Indirect Differential Pulse Voltammetric Determination of Aluminum Biological Samples in the Presence of 3, 4-Dihydroxyphenylalanine

ABSTRACT

Indirect differential pulse voltammetric (DPV) determination of aluminum in the presence of 3, 4-dihydroxyphenylalanine (L-dopa) with glass carbon electrode as working electrode has been described. The method relies on the decrease of DPV anodic peak current of L-dopa with the addition of Al^III The decreasing value of the peak current is linear with the increase of Al^III concentration. Under the optimum experimental conditions (pH 4.8, 6×10^?4 M L-dopa, 0.06M NaAc - HAc ¹buffer solution), the linear ranges are 4.0×10^?7 - 5.2×10^?6 M and 7.2×10^?6 - 4.5×10^?5 M. The relative standard deviation for 8×10^?6 M aluminum is 1.0% (n = 8) and the detection limit is 3.5×10^?7 M. A number of foreign species for interference have been studied. The method has been applied to determine aluminum in drinking water, synthetic renal dialysate and urine samples.     

Voltammetric investigation of Tamsulosin

The electrooxidative behavior and determination of Tamsulosin HCl (TAM), one of the alpha(1)-adrenoceptor antagonist, on a glassy carbon disc electrode were investigated for the first time by using cyclic, linear sweep, differential pulse (DPV) and square wave voltammetry (SWV). TAM showed an irreversible oxidation behavior at all pH values and buffers studied. From the electrochemical response, the main oxidation step was found to be related to the methoxy group on the phenyl ring. DPV and SWV were used to generate peak current versus concentration curves for TAM. A linear response was obtained in the range comprised between 2x10(-6) and 4x10(-4) M for both techniques with detection limit of 3.34x10(-7) M for DPV and 2.45x10(-7) M for SWV. The methods were proposed for the determination of TAM in dosage forms adopting both DPV and SWV modes. The methods were extended to the in vitro determination of TAM in spiked serum samples.     

Speciation of aluminium(III) in natural waters using differential pulse voltammetry with a pyrocatechol violet-modified electrode

A differential pulse voltammetric (DPV) procedure is proposed for the speciation of aluminium in natural waters using Pyrocatechol Violet chemically modified electrodes (PCV-CMEs). This novel speciation idea is based on the selective determination of different AlIII forms under two pH conditions. The labile monomeric Al fraction (mainly inorganic Al) is analysed at pH 4.8 (0.20 mol dm(-3) NaOAc-HOAc) and the total monomeric Al fraction is analysed at pH 8.5 (0.20 mol dm(-3) NH3.H2O-NH4Cl). The difference is thought to be caused by the weak competition ability of PCV to sequester AlIII from AlIII-natural organic matter complexes. This sensitive and simple speciation method has been applied successfully to aluminium speciation in natural waters sampled from different regions of China. Five fractions are measured directly or indirectly: (i) labile monomeric Al; (ii) total monomeric Al; (iii) acid reactive Al; (iv) non-labile monomeric Al; and (v) acid soluble Al. The results are in satisfactory agreement with those obtained by Driscoll's 8-hydroxyquinoline extraction-ion exchange method.     

Application of dopamine as an electroactive ligand for the determination of aluminum in biological fluids.

Dopamine (3,4-dihydroxyphenylethylamine, DA) is applied as an electroactive chelant for indirect determination of aluminum (Al) in biological fluids. It is observed that the decrease of the differential pulse voltammetric (DPV) anodic peak current of DA is linear with the increase of Al concentration. Under optimum experimental conditions (pH 8.6, 2.0 x 10(-4) M DA, and 0.03 M NH4Ac-NH3 x H2O buffer solution), two linear ranges, 5.0 x 10(-8) - 4.0 x 10(-7) M and 4.0 x 10(-7) - 7.2 x 10(-6) M Al(III), are obtained. The detection limit of Al is 1.9 x 10(-8) M and the relative standard deviation for 4 x 10(-6) M Al(III) is 3.1% (N = 8). Many biologically active foreign species have been selected for interference. Excellent recoveries and accuracy have been obtained in the measurements of Al in biological samples such as synthetic renal dialysate, Ringer's solution, human whole blood, cerebrospinal fluid of demented patient, and urine of diabetic patient. The methodological principle that Al complexes with DA on the electroactive position result in the depression of electrochemical activities of DA has been verified by comparing both the electrochemical behaviors and the spectroscopic responses like UV-vis and Raman of DA in the presence and in the absence of Al.     

