A new selenite selective membrane electrode and its application

A new membrane ion selective electrode sensitive to selenite ion has been developed. The electrode consisted of 1,2-phenylenediamine selen complex PIS (piaselenol) as the active material, PVC or SR (silicon rubber) as membrane matrix and DBF (dibutylphtalate) as plasticizer. This electrode showed linear response for selenite ion in the 10(-5)-10(-1)M concentration range. The slope of the linear portion was 21 mV/10-fold change in selenite concentration. The effect of membrane composition and membrane thickness on electrode response was studied and the electrode which contains 2% PIS, 49% PVC and 49% DBF was found to be the most sensitive one to selenite. The slope of the electrode did not change for 2 months and the pH change did not affect the response of the electrode in pH range of 3-9. The interferences of SO(4)(2-), SO(3)(2-), S(2-), HPO4(2-), CI(-), Br(-), and I(-) are investigated and while no interference was observed for SO(4)(2-), SO(3)(2-), S(2-) and I(-), a very small interference was observed for CI(-) and Br(-). The selenium present in anodic slime is determined using this electrode.     

Preparation and application of selenite ion selective electrode

A new selenite ion selective electrode using 4,6-dibromopiaselenole as active material, PVC as membrane matrix and dibutyl phthalate as plasticizer has been developed. An analytically useful potential change occurs from about 10(-6)-10(-1)M Se(IV), and the slope of the linear portion is -23.6 mV/10-fold change in Se(IV) concentration at a temperature of 21 degrees . The electrode shows fairly good selectivity for selenite ion over other anions and has been used for the successful determination of total selenium in human hair.     

Preparation and application of a new glucose sensor based on iodide ion selective electrode

An electrode for glucose has been prepared by using an iodide selective electrode with the glucose oxidase enzyme. The iodide selective electrode used was prepared from 10% TDMAI and PVC according our previous study. The enzyme was immobilized on the iodide electrode by holding it at pH 7 phosphate buffer for 10 min at room temperature. The H₂O₂ formed from the reaction of glucose was determined from the decrease of iodide concentration that was present in the reaction cell. The iodide concentration was followed from the change of potential of iodide selective electrode. The potential change was linear in the 4×10⁻⁴ to 4×10⁻³ M glucose concentration (75-650 mg glucose/100ml blood) range. The slope of the linear portion was about 79 mV per decade change in glucose concentration. Glucose contents of some blood samples were determined with the new electrode and consistency was obtained with a colorimetric method. The effects of pH, iodide concentration, the amount of enzyme immobilized and the operating temperature were studied. No interference of ascorbic acid, uric acid, iron(III) and Cu(II) was observed. Since the iodide electrode used was not an AgI-Ag₂S electrode, there was no interference of common ions such as chloride present in biological fluids. The slope of the electrode did not change for about 65 days when used 3 times a day.     

Organic-inorganic composite cation-exchanger: poly-o-toluidine Zr(IV) phosphate-based ion-selective membrane electrode for the potentiometric determination of mercury

A new heterogeneous precipitate of an organic-inorganic composite cation-exchanger poly-o-toluidine Zr(IV) phosphate was utilized for the preparation of a Hg(II) ion-sensitive membrane electrode for the determination of Hg(II) ions in real aqueous as well as in real samples. The electrode showed good potentiometric response characteristics, and displayed a linear log[Hg(2+)] versus EMF response over a wide concentration range of 1 x 10(-1) - 1 x 10(-6) M with a Nernstian slope of 30 mV per decade change in concentration with a detection limit of 1 x 10(-6). The membrane electrode showed a very fast response time of 5 s and could be operated well in the pH range 2 - 8. The selectivity coefficients were determined by the mixed-solution method, and revealed that the electrode was selective in the presence of interfering cations; however most of these did not show significant interference in the concentration range of 1 x 10(-1) - 1 x 10(-4) M. The lifetime of the membrane electrode was observed to be 120 days. The analytical utility of this electrode was established by employing it as an indicator electrode in the potentiometric titrations of Hg(2+) ions from a synthetic mixture as well as drain water.     

