Potentiometric determination of silver(I) by selective membrane electrode based on derivative of porphyrin.

The performance of silver metal complexes with meso-tetraphenylporphyrin ([H2T(4-CH3)]PP) as ionophores for ion-selective electrodes was studied. The electrode exhibited linear response with Nernstian slope of 59.2 +/- 1.0 mV per decade within the concentration range of 1.0 x 10(-7)-1.0 x 10(-1) M silver ions. The limit of detection as determined from the intersection of the extrapolated linear segments of the calibration plot, was 1.0 x 10(-7) M. The response time of the electrode was < 10 s over the entire concentration range. The silver-selective electrode exhibited good selectivity for Ag(I) with respect to alkali, alkaline earth and heavy metal ions. The electrodes could be used at least three months without a considerable divergence in their potential. The electrodes are suitable for use in aqueous solutions in a wide pH range of 3.0-9.0. They were used as indicator electrodes in titration of Ag(I) with sodium iodide solution and were successfully applied to direct determination of silver in real samples.     

Simultaneous determination of ascorbic acid, uric acid and neurotransmitters with a carbon ceramic electrode prepared by sol-gel technique

A sol-gel carbon composite electrode (CCE) has been prepared by mixing a sol-gel precursor (e.g. methyltrimethoxysilane) and carbon powder without adding any electron transfer mediator or specific reagents. It was demonstrated that this sensor can be used for simultaneous determination ascorbic acid, neurotransmitters (dopamine and adrenaline) and uric acid. Direct electrochemical oxidation of ascorbic acid, uric acid and catecholamines at a carbon composite electrode was investigated. The experimental results were compared with other common carbon based electrodes, specifically, boron doped diamond, glassy carbon, graphite and carbon paste electrodes. It was found that the CCE shows a significantly higher of reversibility for dopamine. In addition, in comparison to the other electrodes used, for CCE the oxidation peaks of uric acid, ascorbic acid and catecholamines in cyclic and square wave voltammetry were well resolved at the low positive potential with good sensitivity. The advantages of this sensor were high sensitivity, inherent stability and simplicity and ability for simultaneous determination of uric acid, catecholamines and ascorbic acid without using any chromatography or separation systems. The analytical performance of this sensor has been evaluated for detection of biological molecules in urine and serum as real samples.     

聚萘二胺修饰电极对痕量物质的检测

综述了聚萘二胺修饰铂电极、玻碳电极和碳糊电极用于检测痕量银离子、铅离子、亚硝酸根及硝酸根阴离子、过氧化氢、葡萄糖和胆甾醇等方面的研究成果，列举了这些电极的优异探测性能，并指出该类电极有望发展成为性能优异的检测电极和传感器。引用文献14篇。     

Chemically modified carbon paste electrode for iodide determination on the basis of cetyltrimethylammonium iodide ion-pair.

A new carbon paste electrode (CPE) for the determination of iodide ion based on a cetyltrimethylammonium iodide (CTMAI) ion pair as an electroactive material is described. The electrode shows a linear response for iodide ion over the concentration range of 4 x 10(-5) M to 1 x 10(-1) M with a lower detection limit of 4 x 10(-5) M at 25 degrees C. The electrode has a Nemstian slope of -55.0 +/- 0.4 mV/decade and a fast potential response of 45 s, which is almost constant over a pH range of 5.0 - 9.0. Selectivity coefficient data of the CTMAI-CPE for some common ions show negligible interference, and the electrode has high selectivity towards the iodide ion. An average recovery of 101.83% with a relative standard deviation of 1.53% has been achieved for the determination of iodide in Flaxedil (gallamine triethiodide) ampoules, a muscle relaxant drug. The electrode has been examined for the determination of iodide in saline water; the results were found to compare favorably with those obtained using Metrohm iodide ISE. The electrode has been utilized as an end-point indicator electrode for the determination of Hg(II) and phenylmercury(I) in their aqueous solutions using potentiometric titration with a potassium iodide standard solution.     

Voltammetry behavior of iodine and selenium on new organo-modified electrodes: Development of a procedure for the determination of iodine and selenium

The voltammetry behavior of iodine and selenium has been studied on new organo-modified electrodes. The conditions have been proposed for the measurement of the analytical signals of iodide and selenium ions on a silver electrode modified by aryl diazonium tosylates containing an amino group in the presence of a 0.1 M solution of N₂H₄ · H₂SO₄ (pH 2–3) without oxygen removal. A new approach and a procedure have been developed for the simultaneous determination of iodine and selenium in tap, drinking, and mineral waters using the organo-modified electrode. The analytical range is from 0.003 to 1.5 mg/L for iodide ions and from 0.003 to 2.0 mg/L for selenite ions.     

