二(乙基黄原酸基)金属配合物为中性载体高选择性碘离子电极的研究

本文研究了二(乙基黄原酸基)金属配合物为中性载体的阴离子选择性电极,其中二(乙基黄原酸基)钴(Ⅱ)对碘离子有高的选择性, 且电极呈现反Hofmeister行为, 其选择次序是: I^->SCN^->NO2^->Br^->ClO4^->SO4^2^->NO3^->Cl^-, 采用交流阻抗和光谱分析技术研究了电极的响应机理, 并将电极用于药品分析,结果令人满意。     

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.     

Semifluorinated Polymers as Ion‐selective Electrode Membrane Matrixes

Most commercially available fluorous polymers are ill suited for the fabrication of ion‐selective electrode (ISE) membranes. Therefore, we synthesized semifluorinated polymers for this purpose. Ionophore‐free ion‐exchanger electrodes made with these polymers show a selectivity range (≈14 orders of magnitude) that is nearly as wide as found previously for liquid fluorous ion‐exchanger electrodes. These polymers were also used to construct ISE membranes doped with fluorophilic silver ionophores. While the resulting ISEs were somewhat less selective than their fluorous counterparts, the semifluorinated polymers offer the advantage that they can be doped both with fluorophilic ionophores and traditional lipophilic ionophores, such as the silver ionophore Cu(II)‐I (o ‐xylylenebis[N,N ‐diisobutyldithiocarbamate]). We also cross‐linked these polymers, producing very durable membranes that retained broad selectivity ranges. K⁺ ISEs made with the cross‐linked semifluorinated polymer and the ionophore valinomycin showed selectivities similar to those of PVC membrane ISEs but with a superior thermal stability, the majority of the electrodes still giving a theoretical (Nernstian) response after exposure to a boiling aqueous solution for 10 h.     

Variability of selectivity coefficients of solid-state ion-selective electrodes

The generalized model for the selectivity mechanism of solid-state ion-selective electrodes has been experimentally verified. The experimental parameters investigated were the concentration of interfering ion, temperature and stirring. Among the systems studied were electrodes sensitive to chloride (bromide, iodide), bromide (chloride, iodide), iodide (chloride, bromide), silver (copper, lead), copper (silver, lead) and lead (silver, copper), the species given in brackets being considered as the interferents. The model has been confirmed except for cases where the concentration of ions formed at the electrode surface by metathesis is too small to be the factor that dictates the electrode potential.     

Determination of SCN- in urine and saliva of smokers and non-smokers by SCN(-)-selective polymeric membrane containing a nickel(II)-azamacrocycle complex coated on a graphite electrode.

The construction, performance characteristics, and application of a novel polymeric membrane coated on a graphite electrode with unique selectivity towards SCN- are reported. The electrode was prepared by incorporating Ni(II)-2,2,4,9,9,11-hexamethyltetraazacyclotetradecanediene perchlorate into a plasticized poly(vinyl chloride) membrane. The influences of membrane composition, pH and foreign ions were investigated. The electrode displays a near Nernstian slope (-57.8 mV decade-1) over a wide concentration range of 1 x 10(-7)-1 x 10(-1) M of SCN- ion. The electrode has a detection limit of 4.8 x 10(-8) M (2.8 ng/cm3) SCN- and shows response times of about 15 s and 120 s for low to high and high to low concentration sequences, respectively. The proposed sensor shows high selectivity towards SCN- over several common organic and inorganic anions. The electrode revealed a great enhancement in selectivity coefficients and detection limit for SCN-, in comparison with the previously reported electrodes. It was successfully applied to the direct determination of SCN- in milk and biological samples, and as an indicator electrode in titration of Ag+ ions with thiocyanate.     

The Synthesis of Styrene/4'-vinyl-benzo-24-crown-8 Copolymer and Its Use in Potassium-Ion Selective Electrodes

A synthetic procedure has been developed for the preparation of styrene/4'-vinyl-benzo-24-crown-8 copolymer (SPV-B24C8). The resulting copolymer was used as a membrane carrier to construct a K+ ion-selective electrode. The electrode exhibits a Nernstian response for K+ ions over a wide concentration range. The nature of the plasticizer, the additive, the concentration of internal solutions in the electrodes and the composition of the membrane were investigated. The performance of the electrode in terms of electrode reproducibility, response stability and regeneration was also studied. The selectivity coefficients of the electrode for potential interferents including alkali, alkaline earth, some transition and heavy metal ions were found to be in the order of 10-3 or less. The electrode was successfully used for the determination of potassium ion in blood serum.     