Construction and analytical applications of plastic membrane electrode for oxymetazoline hydrochloride.

A new oxymetazoline (OM) ion-selective PVC membrane electrode based on the ion associate of OM with phosphotungstic acid was prepared. The electrode exhibits a linear response with a mean calibration graph slope of 57.16 mV decade(-1) at 25 degrees C within the concentration range of 1.96 x 10(-5) - 1 x 10(-2) M OMCl. The change in the pH within the range of 1.0 - 9.4 did not affect the electrode performance. The standard electrode potentials were determined at different temperatures and used to calculate the isothermal coefficient of the electrode (-0.001233 V). The electrode showed a very good selectivity for OM with respect to a large number of inorganic cations and compounds. The standard addition method and potentiometric titration were applied to the determination of (OM) with RSD not exceeding 1.19%.     

Co-immobilization of polymeric luminol,iron(II) tris(5-aminophenanthroline) and glucose oxidase at an electrode surface,and its application as a glucose optrode

The anodic polymerization of 3-aminophthalhydrazide (luminol) and iron(II) tris 5-aminophenanthroline (Fe(phen-NH2)3(2+)) has been reported in this paper. A bilayer electrode was developed based on these polymers and the ITO conductive glass (denoted ITO[Fe(phen-NH2)3(2+)]luminol electrode). This electrode emitted light (lambdaem: 430 nm) as it was brought into contact with H2O2. At pH 10, the resulting electrochemiluminescence (ECL) showed a linear relationship with the concentration of H2O2 in the range of 10 microM(-1) mM. This bilayer electrode also showed an application potential for the detection of glucose after being further modified with glucose oxidase (denoted ITO[Fe(phen-NH2)3(2+)]luminol]GOx electrode). Although the resulting ECL decayed more rapidly in concentrated glucose solutions (e.g., I M) because of the consumption of luminol during use, the decay became less severe in diluted glucose solutions (e.g., 10 mM). According to the flow injection analysis, a linear relationship existed between the ECL and the concentration of glucose from 10(-5)-10(-3) M at pH 9. The detection limit could reach a level of 5 x 10(-5) M at this pH.     

Potentiometric determination of trace silver based on the use of a carbon paste electrode

A carbon paste electrode used as a sensor for silver has been developed and electrode response characteristics have been investigated. The electrode exhibits linear response to the logarithm of the concentration of silver from 5 x 10(-7)M to 1 x 10(-2)M, with a response slope of 63 +/- 2 mV. The detection limit according to IUPAC recommendations is 1 x 10(-7)M. This electrode has been used to determine trace silver in fixing solutions and waste electroplate solutions with good results.     

A coated-metal enzyme electrode for urea determinations

A potentiometric enzyme electrode is reported in which an enzyme immobilized in polyvinyl chloride is used to coat an antimony metal electrode to detect changes in pH when the electrode is immersed in a solution of the enzyme substrat. As an example, urea is determined in solution by using immobilized urease on an antimony electrode, giving a linear concentration range of 5.0 × 10^-4–1.0 × 10^-2 M urea with a slope of 44 mV per decade change in urea concentration. The response slope is stable for about 1 week, with response times in the range 1–2 min, but with absolute potential changes occurring from day to day.     

New plastic membrane and carbon paste ion selective electrodes for the determination of triprolidine.

Triprolidine (Trip) ion selective electrodes of three types: the conventional polymer membrane (I), graphite coated electrode (II) and carbon paste electrode (III), have been prepared, based on the ion pair of triprolidine hydrochloride with sodium tetraphenylborate. The electrodes exhibit a linear response with a mean calibration graph slope of 56.12, 55.00 and 54.32 mV decade(-1) at 25 degrees C for I, II and III, respectively, within the concentration ranges 1.96 x 10(-5) - 1.00 x 10(-2) M for I and 3.84 x 10(-5) - 1.00 x 10(-2) M for II and III. The detection limits are 1.13+/-0.13 x 10(-5), 1.70+/-0.06 x 10(-5) and 1.78+/-0.05 x 10(-5) M for the three electrodes, respectively. The change of pH within the ranges 4.85 - 8.75 and 4.70 - 8.50 for I and III, respectively, did not affect the electrode performance. The standard electrode potentials were determined at different temperatures and were used to calculate the isothermal coefficient of the electrode. The electrodes showed a very good selectivity for Trip with respect to a large number of inorganic cations and compounds. The standard addition method was applied to the determination of TripCl in pure solution, pharmaceutical preparations, and urine samples.     