Electrochemical behavior of ascorbic acid at a 2,2'-[3,6-Dioxa-1,8-octanediylbis(nitriloethylidyne)]-bis-hydroquinone carbon paste electrode

Electrocatalytic oxidation of ascorbic acid (AA) at a carbon paste electrode, chemically modified 2,2'-[3,6-dioxa-1,8-octanediylbis(nitriloethylidyne)]-bis-hydroquinone, was thoroughly investigated. The results of cyclic voltammetry, double potential-step chronoamperometry, linear sweep voltammetry and differential pulse voltammetry (DPV) studies were used for the prediction of the mechanism of electrochemical oxidation of AA mediated with 2,2'-[3,6-dioxa-1,8-octanediylbis(nitriloethylidyne)]-bis-hydroquinone at the surface of the modified electrode. The diffusion coefficient (D = 2.45 x 10(-5) cm(2) s(-1)) and the kinetic parameters such as the electron transfer coefficient (alpha = 0.34) were also determined. The results of DPV using the 2,2'-[3,6-dioxa-1,8-octanediylbis(nitriloethylidyne)]-bis-hydroquinone-modified electrode were applied in a highly sensitive determination of AA in drug samples. A linear range of 3.0 x 10(-6) - 1.2 x 10(-4) M and the detection limit (3sigma) 3.8 x 10(-7) M were obtained for DPV determination of AA in buffered pH 7.00 solutions (0.1 M phosphate buffer).     

Investigation of electrochemical behavior of lipid lowering agent atorvastatin calcium in aqueous media and its determination from pharmaceutical dosage forms and biological fluids using boron-doped diamond and glassy carbon electrodes

The electrochemical behavior of atorvastatin calcium at glassy carbon and boron-doped diamond electrodes has been studied using voltammetric techniques. The possible mechanism of oxidation was discussed with model compounds. The dependence of the peak current and potentials on pH, concentration, scan rate and nature of the buffer were investigated for both electrodes. The oxidation of atorvastatin was irreversible and exhibited a diffusion-controlled fashion on the diamond electrode. A linear response was obtained within the range of 9.65 x 10(-7) - 3.86 x 10(-5) M in 0.1 M H(2)SO(4) solution for both electrodes. The detection limits of a standard solution are estimated to be 2.11 x 10(-7) M with differential pulse voltammetry (DPV) and 2.05 x 10(-7)M with square wave voltammetry (SWV) for glassy carbon electrode, and 2.27 x 10(-7) M with DPV and 1.31 x 10(-7)M with SWV for diamond electrodes in 0.1 M H(2)SO(4) solution. The repeatability of the methods was found good for both electrodes. The methods were fully validated and successfully applied to the high-throughput determination of the drug in tablets, human serum and human urine with good recoveries.     

Trace analysis of aluminum in natural waters with rubeanic acid by adsorption chronopotentiometry

The determination of trace levels of aluminum in natural waters with rubeanic acid (RA) by adsorption chronopotentiometry is developed in this paper. Optimum experimental conditions include an accumulation potential of -0.40 V, accumulation time of 60 s, and a RA concentration of 6x10(-6) M in 0.2 M NaAc-HAc buffer solution (pH 4.6). The response is linear over the 1x10(-8) approximately 4x10(-7) M concentration range. The detection limit is 5.6x10(-9) M and the relative S.D. (at the 3x10(-7) M level) is 2.6%. Possible interferences are evaluated. The method has been applied to the determination of trace levels of Al in various real samples. Direct determination of toxic forms of Al in surface waters by this technique is also explored.     

Chemiluminescence determination of nitrate with photochemical activation in a flow injection system

A chemiluminescence flow injection system is described for the determination of nitrate, involving use of a laboratory-built flow-through photochemical reactor. Optimum analytical conditions were established. The linear range for nitrate is 7 x 10(-8)-1 x 10(-4)M. The sampling frequency is 60 samples per hour. The relative standard deviation for 1 x 10(-7), 1 x 10(-6) and 1 x 10(-5)M nitrate is 0.97, 0.84 and 0.76%, respectively. The method has been applied to the determination of nitrate in natural water samples, and recoveries of 96-103% have been attained.     

A new spectrofluorometric method for the determination of ascorbic acid based on its activating effect on a hemoglobin-catalyzed reaction.

