Application of adsorptive stripping voltammetry to the determination of bismuth and copper in the presence of morin

A new method is presented for the determination of bismuth and copper based on cathodic adsorptive stripping of complexes of Cu(II) and Bi(III) with 2′,3,4′,5,7-pentahydroxyflavone (morin) at a hanging mercury drop electrode (HMDE). The effect of various parameters such as pH, concentration of morin, accumulation potential and accumulation time on the selectivity and sensitivity were studied. The optimum conditions for determination of copper include nitric acid concentration 0.1 M, morin concentration 0.6 μM and accumulation potential of −300 mV. Those conditions for the determination of bismuth include 0.15 M acid concentration, 0.6 μM morin and accumulation potential of −300 mV. Under these optimum conditions and for an accumulation time of 60 s, the measured peak current at −20 to 25 mV is proportional to the concentration of copper and bismuth over the range of 0.2-130 and 5-50 ng ml⁻¹, respectively. At high concentration of morin (35 μM morin) and accumulation potential of −300 mV (versus Ag/AgCl reference electrode) the peak current is proportional only to the concentration of copper and bismuth has no contribution to the current. At low concentration of morin (0.5 μM morin) and accumulation potential of 100 mV (versus Ag/AgCl reference electrode) the peak current is proportional only to the concentration of bismuth. The method was applied to the determination of copper and bismuth in some real and synthetic samples with satisfactory results.     

Determination of subnanomolar concentrations of cobalt by adsorptive stripping voltammetry at a bismuth film electrode

Procedures for trace cobalt determinations by adsorptive stripping voltammetry at in situ and ex situ plated bismuth film electrodes are presented. These exploit the enhancement of the cobalt peak obtained by using the Co(II)–dimethylglyoxime–cetyltrimethylammonium bromide–piperazine-N,N-bis(2-ethanesulfonic acid) system. The calibration graph for an accumulation time of 120 s was linear from 2 × 10^–10 to 2 × 10^–8 mol L^–1. The relative standard deviation from five determinations of cobalt at a concentration of 5 × 10^–9 mol L^–1 was 5.2%. The detection limit for an accumulation time of 300 s was 1.8 × 10^–11 mol L^–1. The proposed procedure was applied to cobalt determination in certified reference materials and in tap and river water samples.     

Genetic algorithms based on wavelet transform for resolving simulated overlapped spectra

Wavelet transform-based genetic algorithms are proposed for resolving simulated overlapped spectra. Wavelet transform as a derivative method is used for de-noising, for deducting background absorption as well as for peak finding in order to get an estimation of parameters of unresolved spectra. Then genetic algorithms, using the estimations of parameters as input values, are employed to resolve unresolved bands. As a consequence, a good optimized solution was achieved since the reliable estimation of initial values can greatly facilitate the convergence of genetic algorithms and the calculation time is shortened accordingly.     

Determination of trace amount of bismuth(III) by adsorptive anodic stripping voltammetry at carbon paste electrode

A sensitive method is described for the determination of trace bismuth based on the bismuth-bromopyrogallol red (BPR) adsorption at a carbon paste electrode (CPE). The overall analysis involved a three-step procedure: accumulation, reduction, and anodic stripping. Optimal conditions were found to be an electrode containing 25% paraffin oil and 75% high purity graphite powder, a 0.30 mol l⁻¹ HCl solution containing 2.0×10⁻⁵ mol l⁻¹ BPR as supporting medium; accumulation potential and time, −0.10 V, 3 min; reduction potential and time, −0.35 V, 60 s; scan rate 100 mV s⁻¹; scan range from −0.35 to 0.15 V. It was found that the Bi(III)-BPR complex could be accumulated on the electrode surface during the accumulation period. Then the Bi(III) in the Bi(III)-BPR complex on the CPE surface was reduced to Bi(0) during reduction interval and finally reoxidized during the anodic stripping step for voltammetric quantification. Factors affecting the accumulation, reduction, and stripping steps were investigated. Interferences by other ions were studied as well. The detection limit was found to be 5×10⁻¹⁰ mol l⁻¹ with a 3 min accumulation time. The linear range was from 1.0×10⁻⁹ to 5.0×10⁻⁷ mol l⁻¹. Application of the procedure to the determination of bismuth in water and human hair samples gave good results.     

