles and 1,3-dipropylimidazolium bromide as a binder. The oxidation peak potential of EP at the surface of the ionic liquid ZnO nanoparticle CPE (IL/ZnO/NP/CPE) appeared at 350 mV, which was about 80 mV lower than the oxidation peak potential at the surface of the traditional carbon CPE under a similar condition. On other hand, the oxidation peak current was increased for about three times at the surface of IL/ZnO/NP/CPE compared to CPE. The linear response range and detection limit were found to be 0.09–800 μmol L^?1 and 0.06 μmol L^?1, respectively. Other physiological species did not interfere in the determination of EP at the surface of the proposed sensor in the optimum condition. The proposed sensor was successfully applied for the determination of EP in real samples.     

Determination of europium(III) in environmental samples using a flow injection analysis system with on-line preconcentration and spectrophotometric detection

A simple and accurate flow injection analysis system coupled with spectrophotometric detector was developed for preconcentration and determination of europium(III) in aqueous samples. The developed flow system includes a europium preconcentration step in a column packed with Amberlite XAD-4 resin impregnated with nalidixic acid at pH 7.0. The europium complex was desorbed from the resin by 0.1 mol L^?1 HCl and mixed with arsenazo-III solution (0.05 % solution in 0.1 mol L^?1 HCl) and taken to the flow through cell of spectrophotometer where its absorbance was measured at 661 nm. The optimum preconcentration system, chemical and FIA variables were investigated. The preconcentration factors obtained were 115 and 500, detection limits of 0.43 and 0.1 μg L^?1, sample throughputs of 40 and 10 were obtained for preconcentration time of 60 and 300 s respectively. The proposed system showed good precision and accuracy with relative standard deviation of 1.5 %. The method has been applied to the determination of europium(III) in real water samples and certified reference material IAEA-SL-1 (Lake sediment).     

Synthesis and characterisation of novel chelating resin for selective preconcentration and trace determination of Pb(II) ions in aqueous samples by innovative microsample injection system coupled flame atomic absorption spectrometry

Expanded polystyrene (EPS) foam waste (white pollutant) was utilised for the synthesis of novel chelating resin i.e. EPS-N = N-α-Benzoin oxime (EPS-N = N-Box). The synthesised resin was characterised by FT-IR spectroscopy, elemental analysis, and thermogravimetric analysis. A selective method for the preconcentration of Pb(II) ions on EPS-N = N-Box resin packed in mini-column was developed. The sorbed Pb(II) ions were eluted with 5.0 mL of 2.0 mol L^?1 HCl and determined by microsample injection system coupled flame atomic absorption spectrometry (MIS-FAAS). The average recovery of Pb(II) ions was achieved 95.5% at optimum parameters such as pH 7, resin amount 400 mg, flow rates 1.0 mL min^?1 (of eluent) and3.0 mL min^?1 (of sample solution). The total saturation capacity of the resin, limit of detection (LOD) and limit of quantification (LOQ) of Pb(II) ions were found to be 30 mg g^?1, 0.033 μg L^?1 and 0.107 μg L^?1, respectively with preconcentration factor of 300. The accuracy, selectivity and validation of the method was checked by analysis of sea water (BCR-403), wastewater (BCR-715) and Tibet soil (NCS DC-78302) as certified reference materials (CRMs). The proposed method was applied successfully for the trace determination of Pb(II) ions in aqueous samples.     

Fabrication of a nanostructured TiO2/carbon nanotube composite electrode for voltammetric and impedimetric determination of NTO explosive in the water and soil samples

An electrochemical oxidation route was developed for sensitive and selective assay of nitrotriazolone (NTO) explosive in some environmental samples on a multi-walled carbon nanotube (MWCNTs)/TiO₂ nanocomposite paste electrode, for prevention of the analytical interference of conventional reducible energetic compounds. Detailed evaluations were made for the electrochemical behaviour of NTO on the modified electrode by adsorptive stripping voltammetry, electrochemical impedance spectroscopy (EIS) and chronoamperometry techniques in the pH range of 2.0–10.0. Parameters such as diffusion coefficient constant of NTO were calculated, and various experimental conditions were also optimised. Under optimal conditions the calibration curve had two linear dynamic ranges of 130.0–3251.5 μg L^?1 and 6.5–26.0 mg L^?1 with a detection limit of 26.0 μg L^?1 (0.2 μmol L^?1) and precision of <3%. This electrochemical sensor was further applied to determine NTO in real soil and water samples with satisfactory results.     