Optimization of polymeric triiodide membrane electrode based on clozapine-triiodide ion-pair using experimental design

Central composite design (CCD) and response surface methodology (RSM) were developed as experimental strategies for modeling and optimization of the influence of some variables on the performance of a new PVC membrane triiodide ion-selective electrode. This triiodide sensor is based on triiodide-clozapine ion-pair complexation. PVC, plasticizers, ion-pair amounts and pH were investigated as four variables to build a model to achieve the best Nernstian slope (59.9 mV) as response. The electrode is prepared by incorporating the ion-exchanger in PVC matrix plasticized with 2-nitrophenyl octal ether, which is directly coated on the surface of a graphite electrode. The influence of foreign ions on the electrode performance was also investigated. The optimized membranes demonstrate Nernstian response for triiodide ions over a wide linear range from 5.0 x 10(-6) to 1.0 x 10(-2)mol L(-1) with a limit of detection 2.0 x 10(-6) mol L(-1) at 25 degrees C. The electrodes could be used over a wide pH range 4-8, and have the advantages of easy to prepare, good selectivity and fast response time, long lifetime (over 3 months) and small interferences from hydrogen ion. The proposed electrode was successfully used as indicator electrode in potentiometric titration of triiodide ions and ascorbic acid.     

Schiff碱型和仲胺型双冠醚II: 用双冠醚作载体的PVC膜钾离子选择性电极

用六个含二个苯并-15-冠-5单元的席夫碱型和仲胺型新型双冠醚作载体制备了钾离子选择性PVC膜电极,并研究了它们的电极行为,这些电极对所有的其它碱金属和碱土金属离子展现出显著的钾离子选择性,可期望有一定的应用价值.     

Calixarene-based potentiometric ion-selective electrodes for silver

Four lipophilic sulphur and/or nitrogen containing calixarene derivatives have been tested as ionophores in Ag(I)-selective poly (vinyl chloride) membrane electrodes. All gave acceptable linear responses with one giving a response of 50 mV/dec in the Ag(I) ion activity range 10(-4)-10(-1)M and high selectivity towards other transition metals and sodium and potassium ions. This ionophore was also tested as a membrane coated glassy-carbon electrode where the sensitivity and selectivity of the conventional membrane electrode was found to be repeated. The latter electrode was then used in potentiometric titrations of halide ions with silver nitrate.     

Biomass-modified carbon paste electrodes for monitoring dissolved metal ions

Electrodes were prepared by incorporating dried, nonliving biomass of a common lichen, Ramalina stenospora, and Sphagnum (peat) moss in carbon paste. The electrodes were tested on solutions containing Pb(II) and Cu(II) ions by immersing the electrode in the solution for selected periods of time to accumulate ions. Following this the electrode was connected to a potentiostat and the applied voltage scanned from −1.0 to +0.5 V vs. SCE. Any adsorbed metal ions were stripped back into solution at the appropriate oxidizing voltage. The ratio of biomass to mineral oil to graphite has been found to be crucial to electrode performance. Different ratios of the three components using the lichen Ramalina stenospora were evaluated for maximum electrode performance. Only two electrode compositions gave a good electrode response for lead. Electrodes containing peat moss were superior in performance to lichen-containing electrodes for lead. Electrodes based on the lichens Cladina evansii and Letharia vulpina, the marine algae Ulva lactuca and Sargassum fluitans, the blue-green alga Spirulina platensis, and the aquatic plant Eichhornia crassipes did not respond to lead at all. All functioning electrodes studies showed a poor response toward copper(II) ions.     

New cesium ion-selective electrodes based on anilino-(1,3-dioxo-2-indanylidene) acetonitrile derivatives

Cesium ion-selective PVC membrane electrodes based on anilino-(1,3-dioxo-2-indanylidene) acetonitrile derivatives as a novel class of neutral ionophores were examined. The ionophores were p-methoxyanilino-(1,3-dioxo-2-indanylidene) acetonitrile, p-methylanilino-(1,3-dioxo-2-indanylidene) acetonitrile and p-N,N-dimethylanilino-(1,3-dioxo-2-indanylidene) acetonitrile. The anilino-(1,3-dioxo-2-indanylidene) acetonitrile proved to work well with cesium, the corresponding electrodes display a response to this ion. The most favourable ionophore was p-methoxyanilino-(1,3-dioxo-2-indanylidene) acetonitrile, especially when the secondary ion exchanger potassium tetrakis (4-chlorophenyl) borate was incorporated in 2-nitrophenyl octyl ether for ion-selective electrode membrane construction. The response function was linear within the concentration range 10(-1)-2.5x10(-5) mol l(-1) and the slope was 52 mV decade(-1). The detection limit remained at 6.3x10(-6) mol(-1). The selectivity and response time of the electrode was studied and it was found that the electrode exhibited good selectivity for cesium over alkali, alkaline earth and some transition metal ions. The electrode response was stable over a wide pH range. The lifetime of the electrode was about 1 month.     