Prediction of protein secondary structure based on continuous wavelet transform

In this paper, continuous wavelet transform (CWT) is used to extract the number and the relevant positions of the α-helices and short peptides connecting α-helices and β-strands (connecting peptides) from the amino acid sequences of proteins. The amino acid sequence is first mapped into hydrophobicity sequence, and then transformed into CWT value of sequence domain in appropriate scale via CWT. The number and the relevant positions of the α-helices and connecting peptides can be extracted easily and accurately according to the minima of wavelet coefficient in corresponding CWT plot of hydrophobic value sequences with appropriate scale. The analytical results demonstrate that α-helices and connecting peptides can be predicted conveniently and rapidly when this method is used in the processing of 100 non-homologous sequences. However, this method is not suitable for predicting the length of α-helices and connecting peptides.     

Feature analysis of protein structure by using discrete Fourier transform and continuous wavelet transform

In this paper, discrete Fourier transform (DFT) and continuous wavelet transform (CWT) are used to predict the protein structure. Hydrophobicity plays a key role in the form of protein structure. The amino acid sequence is first mapped into hydrophobicity sequence, and then process it by DFT and CWT so that power spectral density is gained. The results show that continuous wavelet transform can extract the features of protein structure effectively and availably and has a tremendous development foreground.     

Application of adsorptive stripping voltammetry to the simultaneous determination of bismuth and copper in the presence of nuclear fast red

A sensitive and selective method for the simultaneous determination of copper and bismuth by adsorptive stripping was developed using nuclear fast red (2-anthracenesulfonic acid, 4-amino-9,10-dihydro-1,3-dihydroxy-9,10-dioxo-, monosodium salt) as selective complexing agent onto hanging mercury drop electrode. In a single scan both metals gave peaks that were distinctly separated by 85 mV allowing their determination in the presence of each other. Optimal analytical conditions were found to be: nuclear fast red concentration of 80 μM, pH of 2.8 and adsorptive potential of −300 mV versus Ag/AgCl. With accumulation time of 180 s the peaks currents are proportional to concentration of copper and bismuth over the 1-100 and 5-60 ng mL⁻¹ range with detection limits of 0.2 and 1.2 ng mL⁻¹, respectively. The procedure was applied to simultaneous determination of copper and bismuth in some real samples.     

The versatility of salicylaldehyde thiosemicarbazone in the determination of copper in blood using adsorptive stripping voltammetry

The adsorptive cathodic stripping voltammetry technique (AdCSV) is used to determine copper(II) using salicylaldehyde thiosemicarbazone (N, S- donor) as a complexing agent on hanging mercury drop electrode at pH 9.3. Variable factors affecting the response, i.e. the concentration of ligand, pH, adsorption potential and adsorption time are assessed and optimized. The adsorbed complex of copper(II) and salicylaldehyde thiosemicarbazone gives a well defined cathodic stripping peak current at −0.35 V, which has been used for the determination of copper in the concentration range of 7.85 × 10⁻⁹ to 8.00 × 10⁻⁶ M with accumulation time of 360 s at −0.1 V versus Ag/AgCl. This technique has been applied for the determination of copper in various digested samples of whole blood at trace levels.     

Determination of ultra trace amount of enrofloxacin by adsorptive cathodic stripping voltammetry using copper(II) as an intermediate

In this work, a simple and sensitive electroanalytical method was developed for the determination of enrofloxacin (ENRO) by adsorptive cathodic stripping voltammetry (ADSV) using Cu(II) as a suitable probe. The complex of copper(II) with ENRO was accumulated at the surface of a hanging mercury drop electrode at −0.10 V for 40 s. Then, the preconcentrated complex was reduced and the peak current was measured using square wave voltammetry (SWV). The optimization of experimental variables was conducted by experimental design and support vector machine (SVM) modeling. The model was used to find optimized values for the factors such as pH, Cu(II) concentration and accumulation potential. Under the optimized conditions, the peak current at −0.30 V is proportional to the concentration of ENRO over the range of 10.0-80.0 nmol L⁻¹ with a detection limit of 0.33 nmol L⁻¹. The influence of potential interfering substances on the determination of ENRO was examined. The method was successfully applied to determination of ENRO in plasma and pharmaceutical samples.     