Potentiometric carbon paste sensors for lead(II) based on dithiodibenzoic and mercaptobenzoic acids.

Dithiodibenzoic (DTB) acid and mercaptobenzoic (MB) acid were studied to characterize their abilities as modifier agents for lead(II) sensors. For both sensors, the best results were obtained with modified carbon paste electrodes with 24.1% of ligand. The pH influence on the potentiometric response was studied. The selectivity coefficients for both modified electrodes were tabulated. A potentiometric sensor based on DTB acid exhibited a more sensitive and selective response to lead ions than an MB electrode. The limits of detection for the DTB and MB electrodes were very similar, 5.01 x 10(-8) M and 3.98 x 10(-8) M, respectively, for lead(II) activity. The DTB sensor was applied to lead(II) ion determination in real samples and as an indicator electrode in potentiometric titrations. Natural and commercial humic acids were titrated using the DTB electrode to estimate the stability constant between these organic compounds and the lead(II) ions with successful results.     

New Strategy for Dehydrogenase Amperometric Biosensors Using Surfactant to Enhance the Sensitivity of Diaphorase/Ferrocene Modified Carbon Paste Electrodes for Electrocatalytic Oxidation of NADH

A carbon paste electrode (CPE) modified with diaphorase (DAP) and ferrocene (FcH) has been developed for determination of NADH at low working potential. The sensitivity and operational stability, towards the detection of the reduced form of the nicotinamide adenine dinucleotide (NADH) in flow injection analysis (FIA), were greatly improved (5 times) upon adding Tween 20 into the electrode matrix. The magnitude of the amperometric signal was dependent on DAP, FcH and surfactant loading, into the modified carbon paste electrode. A rapid and repeatable response was observed to the variation of NADH concentration in the vicinity of the electrode surface. Such advantages of the DAP/FcH/Tween 20 modified carbon paste were successfully used in the construction of L ‐lactate dehydrogenase modified electrodes. The use of this new approach can be generalized to other dehydrogenases and represents a decisive step for a versatile preparation method of amperometric biosensors.     

Electrochemical Oxidation and Analytical Applications of Cholesterol at Modified Carbon Paste Electrode

The present paper describes the carbon paste electrodes modified with parafin oil and oleic acid, and the electrochemical oxidation of cholesterol at these modified electrodes. A few years ago, an oleic acid modified carbon paste electrode was proposed and applied to the selective determination of estrogens. Basing on the similar considerations, we found that cholesterol has about the same structure as estrogens. The results of voltammetric measurement indicated that cholesterol at the modified carbon paste electrodes employing the oleic acid as the modifying reagent can yield a sensitive electrochemical response. A detection limit of 1.5×10^-7mol/L cholesterol was estimated after a time of 4 min. by 1.5 order differential stripping analysis. The peak current is linearly proportional to the cholesterol concentration in the range of 3.O×10^-5——5.0×10^-7mol/L.     

辛可宁修饰碳糊电极的应用研究——铋的阳极溶出伏安法测定

报道了利用辛可宁修饰碳糊电极测定铋的方法,在1mol/LH2SO4溶液中,通过在－1.00V电位下富集Bi3＋后,在－0.20～＋0.15V电位范围内作阳极溶出伏安法测定。在－0.022V处有一灵敏的氧化峰,峰电流与Bi     

Comparisons of disposable and conventional silver working electrode for the determination of iodide using high-performance anion-exchange chromatography with pulsed amperometric detection

The paper compared the performance of two kinds of silver working electrode in electrochemical detector-the disposable and conventional electrode for the determination of iodide using high-performance anion-exchange chromatography (HPAEC) hyphenated with pulsed amperometric detection (PAD). The comparisons were carried out on the time of equilibration, long and short-term reproducibility, limits of detection and linearity of calibration. Results showed that disposable working electrode manifested equal or better results than conventional working electrode and could be used for iodide analysis. Besides, the disposable electrode could work for consecutive 2660 min (about 44 h, 10 min needed for each run) with no degradation. Due to its "disposable" property, disposable working electrode could be discarded if the detection sensitivity decreased to 80% so the time for polishing and reconditioning was spared and good reproducible results could be obtained. At last, the disposable electrode was applied for the determination of iodide in soil and sea water samples with the spiked recovery ranging from 96-104% and the detection limit of 0.5 microg/L (10 microL injection, three times of the baseline noise).     