A spectrofluorometric method for the determination of ascorbic acid (AA) based on its activation on the hemoglobin-catalyzed reaction was proposed. The fluorescence intensity of the product was measured under the optimal experimental conditions, i.e. 4.0 x 10(-6) M H2O2, 6.0 x 10(-5) M p-cresol, 1.2 M NH3-NH4Cl (pH 10.4) and 2.0 x 10(-7) M hemoglobin. The order of additions of the reagents was also studied. The activation of AA was found to be associated with a high ammonia concentration. The linear range of the method was 9.0 x 10(-10)-3.6 x 10(-8) M of AA. The detection limit was calculated to be 3.0 x 10(-10) M. The relative standard deviation of this method is 1.6% at 7.0 x 10(-9) M for 11 determinations.     

Voltammetric determination of sinomenine in biological fluid using a glassy carbon electrode modified by a composite film of polycysteic acid and carbon nanotubes

Polycysteic acid based electrochemical oxidation of L-cysteine (CySH) and carbon nanotubes (CNTs) formed a composite thin film material at a glassy carbon electrode (GCE) that was used a novel modifier for electroanalytical determination of sinomenine which is used for rheumatoid arthritis treatment. The determination of sinomenine at the composite modified electrode was studied by differential pulse voltammetry (DPV). The peak current obtained at + 0.632 V (vs SCE) from DPV was linearly dependent on the sinomenine concentration in the range of 1.0 x 10(-7) to 6.0 x 10(-5) M in a B-R buffer solution (0.04 M, pH 1.81) with a correlation coefficient of 0.998. The detection limit (S/N = 3) was 5.0 x 10(-8) M. The electrochemical reaction mechanism of sinomenine was also discussed. This new method was then applied to the high-throughput determination of sinomenine in human serum samples with satisfactory results. This polycysteic acid/CNTs composite film may be considered to be a promising, low-cost, durable, and biocompatible material for the modification of sensors in applications to pharmaceutical and biomedical analysis.     

Electrochemical study of zolpidem at glassy carbon electrode and its determination in a tablet dosage form by differential pulse voltammetry

The oxidative behaviour of, a hypnotic drug, zolpidem was studied at glassy carbon electrode in Britton-Robinson buffer over the pH range 2.0-11.0 using cyclic, linear sweep and differential pulse voltammetry. Oxidation of the drug was effected in a single irreversible, diffusion-controlled step. Using differential pulse voltammetry (DPV), the drug yielded a well-defined voltammetric response in Britton-Robinson buffer, pH 8.0 at +0.889 V (vs. Ag/AgCl) on glassy carbon electrode. This process could be used to determine zolpidem concentrations in the range 5.0 x 10(-7) M to 1.0 x 10(-5) M with a detection limit of 2.0 x 10(-7) M. The method was applied, without any interference from the excipients, to the determination of the drug in a tablet dosage form.     

Novel nitrite sensing using a palladium-polyphenosafranine nano-composite.

A novel palladium-polyphenosafranine nano-composite (PPS-Pd) was synthesized by electrochemical co-deposition at a glassy carbon electrode (GCE) for fabrication of a nitrite sensor, PPS-Pd/GCE. This PPS-Pd film was characterized by X-ray photoelectron spectroscopy (XPS) and field emission scanning electron microanalysis (SEM). It was found that the PPS-Pd nano-composite consisted of Pd nanoparticles smaller than 10 nm in diameter which stick together due to the polymer, forming a Pd-embedded PPS layer structure. The sensing ability was investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and differential pulse amperometry (DPA). The PPS-Pd/GCE had excellent catalytic activity toward the oxidation of nitrite: high current sensitivity of 0.365 A/M cm(-2), good reproducibility, good stability and fast response. In neutral solutions, a linear concentration range of 1.0 x 10(-6) to 1.1 x 10(-3) M (R(2) = 0.999) with the detection limit (s/n = 3) of 3 x 10(-7) M nitrite was obtained for DPV determination.     