A novel method for D-arabinitol determination based on a nano-structured sensing film by one-step electrodeposition

Copper nanoparticles (Cu-NPs) were incorporated into chitosan hydrogel to form a film on the surface of a glassy carbon electrode (GCE) leading to a sensing element for D-arabinitol with excellent oxidative catalytic activity. The electrochemical response to D-arabinitol was studied by cyclic voltammetry and differential pulse voltammetry. Operational parameters affecting the response were examined and optimized, and a simple and sensitive method was established for the determination of D-arabinitol. Response is linear in the concentration range from 10 μmol·L^?1 to 10 mmol·L^?1, and the limit of detection is 1.0 μmol·L^?1. The method may be combined with separation techniques in order to analyze for the ratio of D- and L-arabinitol which is a diagnostic marker for candidiasis.     

Electroanalytical Method for Determining Pyrogallol in Biodiesel in the Presence of a Surfactant

A sensitive, straightforward electroanalytical method for determining pyrogallol (PY) in biodiesel in the presence of a surfactant was developed using a voltammetric technique and screen‐printed electrodes. The influence of surfactant addition (sodium dodecyl sulfate (SDS), Triton X‐100 (TX‐100), cetyltrimethylammonium bromide (CTAB), tetrabutylammonium iodide (TBAI), tetrabutylammonium bromide (TBAB), or tetraethylammonium bromide (TEAB)) on the supporting electrolyte (0.04 mol L^?1 Britton? Robinson buffer) was evaluated. Only CTAB significantly increased the oxidation peak current. Under optimal conditions, the method demonstrated linearity over the concentration range of 0.8–9.0×10^?6 mol L^?1, with limits of detection and quantification of 4.9×10^?7 and 1.5×10^?6 mol L^?1, respectively. The results were satisfactory, relative to those obtained using high‐performance liquid chromatography (HPLC).     

Amperometric determination of the insecticide fipronil using batch injection analysis: comparison between unmodified and carbon-nanotube-modified electrodes

The electrochemical oxidation of fipronil is investigated on unmodified and multi-walled carbon-nanotube (MWCNT)-modified glassy carbon electrodes (GCEs), and its amperometric determination using batch injection analysis (BIA) is demonstrated. An oxidation peak was observed at 1.5 V in a 0.1 mol L^?1 HClO₄/acetone solution (50:50, v/v) on both surfaces. Although MWCNT-modified GCE provided greater sensitivity, the unmodified GCE showed low RSD value, wider linear range, and reduced adsorption of fipronil or its oxidized products on the electrode surface. A detection limit of 4.7 μmol L^?1 and linear range of 25–300 μmol L^?1 were obtained using a bare GCE. The method was applied in veterinary formulations with results in agreement with those obtained by high-performance liquid chromatography.     

Determination of cyanide,thiocyanate, cyanate,hexavalent chromium,and metal cyanide complexes in various mixtures by ion chromatography with conductivity detection

The first aim of this study was to develop a selective, sensitive, and reliable method for direct simultaneous determination of cyanate, thiocyanate, and hexavalent chromium by ion chromatography (IC) with conductivity detection. The other target was to successfully determine cyanides by utilizing same chromatographic system. Yet, since cyanides can not be detected by the direct method, free cyanide ions were converted into cyanate with chloramine-T at alkaline pH. In addition, strongly complexed metal cyanides were converted into cyanate by using photo-oxidation following chloramine-T. Total cyanate ion obtained from developed methods were analyzed with IC. The chromatographic separations on anion exchange column were accomplished by optimized multistep gradient eluent program using NaOH as the eluent. Proposed method was applied for the simultaneous determination of cyanide and hexavalent chromium in electroplating bath solutions and in industrial wastewater. Cyanide and hexavalent chromium could be measured in the linear dynamic ranges of 0.6–961.5 and 0.9–118.5 µmol L^?1, respectively. The limit of detection and limit of quantification of cyanide were 0.18 and 0.61 µmol L^?1, and these values for chromium(VI) were 0.26 and 0.86 µmol L^?1, respectively.     