Voltammetric determination of cysteamine at multiwalled carbon nanotubes paste electrode in the presence of isoproterenol as a mediator

A sensitive electrochemical sensor for the determination of cysteamine(CA) was developed using a modified multiwall carbon nanotube paste electrode(MWCNTPE) with isoproterenol(ISPT) as a mediator.This modified electrode showed very high electrocatalytic activity for the anodic oxidation of CA.Under the optimized conditions,the electrocatalytic peak current showed a linear relationship with CA concentration in the range of 0.3–450.0 mmol/L with a detection limit of 0.09 mmol/L CA.The modified electrode was used for the determination of CA in real samples such as urine and drug samples.     

Highly sensitive determination of promazine in pharmaceutical and biological samples using a ZnO nanoparticle-modified ionic liquid carbon paste electrode

In this work we describe the first report for the determination of promazine using a nanostructuremodified ionic liquid carbon paste electrode in aqueous solutions. To achieve this goal, a novel modified carbon paste electrode using ZnO nanoparticles and 1-methyl-3-butylimidazolium bromide as a binder(ZnO/NPs/ILs/CPE) was fabricated. The oxidation peak potential of promazine at the surface of the ZnO/NPs/ILs/CPE appeared at 685 m V, which was about 65 m V lower than the oxidation potential at the surface of CPE under similar conditions. Also, the peak current was increased to about 4.0 times higher at the surface of ZnO/NPs/ILs/CPE compared to that of CPE. The linear response range and detection limit were found to be 0.08–450 and 0.04 mmol/L, respectively. The modified electrode was successfully used for the determination of promazine in real samples with satisfactory results.     

Ion-selective carbon-paste electrodes for halides and silver(I) ions

The behaviour of a simple type of ion-selective electrode for halogens and silver has been studied. The electrode consists of a plastic body filled with carbon paste, the surface of which can be easily renewed. The paste composition is based on carbon-nujol (5:1, w/v) or carbon-paraffin wax (3:1,w/w) containing a prepared mixture of silver halide-silver sulphide (1–30%). The electrodes have low ohmic resistance and show a rapid Nernstian response (within 2–5 mV) for halide and silver ions down to 5·10^-5M chloride, 1·10^-5M bromide and 5·10^-7M iodide with the respective electrodes. Ions forming very stable complexes with halide or silver and those having strong oxidizing or reducing action interfere.     

Determination of trace metals by anodic stripping voltammetry using a bismuth-modified carbon nanotube electrode

A bismuth-modified carbon nanotube electrode (Bi-CNT electrode) was employed for the determination of trace lead, cadmium and zinc. Bismuth film was prepared by in situ plating of bismuth onto the screen-printed CNT electrode. Operational parameters such as preconcentration potential, bismuth concentration, preconcentration time and rotation speed during preconcentration were optimized for the purpose of determining trace metals in 0.1M acetate buffer solution (pH 4.5). The simultaneous determination of lead, cadmium and zinc was performed by square wave anodic stripping voltammetry. The Bi-CNT electrode presented well-defined, reproducible and sharp stripping signals. The peak current response increased linearly with the metal concentration in a range of 2-100 microg/L. The limit of detection was 1.3 microg/L for lead, 0.7 microg/L for cadmium and 12 microg/L for zinc (S/N=3). The Bi-CNT electrode was successfully applicable to analysis of trace metals in real environments.     

Determination of trace amounts of lead and cadmium using a bismuth/glassy carbon composite electrode

We examined the use of a bismuth-glassy carbon (Bi/C) composite electrode for the determination of trace amounts of lead and cadmium. Incorporated bismuth powder in the composite electrode was electrochemically dissolved in 0.1 M acetate buffer (pH 4.5) where nanosized bismuth particles were deposited on the glassy carbon at the reduction potential. The anodic stripping voltammetry on the Bi/C composite electrode exhibited well-defined, sharp and undistorted peaks with a favorable resolution for lead and cadmium. Comparing a non-oxidized Bi/C composite electrode with an in-situ plated bismuth film electrode, the Bi/C composite electrode exhibited superior performance due to its much larger surface area. The limit of detection was 0.41 μg/L for lead and 0.49 μg/L for cadmium. Based on this study, we are able to conclude that various types of composite electrodes for electroanalytical applications can be developed with a prudent combination of electrode materials.     