微波消解-铋膜修饰电极阳极溶出法测定大米中镉

建立了大米中Cd的微波消解壤膜电极阳极溶出伏安快速测定方法.在0.2 mol/L HAc-NaAc缓冲溶液(pH 4.0)中,Cd(Ⅱ)在-650mV附近出现一灵敏的溶出峰,其质量浓度在1～360 μg/L范围内与峰高成正比,检出限可达0.05 μg/L,回收率为93.5％～106.3％;本法已用于大米中Cd的测定,并...     

掺杂硒碳糊电极阳极溶出法测定铋

建立了一种测定痕量铋的新方法,即利用掺杂硒碳糊电极作为工作电极的阳极溶出法.在0.1 mol/L的HCl底液中,Bi3+于+0.05V(vs.Ag/AgCl)出现灵敏的氧化溶出峰,铋离子的浓度在1.0×10-5～1.0×10-9 mol/L范围内其对数值lgc与铋的氧化峰电流值呈线性关系,检出限达1.0×10 -10 ...     

Determination of cadmium with a sequential injection lab-on-valve by anodic stripping voltammetry using a nafion coated bismuth film electrode

This work exploited a sequential injection lab-on-valve (LOV) system for the determination of cadmium by anodic stripping voltammetry (ASV). A miniaturized electrochemical flow cell (EFC) was fabricated in LOV, in which a nafion coated bismuth film electrode was used as working electrode. The cadmium was electrodeposited on the electrode surface in bismuth solution, and measured with the subsequential stripping scan. Under optimal conditions, the proposed system responded linearly to cadmium concentrations in a range 2.0-100.0 μg L⁻¹. The detection limit of this method was found to be 0.88 μg L⁻¹. By loading a sample volume of 800 μL, a sampling frequency of 22 determinations h⁻¹ was achieved. The repeatability expressed as relative standard derivation (R.S.D.) was 3.65% for 20 μg L⁻¹ cadmium (n = 11). The established method was applied to analysis of trace cadmium in environmental water samples and the spiked recoveries were satisfactory.     

Determination of total copper in haemodialysis water by differential-pulse anodic stripping voltammetry

An anodic stripping voltammetric method was developed in order to determine copper in the water used to prepare haemodialysis solutions. The interference from organic matter was overcome by high-pressure bomb mineralization. The electrochemical results were compared with those obtained by using graphite furnace atomic absorption spectrometry and the correlation was excellent (r = 0.983, p < 0.001). The detection limit was 0.2 μg l^?1 copper.     

Adsorptive stripping voltammetry of nickel with 1-nitroso-2-napthol using a bismuth film electrode

A sensitive procedure is presented for the voltammetric determination of nickel. The procedure involves an adsorptive accumulation of nickel 1-nitroso-2-napthol (NN) complex on a bismuth film electrode prepared ex situ by electrodeposition. The most suitable operating conditions and parameters such as pH, ligand concentration (C_NN), adsorptive potential (E_ads), adsorptive time (t_ads), scan rate and others were selected and the determination of nickel in aqueous solutions using the standard addition method was possible. The adsorbed Ni-NN complex gives a well defined cathodic stripping peak current at −0.70 V, which was used for the determination of nickel in the concentration range of 10.0-70.0 μg L⁻¹ (pH 7.5; C_NN 6.5 μmol L⁻¹; E_ads −0.30 V; t_ads 60 s) with a detection limit of 0.1 μg L⁻¹. The relative standard deviation for a solution containing 10.0 μg L⁻¹ of Ni(II) was 3.5% (n = 4). The proposed method was validated determining Ni(II) in certified reference waste water (SPS-WW1) and Certified Reference Water for Trace Elements (TMDA 51.3) with satisfactory results. Then lake water samples were analyzed.     

Determination of cobalt by adsorptive stripping voltammetry with double accumulation and stripping steps

A double accumulation and stripping steps were proposed to increase the sensitivity of Co(II) determination by catalytic adsorptive stripping voltammetry (AdSV). Electrodes with large and small surface area were used for the first and second accumulation step, respectively. As the accumulation of Co(II) complex at the first electrode was finished, the electrode was placed at a short distance opposite the second one. Then the Co(II) complex desorbed from the first electrode was accumulated at the second electrode. Taking into account the small volume of space between the electrodes, the concentration of the Co(II) complex in solution between the electrodes was drastically higher than that in the bulk solution. The accumulation step at the second electrode was performed from the solution with higher concentration of Co(II) and therefore the detection limit was lowered. The calibration graph of Co(II) determination for accumulation time of 120 s at both electrodes was linear from 1.18 to 58.9 ng L^?1. The detection limit for Co(II) was equal to 0.47 ng L^?1 and it is so far the lowest detection limit obtained for Co(II) using mercury-free electrodes. The proposed method was applied to Co(II) determination in water certified reference material.     