Nitrate-selective membrane electrode based on bis(2-hydroxyanil)acetylacetone lead(II) neutral carrier.

A nitrate-selective electrode based on a recently synthesized bis(2-hydroxyanil)acetylacetone lead(II) complex [(haacac)Pb] has been developed. Among different compositions studied, a membrane containing 30.7% poly(vinyl chloride) (PVC), 61.3% dibutyl phthalate (DBP) as a plasticizer, 3% methyltrioctylammonium chloride (MTOAC) as a cationic additive and 5% ionophore (all w/w) exhibited the best potentiometric response toward nitrate ion in aqueous solutions. The potentiometric response of the electrode was linear with a Nernstian slope of -58.8 mV decade(-1) within the NO3- concentration range of 2 x 10(-5)-1 x 10(-1) mol dm(-3). The response time of the electrode was < or =10 s over the entire linear concentration range of the calibration plot. The electrode is suitable for use within the pH range of 5.3-11. The selectivity coefficients for the proposed electrode were improved for some interferences, when compared with those of commercially available nitrate-selective electrodes.     

Determination of sulfate ion by potentiometric back-titration using sodium tetrakis (4-fluorophenyl) borate as a titrant and a titrant-sensitive electrode

A potentiometric back-titration method for the determination of sulfate ions using a plasticized poly(vinyl chloride) membrane electrode sensitive to a titrant is described. The method is based on ion association between the excess of 2-aminoperimidinium added to the sulfate ion in the sample and sodium tetrakis (4-fluorophenyl) borate (FPB) in the titrant. The titration end-point was detected as a sharp potential change due to an increase in the concentration of the free FPB at the equivalence point. The end-point was detected even in the presence of a 20-fold excess of common cations and anions relative to the concentration of the sulfate ion within approximately 2% of titration error. A linear relationship between the concentration of the sulfate ion and the end-point volume of the titrant exists in the sulfate ion concentration range from 2x10(-4) to 3x10(-3) mol l(-1) using 10(-2) mol l(-1) FPB solutions as the titrant. The present method could be applied to determine sulfate ions in sea water.     

Anion selective polymeric membrane electrodes based on cyclopalladated amine complexes

The potentiometric anion selectivity of two polymer membrane based electrodes (I and II) formulated with two new cyclopalladated amine complexes as the active components are examined. The electrodes exhibit a non-Hofmeister selectivity pattern with a significantly enhanced response towards thiocyanate, iodide and nitrite. The graph potential versus log c is linear over the concentration range 10(-6)-6x10(-2) M thiocyanate with electrode I and 10(-6)-10(-3) M with electrode II; 10(-5)-10(-2) M iodide with electrode I and 10(-3)-6x10(-2) M with electrode II; and 10(-3)-6x10(-2) M nitrite with both electrodes. The influence of the plasticizer and pH are studied. The potentiometric selectivity coefficients for I, II and blank membrane electrodes are reported. The selective interaction between Pd(II) thiocyanate, iodide and nitrite is postulated to be the reason for its higher response.     