Determination of traces of copper by anodic stripping voltammetry at a rotating carbon paste disk electrode modified with poly(1,8-diaminonaphtalene)

In the present work, carbon paste electrodes (CPE) modified with conducting polymers 1,8-diaminonaphtalene (DAN) was developed for the voltammetric determination of Cu(II). The modified electrode exhibited a significantly increased sensitivity and selectivity for Cu²⁺ compared with a bare carbon paste electrode. Copper(II) was preconcentrated at open circuit on the modified electrode. The measurements were carried out using a rotating disk electrode (RDE) as working electrode. The experimental parameters for the determination of Cu(II) were optimized. The Cu(II) ions were chemically deposited onto the surface of poly DAN-CPE in an acidic medium. Under the optimum conditions, a linear calibration graph was obtained in the concentration range of 0.1 to 250 ppb with a correlation coefficient of 0.9998. The relative standard deviation for 6 successive determinations was 4.7%. A study of interfering substances was also performed, and the method was applied to the direct determination of copper in real samples like tap water and orange juice samples. The article is published in the original.     

Determination of Iodide and Idoxuridine at a Glutaraldehyde‐Cross‐Linked Poly‐L‐Lysine Modified Glassy Carbon Electrode

The detection limit (about 0.017 μg mL^?1) for voltammetric determination of iodide (peak at +0.87 V vs. Ag/AgCl at pH 2) at a glutaraldehyde‐cross‐linked poly‐L ‐lysine modified glassy carbon electrode involving oxidation to iodine was found to be several orders of magnitude lower than that for the voltammetric determination on a bare glassy carbon electrode. This method was applied successfully to the determination of iodide in two medicinal formulations. Idoxuridine was determined indirectly at the same electrode by accumulating it first at ?0.8 V vs. Ag/AgCl. At this potential the C? I bond in the adsorbed idoxuridine is reduced giving iodide, which is then determined at the modified electrode. The method was successfully applied to the determination of idoxuridine in a urine sample.     

Used gold nano-particles as an on/off switch for response of a potentiometric sensor to Al(III) or Cu(II) metal ions

The potentiometric response of a carbon paste electrode modified with silica sol-gel and mercaptosuccinic acid (MSA) in the presence and absence of gold nano-particles was studied. The results showed that the electrode with gold nano-particles was responded to Al(3+) ions as a hard metal ion. On the other hand, the electrode without gold nano-particles was responded to copper ions as a soft metal ion. The electrodes without and with gold nano-particles exhibits a Nernstian slope of 29.1 and 19.2 mV decade(-1) for copper and aluminum ions over a wide concentration range of 4.3×10(-7)-1.0×10(-2) and 4.5×10(-7)-1.6×10(-3) mol L(-1), respectively. The detection limits of electrodes were 4.0×10(-7) and 1.6×10(-7) mol L(-1) for copper and aluminum ions, respectively.     

Flow-injection determination of iodide with a silver electrode

A procedure is developed for the flow-injection determination of iodide using a modified silver electrode; it extends the analytical range of iodide by an order of magnitude as compared to potentiometric determination using an iodide-selective electrode with a polycrystalline membrane. The detection limit is 7 μg/L. The procedure was used to determine iodide in natural mineral waters and model solutions. The throughput was 20–25 samples/h.     

Voltammetric characteristics of diazinon on carbon paste electrode modified with tris(ethylenediamine) cobalt(II) iodide

In this study, cyclic and differential pulse voltammetric methods were used to investigate the electrochemical behavior of diazinon at carbon paste electrode modified with tris(ethylenediamine) cobalt(II) iodide ([Co(en)₃]I₂). Cobalt complex showed an anodic peak at 620 mV (vs. Ag/AgCl, in KNO₃ 0.1 M as supporting electrolyte) at carbon paste modified electrode. In the presence of diazinon, anodic peak intensity increased with increasing concentration of diazinon that confirmed electrocatalytic activity of cobalt complex for oxidation of diazinon (EC’ mechanism). Under optimized conditions, a linear calibration curve for diazinon was obtained in the range from 0.05 to 27 mg/L with detection limit 0.0075 mg/L (3S _b /m). Applications of the modified electrode to the determination of diazinon in different water samples were also tested. The results showed a very good precision (RSD < 0.04%) and very stable voltammetric response towards diazinon.