A new red-region substrate, tetra-substituted amino aluminium phthalocyanine, for the fluorimetric determination of H2O2 catalyzed by mimetic peroxidases

A new red-region fluorogenic substrate, tetra-substituted amino aluminium pthalocyanine, was developed for the selective determination of H2O2 based on the catalytic effect of mimetic peroxidases, viz., hemin or iron tetrasulfonatophthalocyanine (FeTSPc). Under the optimum conditions, the linearity of the calibration graph for the determination of H2O2 with hemin (or FeTSPc) as the catalyst was in the range from 0.0 to 3.0 x 10(-7) mol L-1 (or from 0.0 to 2.0 x 10(-6) mol L-1). The detection limits were 3.7 x 10(-9) and 4.9 x 10(-9) mol L-1 H2O2, respectively. The relative standard deviation (n = 7) was within 1.5% in the middle of the linear range. The peroxidase activity of the mimetic enzymes hemin and FeTSPc, the effects of some experimental conditions and the influence of foreign substances were investigated. With this substrate, 0.0-7.5 x 10(-8) mol L-1 hemin and 0.0-2.0 x 10(-6) mol L-1 FeTSPc can be determined with an accuracy and precision of about 1.3%. The potential application of the reagent was tested by the determination of H2O2 in rainwater.     

Voltammetric determination of terbinafine in biological fluid at glassy carbon electrode modified by cysteic acid/carbon nanotubes composite film

The electrochemical oxidation of L-cysteine (CySH) in presence of carbon nanotubes (CNTs) formed a composite film at a glassy carbon electrode (GCE) as a novel modifier for directly electroanalytical determination of terbinafine without sample pretreatment in biological fluid. The determination of terbinafine at the modified electrode with strongly accumulation was studied by differential pulse voltammetry (DPV). The peak current obtained at +1.156 V (vs. SCE) from DPV was linearly dependent on the terbinafine concentration in the range of 8.0 x 10(-8)-5.0 x 10(-5 )M in a B-R buffer solution (0.04 M, pH 1.81) with a correlation coefficient of 0.998. The detection limit (S/N=3) was 2.5 x 10(-8 )M. The low-cost modified electrode showed good sensitivity, selectivity, and stability. This developed method had been applied to the direct determination of terbinafine in human serum samples with satisfactory results. It is hopeful that the modified electrode will be applied for the medically clinical test and the pharmacokinetics in future.     

Spectrofluorimetric method for determination of aluminium with chromotropic acid and its application to water samples

A rapid and sensitive method for the trace level determination of aluminium based on the formation of a 1:1 complex with chromotropic acid (1,8-dihydroxynaphthlene-3,6-disulfonic acid) in an methanol medium is reported. The fluorescence intensity of the system was 50 times greater than that of the system without aluminium. This method is very sensitive and selective for the direct determination of aluminium ion. The fluorescence is excited at 346 nm and measured at 370 nm. The optimum conditions are a chromotropic acid concentration of 5.0 ml (1.0x10(-4) M) and pH 4.0+/-0.5 (acetic acid-sodium acetate buffer). The fluorescence intensity is a linear function of the concentration of Al(III) in the range 2-100 ng ml(-1) and the detection limit is 1.0 ng ml(-1). The method has been applied successfully to the determination of trace amount of Al(III) in tap, river and sea-water samples.     

Facile separation and determination of Aconitine alkaloids in traditional Chinese medicines by CE with tris(2,2'-bipyridyl) ruthenium(II)-based electrochemiluminescence detection

A facile CE method coupled with tris(2,2'-bipyridyl) ruthenium(II)-based electrochemiluminescence [Ru(bpy)(3) (2+)] detection was developed for simultaneous determination of Aconitum alkaloids, i.e., hypaconitine (HA), aconitine (AC), and mesaconitine (MA) in baseline separation. The optimal separation of these Aconitum alkaloids was achieved in a fused-silica capillary column (50 cm x 25 microm id) with 30 mM phosphate solution (pH 8.40) as running buffer at 12 kV applied voltage. The three alkaloids can be determined within 10 min by a single run. The calibration curves showed a linear range from 2.0 x 10(-7) to 2.0 x 10(-5) M for HA, 3.4 x 10(-7) to 1.7 x 10(-5) M for AC, and 3.8 x 10(-7) to 1.9 x 10(-5) M for MA. The RSDs for all analytes were below 3.01%. Good linear relationships were found with correlation coefficients for all analytes exceeding 0.993. The detection limits were 2.0 x 10(-8) M for HA, 1.7 x 10(-7) M for AC, and 1.9 x 10(-7) M for MA under optimal conditions. This method was successfully applied to determine the three alkaloids in Aconitum plants.     