Determination of Captropril using adsorptive cathodic differential pulse stripping voltammetry with the HMDE

A voltammetric method for the determination of 3-mercapto-D-2-methylpropanoyl-L-proline, a hypotensive drug whose pharmaceutical name is Captopril (CPT), in the concentration range from 9.0×10⁻¹⁰M to 3×10⁻⁶M, is described. In this range the peak current increases linearly with drug concentration even when different collection periods are used. A self-cleaning Hanging Mercury Drop Electrode (HMDE) was used and a negative Differential Pulse potential (DP) was applied to the indicator electrode. The stripping peak of CPT splits into two peaks as soon as the concentration is increased over about 10⁻⁵M; in the oxidation DP scan, instead, this splitting is observed at a concentration of 2.0×10⁻⁴M. Some attempts were made to verify the suitability of other techniques such as Alternating Current polarography (AC) and the use of a different electrode, the Wax-Impregnated Graphite Electrode (WIGE).     

Simultaneous determination of copper, zinc and lead by adsorptive stripping voltammetry in the presence of Morin

A sensitive and selective method for the simultaneous determination of copper, zinc and lead is presented. The method is based on the adsorptive accumulation of 2′,3,4′,5,7-pentahydroxyflavone (Morin) complexes of these elements onto a hanging mercury drop electrode, followed by reduction of adsorbed species by voltammetric scan using differential pulse modulation. Optimal analytical conditions were found to be Morin concentration of 2.0 μM, pH of 4.0, and an adsorption potential at −500 mV versus Ag/AgCl. With an accumulation time of 60 s, the peak currents are proportional to the concentration of copper, lead and zinc over the 1 to 60, 0.3-80 and 1-70 ng ml⁻¹ range with detection limits of 0.06, 0.08 and 0.06 ng ml⁻¹, respectively. The procedure was applied to the simultaneous determination of copper, lead and zinc in some real and synthetic artificial real samples with satisfactory results.     

Extending the dynamic range of copper determination in differential pulse adsorption cathodic stripping voltammetry using wavelet neural network

A wavelet neural network (WNN) model is proposed for extending the dynamic range of Cu(II) determination by differential pulse adsorption cathodic stripping voltammetry (DP-AdSV) using xylenol orange (XO) as a suitable ligand. All of voltammograms data consisting of Cu(II) and Cu(II)–XO peak currents were used in WNN model. The WNN model consisted of three layers (2-8-1) with the Morlet mother wavelet transfer function in the hidden layer. The model was able to extend the dynamic range of Cu(II) from its narrow linear range (1–50 ng ml⁻¹) to the higher dynamic range (1–1500 ng ml⁻¹). The results of the WNN model was also compared with artificial neural network (ANN) model and it was demonstrated the superiority of the WNN model relative to ANN model.     

Simultaneous determination of copper, bismuth and lead by adsorptive stripping voltammetry in the presence of thymolphthalexone.

A novel, sensitive and selective adsorptive stripping procedure for simultaneous determination of copper, bismuth and lead is presented. The method is based on the adsorptive accumulation of thymolphthalexone (TPN) complexes of these elements onto a hanging mercury drop electrode, followed by reduction of adsorbed species by voltammetric scan using differential pulse modulation. The influences of control variables on the sensitivity of the proposed method for the simultaneous determination of copper, lead and bismuth were studied using the Derringer desirability function. The optimum analytical conditions were found to be TPN concentration of 4.0 microM, pH of 9.0, and accumulation potential at -800 mV vs. Ag/AgCl with an accumulation time of 80 s. The peak currents are proportional to the concentration of copper, bismuth and lead over the 0.4-300, 1-200 and 1-100 ng mL(-1) ranges with detection limits of 0.4, 0.8 and 0.7 ng mL(-1), respectively. The procedure was applied to the simultaneous determination of copper, bismuth and lead in the tap water and some synthetic 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.