聚乙烯醇/酸化碳纳米管高亲水性三维孔电极膜的制备与电化学性能

在酸化碳纳米管的基础上, 采用电泳沉积和冷冻-解冻循环交联工艺制备了高亲水性聚乙烯醇/酸化碳纳米管(PVA/a-MWCNTs)水凝胶电极膜. 该电极膜具有三维连通纳米孔结构, 同时还具有高电活性面积、 低表面电荷传递电阻以及良好的扩散通透性等电化学特性. 该电极膜对多巴胺(DA)有很好的电化学响应特性, 并且对多巴胺的电化学还原电流不受抗坏血酸(AA)干扰, 在过量抗坏血酸存在下, PVA/a-MMWCNTs水凝胶电极膜对多巴胺还原电流的一阶导数与多巴胺的浓度在2×10^-6 ~2×10^-3 mol/L范围内呈线性关系, 检出限达到1×10^-6 mol/L, 灵敏度达到12.3 μA/(mmol·L^-1), 同时还表现出了较好的电极稳定性和重现性.     

Sorption of selenite ions on hematite

The sorption of selenite from aqueous solutions onto hematite was investigated as a function of pH (2-12), ionic strength (0.01-0.1 M), and concentration of selenium (10(-7)-10(-2) M). The sorption may proceed according to two processes: surface complexation, followed by the precipitation of ferric selenite starting at approximate [Se] = 4 x 10(-4) M (surface coverage>ca. 2 at nm(-2)). The sorption isotherms have been fitted by a Tempkin equation. A surface complexation model (2-pK/Constant Capacitance Model) was used to fit the sorption data. The nature of the surface species of selenite cannot be determined by modeling since monodentate >FeOSe(O)O- or >FeOSe(O)OH and bidentate (>FeO)2SeO surface complexes are both able to fit the experimental data. The reversibility and kinetics of sorption were also studied. The affinity of selenite ions toward hematite, expressed as the distribution coefficient with respect to the surface area (K(D) in L m(-2)), was compared with results published for other ferric oxides (goethite and amorphous ferric oxide). It was found that the reactivity toward selenite is similar, contrary to acid-base properties which depend on the nature of the oxide and its level of purity.     

2-氨基酚在离子液体-壳聚糖复合修饰电极上的电化学行为及其测定

本文采用离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF6)和壳聚糖(Chi)作为修饰剂,制备了新型修饰电极BMIMPF6-Chi/GCE,采用该修饰电极研究了2-氨基酚(OAP)的电化学行为,并对其进行了分析检测。实验结果表明,在pH=6.5的PBS缓冲液中,OAP于0.197V处出现一个明显的氧化峰,逆向扫描无还原峰,说明OAP在该电极上的电化学行为是不可逆的。OAP氧化峰电流与扫速的1/2次方在40～280 mV.s-1的范围内呈良好的线性关系,表明该电极过程受扩散控制。在最佳实验条件下,OAP峰电流与其浓度在4.0×10-7～2.0×10-4mol.L-1范围内呈良好的线性关系,Ipa(μA)=-0.534-18.424c(10-4mol.L-1),R=0.999,检出限1.4×10-7mol.L-1(S/N=3),回收率为96.8～103.7%。     

Bis(2-hydroxyacetophenone)ethylenediimine as a neutral carrier in a coated-wire membrane electrode for lead(II).

A coated-wire ion-selective electrode (CWISE), based on a Schiff base as a neutral carrier, was successfully developed for the detection of Pb(II) in aqueous solution. CWISE exhibited a linear response with a Nernstian slope of 29.4 +/- 0.5 mV/decade within the concentration range of 1.0 x 10(-5) - 1.0 x 10(-1) M lead ion. CWISE has shown detection limits of 5.0 x 10(-6) M. The electrode exhibited good selectivity over a number of alkali, alkaline earth, transition and heavy metal ions. This sensor yielded a steady potential within 10 to 20 s at a linear dynamic range. The electrode was suitable for use in aqueous solutions in a pH range of 2.0 to 5.0. Applications of this electrode for the determination of lead in real samples and as indicator electrode for potentiometric titration of Pb2+ ion using K2CrO4 are reported.     

Construction of a new Hg(2+)-selective liquid-state electrode

The construction and basic characteristics of a new liquid-state Hg(2+)-selective membrane electrode are discussed. The membrane consists of the PAN chelate of Hg(II), dissolved in CHCl(3). The linear response range of the electrode is 10(-1) -10(-5)M Hg(2+) with a slope of 28.5 mV/decade of concentration. The response time of the electrode in dilute solutions is less than 3 min, and in concentrated solutions it is only a few sec. The electrode has been used in precipitation or complexation titrations in which Hg(2+) is involved (e.g., in the determination of some organic compounds in drug synthesis).     