Determination of nitrite in environmental waters by flow injection catalytic spectrophotometry

ABSTRACT

The flow injection catalytic spectrophotometry is proposed for the determination of nitrite based on the catalytic effect on the redox reaction between methylene blue and potassium bromate in acidic medium. The reaction is monitored spectrophotometrically by measuring the decrease in the absorbance of methylene blue at the maximum absorption wavelength of 664 nm. The method is characterised by low solvent consumption and easy automatic continuous analysis. It has higher sensitivity and lower detection limit. Experimental analysis conditions of the flow injection-catalytic photometry are optimised, and the best analysis conditions are: the concentration of the potassium bromate is 0.068 mol L^?1; the concentration of the phosphoric acid in oxidation liquid is 0.045 mol L^?1; the concentration of the methylene blue in colour-substrate solution is 2.4 mg L^?1, the volume of sample ring is 200 μL; the reaction coil is around 7 m in length; the inject time is 50 s and analysis time is 70 s. Under the optimal conditions, the linear range is from 10 to 500 μg L^?1 and the detection limit is 1 μg L^?1. The nitrate standard solution is continuously determined with a mass concentration of 300 μg L^?1. The RSD is determined to be 1.41% (n = 10). The nitrite in water samples, which were from the Half Acre pond, the Ink River and the Small West lake in a campus, was determined respectively by this method. A satisfactory standard addition recovery of 96.7%–103.9% was obtained.     

Determination of prazosin in pharmaceutical samples by flow injection analysis with multiple-pulse amperometric detection using boron-doped diamond electrode

This work describes the development of a simple, fast and low-cost method for determining prazosin (PRA) in pharmaceutical samples by flow injection analysis with multiple-pulse amperometric (FIA-MPA) detection using a boron-doped diamond film electrode. Electrochemical detection of PRA was optimized in phosphate buffer pH 4.0 by cyclic voltammetry, in which PRA presented two oxidation processes around at 0.97 and 1.40 V versus Ag/AgCl (3.0 mol L^?1 KCl). In these conditions, PRA also showed one reduction process at ?0.75 V that is dependent on the oxidation processes. Thus, the determination of PRA by FIA-MPA detection consisted on the application of a two-potential waveform, E ₁ (generator potential)?=?1.6 V/400 ms and E ₂ (collector potential)?=??1.0 V/30 ms, with sample loop of 150 μL and flow rate of 3.0 mL min^?1. The method showed good repeatability (RSD?<?3.0 %) and high analytical frequency (70 injections per h). The working linear range was obtained from 2 to 200 μmol L^?1 with a limit of detection of 0.5 μmol L^?1. The recovery tests in all samples were approximately 100 %, and the results were compared with chromatographic methods.     

A Direct Chemiluminescence Method for the Determination of Prulifloxacin Using Tris-(4,7-Diphenyl-1,10-Phenanthrolinedisulfonic Acid) Ruthenium(II)–Cerium(IV) System

Abstract

A simple, rapid, injection chemiluminescence method is described for the determination of prulifloxacin, a commonly used antibiotic. A strong chemiluminescence signal was detected when a mixture of the analyte and tris-(4,7-diphenyl-1,10-phenanthrolinedisulfonic acid)ruthenium(II) was injected into cerium(IV) sulfate. The chemiluminescence signal is proportional to the concentration of prulifloxacin in the range 4.0 × 10^?8–9.0 × 10^?6 mol L^?1. The detection limit is 1.0 × 10^?8 mol L^?1, and the relative standard deviation is 2.2% (n = 11) for the determination of 8.0 × 10^?7 mol L^?1 prulifloxacin. The proposed method was successfully applied to the determination of prulifloxacin in pharmaceutical preparations in capsules, spiked serum, and urine samples.     

Self-assembled sensor based on boron-doped diamond and its application in voltammetric analysis of picloram

A self-assembled sensor based on a boron-doped diamond was investigated as a sensitive tool for voltammetric analysis of a member of a pyridine herbicide family - picloram. A cyclic voltammetry and a differential pulse voltammetry were applied for investigation of the voltammetric behaviour and quantification of this herbicide. Picloram yielded one well-developed irreversible oxidation signal at a very positive potential about +1.5 V vs. Ag/AgCl/3 mol L^?1 KCl electrode in an acidic medium and 1 mol L^?1 H₂SO₄ was chosen as a suitable supporting electrolyte. Operating parameters of differential pulse voltammetry were optimized and the proposed voltammetric method provided a high repeatability (a relative standard deviation of 20 repeated measurements at a concentration level of picloram of 50 µmol L^?1 equaled to 2.58%), a linear concentration range from 2.5 to 90.9 µmol L^?1 and a low limit of detection (LD = 1.64 µmol L^?1). Practical usefulness of the ‘environmentally-green’ electrochemical sensor was verified by an analysis of spiked water samples with satisfactory recoveries.