Determination of gallium by square-wave voltammetry anodic stripping, based on the electrocatalytic action of 2,2'-bipyridine in dimethylsulphoxide: comparison with an aqueous NaSCN/NaClO(4) electrolyte

Deposition potential, deposition time, square-wave frequency, 2,2'-bipyridine concentration, and gallium concentration have been studied in detail, for the determination of trace concentration levels of the metal by square-wave voltammetry anodic stripping analysis, in dimethylsulphoxide. Optimum conditions have been found for gallium(III) determination and results compared to those obtained in 0.5M NaSCN + 4.2M NaClO(4) aqueous electrolyte by obtaining calibration graphs for the range 1 x 10(-8)M-1 x 10(-5)M gallium. Accuracy (+/- 3%) and precision (4-6% SD) of this method were assessed with both 4 x 10(-8)M and 4 x 10(-7)M gallium solutions used as synthetic samples. The efficiency of solvent extraction of gallium with di-isopropyl ether was found to be 99.98% at a 4 x 10(-7)M gallium concentration. The proposed method was applied to the determination of the gallium content in rock mineral samples (using the above mentioned solvent extraction procedure), are compared to those obtained with the NaSCNNaClO(4) based electrolyte. No statistically significant difference was observed. Analytical procedures followed are given in detail.     

Simultaneous determination of beryllium and aluminium in mixtures using derivative spectrophotometry

The spectrophotometric determination of beryllium and aluminium with 5,8-dihydroxy-1,4-naphthoquinone in the presence of a non-ionic surfactant is reported. Absorption maxima, molar absorptivity and Sandell's Sensitivity of 1:2 (M:L) beryllium and aluminium complexes are, 585 nm and 598 nm, 1.63 x 10(4) l.mole(-1).cm(-1) and 2.04 x 10(4) l.mole(-1).cm(-1), and 0.55 ng/cm(2) and 1.32 ng/cm(2) respectively. Beer's law is obeyed between 7.20-3.96 x 10(2) ng/ml beryllium and 1.08 x 10(1)-1.08 x 10(3) ng/ml aluminium. A method for simultaneous determination of beryllium and aluminium in their mixture using derivative spectra is described. The range 3.6 x 10(1)-3.6 x 10(2) ng/ml beryllium could be determined in the presence of 1.08 x 10(2)-1.08 x 10(3) ng/ml aluminium, and vice versa.     

Electrochemistry and voltammetric determination of colchicine using an acetylene black-dihexadecyl hydrogen phosphate composite film modified glassy carbon electrode

The electrochemical behavior of colchicine at an acetylene black-dihexadecyl hydrogen phosphate (denoted as AB-DHP) composite film coated glassy carbon electrode (GCE) was investigated using cyclic voltammetry (CV), linear sweep voltammetry (LSV) and differential pulse voltammetry (DPV). Compared with the poor electrochemical signal at the unmodified GCE, the electrochemical response of colchicine at the AB-DHP film modified GCE was greatly improved, as confirmed from the significant peak current enhancement. The remarkable peak current enhancement indicates that the AB-DHP modified GCE has great potential in the sensitive determination of colchicine. Thus, all the experimental conditions, which influence the electrochemical response of colchicine, were studied and the optimum conditions were achieved. Finally, a sensitive and simple voltammetric method with a good linear relationship in the range of 1.0 x 10(-7) approximately 4.0 x 10(-5) mol/L, was developed for the determination of colchicine. The detection limit of colchicine was also examined and a low value of 4.0 x 10(-8) mol/L for 4-min accumulation was obtained (S/N=3). This electrode was successfully applied to detect colchicine in human urine samples.     

用左旋多巴-示差脉冲伏安法间接测定生物样品中的铝

人体内摄入过多的铝可能导致或促进阿尔茨海默氏病 ( Alzheimer s disease)、帕金森氏病( Parkinson s disease)及透析脑病 ( Dialysis encephalopathy)的发病 [1] .原子吸收光谱法、能量分布 X射线光谱法、 X射线微探针分析法、激光微探针质量分析法和核显微法曾用于测定脑铝 .这些方法在样品制作过程中易被污染 [2 ,3] ,仪器昂贵 ,灵敏度不高 ,而且均不能用于人体液和脑铝的在体检测 .由于铝的还原电位约 - 1 .7V,易受 H+干扰 ,直接测定铝有困难 .吸附伏安法利用铝与染料的配合物的电化学响应来测定环境和生物制品中的铝 ,检测下限达 1…