Chemically modified carbon paste electrode for determination of copper(II) by potentiometric method

The utility of carbon paste electrode modified with DTPT (3,4-dihydro-4,4,6-trimethyl-2(1H)-pyrimidine thione) for the potentiometric determination of Cu(II) in aqueous medium is demonstrated. The electrode exhibits linear response to Cu(II) over a wide concentration range (9.77x10(-7)-7.6x10(-2)) with Nernstian slope of 30+/-2 mV per decade. It has a response time of about 45 s and can be used for a period of two months with good reproducibility. The detection limit of this electrode was 7.0x10(-7) M. The proposed electrode shows a very good selectivity for Cu(II) over a wide variety of metal ions. This chemically modified carbon paste electrode was successfully used for the determination of Cu(II) in electronics waste sample solution.     

Uranyl-selective PVC membrane electrodes based on some recently synthesized benzo-substituted macrocyclic diamides

Four different recently synthesized macrocyclic diamides were studied to characterize their abilities as uranyl ion carriers in PVC membrane electrodes. The electrodes based on macrocycle 1,18-diaza-3,4;15,16-dibenzo-5,8,11,14,21,24-hexaoxacyclohexaeicosane-2,17-dione resulted in a Nernstian response for UO(2)(2+) ion over wide concentration ranges. The linear concentration range for the polymeric membrane electrode (PME) is 3.0x10(-6)-8.2x10(-3) M with a detection limit of 2.2x10(-6) and that for the coated graphite electrode (CGE) is 5.0x10(-7)-1.5x10(-3) M with a detection limit of 3.5x10(-7) M. The electrodes manifest advantages of low resistance, very fast response and, most importantly, good selectivities relative to a wide variety of other cations.     

Quartz Crystal Microbalance for Selenite Sensing Based on Growth of Cadmium Selenite Crystals Immobilized on a Monolayer of Phosphorylated 11-Mercapto-1-Undecanol

 A quartz crystal microbalance (QCM) sensor for selenite ions in aqueous solution was constructed based on crystal formation of cadmium selenite, immobilized with a self-assembly monolayer (SAM) of phosphorylated 11-mercapto-1-undecanol (MUD) on a QCM gold electrode surface. The mass change caused by the selective adsorption of selenite ions on the cadmium selenite crystals at the solid/solution interface was detected by the QCM. The response (−ΔF) of the modified QCM oscillator increased with increasing selenite ion concentrations in sample solutions, ranging from 9.7×10⁻⁵ to 9.0×10⁻⁴ M at pH 7.4. The synthetic process of anchoring cadmium selenite crystals on the phosphorylated MUD organic film was also followed by using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The atomic concentrations measured by XPS confirmed the crystal growth of cadmium selenite on the phosphorylated MUD SAM at the QCM gold electrode surface. From the AFM images, changes in surface topographic features were followed: the MUD SAM and phosphorylated MUD on the QCM gold electrode had similar surface roughness; however the difference for the cadmium selenite film on the phosphorylated MUD SAM was clearly seen. The observed QCM frequency change of the modified QCM oscillator per unit time was found to be proportional to the square of the supersaturation of cadmium selenite, indicating the crystal growth of cadmium selenite at the solid/solution interface. The modified QCM oscillator exhibited selectively strong QCM response to SeO₃ ²⁻ ion. In contrast, the responses to tested interfering anions were almost negligible. The order of anion selectivities of the present modified QCM sensor was SeO₃ ²⁻≫CO₃ ²⁻>SeO²⁻ ₄, SO₄ ²⁻, Br⁻, I⁻, NO₃ ⁻. These selectivities were basically attributable to the differences in solubility products and solubilities for the salts of each anion with cadmium (II) ion. Received May 12, 1998. Revision December 29, 1998.