The potentiometric behavior of polymer-supported metallophthalocyanines used as anion-selective electrodes

Liquid polymer membrane electrodes based on nickel and manganese phthalocyanines were examined for use as anion-selective electrodes. The electrodes were prepared by incorporating the ionophores into plasticized poly(vinyl chloride) membranes, which were directly coated onto the surfaces of graphite electrodes. The resulting electrodes demonstrate near-Nernstian responses over a wide linear range of perchlorate anion (5 × 10⁻⁷ to 1 × 10⁻¹ M). The electrodes have a fast response time, submicromolar detection limits (5 × 10⁻⁷ M perchlorate), and could be used over a wide pH range of 3.5–10. The influences of lipophilic cationic and anionic additives on the response properties of the electrodes were investigated. The proposed sensors revealed high selectivity for perchlorate over a number of common inorganic and organic anions. The highest selectivity was observed for the electrode based on manganese phthalocyanine in the presence of the lipophilic anionic additive sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. Application of the electrodes to determine perchlorate in tap water and human urine is also reported.      

Solid-state reference electrodes based on carbon nanotubes and polyacrylate membranes

A novel potentiometric solid-state reference electrode containing single-walled carbon nanotubes as the transducer layer between a polyacrylate membrane and the conductor is reported here. Single-walled carbon nanotubes act as an efficient transducer of the constant potentiometric signal originating from the reference membrane containing the Ag/AgCl/Cl⁻ ions system, and they are needed to obtain a stable reference potentiometric signal. Furthermore, we have taken advantage of the light insensitivity of single-walled carbon nanotubes to improve the analytical performance characteristics of previously reported solid-state reference electrodes. Four different polyacrylate polymers have been selected in order to identify the most efficient reservoir for the Ag/AgCl system. Finally, two different arrangements have been assessed: (1) a solid-state reference electrode using photo-polymerised n-butyl acrylate polymer and (2) a thermo-polymerised methyl methacrylate:n-butyl acrylate (1:10) polymer. The sensitivity to various salts, pH and light, as well as time of response and stability, has been tested: the best results were obtained using single-walled carbon nanotubes and photo-polymerised n-butyl acrylate polymer. Water transport plays an important role in the potentiometric performance of acrylate membranes, so a new screening test method has been developed to qualitatively assess the difference in water percolation between the polyacrylic membranes studied. The results presented here open the way for the true miniaturisation of potentiometric systems using the excellent properties of single-walled carbon nanotubes.     

New polymeric membrane cadmium(II)-selective electrodes using tripodal amine based ionophores

Fabrication of PVC membrane electrodes incorporating selective neutral carriers for Cd(2+) was reported. The ionophores were designed to have different topologies, donor atoms and lipophilicity by attaching tripodal amine (TPA) units to the lipophilic anthracene (ionophore I) and p-tert-butylcalix[4]arene (ionophores II, III and IV). The synthesized ionophores were incorporated to the plasticized PVC membranes to prepare Cd(II) ion selective electrodes (ISEs). The membrane electrodes were optimized by changing types and amounts of ionic sites and plasticizers. The selectivity of the membranes fabricated from the synthesized ionophores was evaluated, the relationship between structures of ionophores and membrane characteristics were explored. The ionophore IV which composed of two opposites TPA units on the calix[4]arene compartment showed the best selectivity toward Cd(2+). The best membrane electrode was fabricated from ionophore IV (10.2 mmol kg(-1)) with KTpClPB (50.1 mol% related to the ionophore) as an ion exchanger incorporated in the DOS plasticized PVC membrane (1:2; PVC:DOS). The Cd-ISE fabricated from ionophore IV exhibited good properties with a Nernstian response of 29.4±0.6 mV decade(-1) of activity for Cd(2+) ions and a working concentration range of 1.6×10(-6)-1.0×10(-2)M. The sensor has a fast response time of 10s and can be used for at least 1 week without any divergence in potential. The electrode can be used in the pH range of 6.0-9.0. The proposed electrodes using ionophores III and IV were employed as a probe for determining Cd(2+) from the oxidation of CdS QDs solution and the real treatment waste water sample with excellent results.     

Ion-selective characteristics of heavy metal myristate liquid membrane electrodes

Liquid membrane electrodes of myristate soaps of heavy metals, namely copper, cadmium, zinc, nickel, cobalt, strontium and barium in a benzene-n-butanol mixture were prepared. Each electrode showed nernstian response in common metal ion test solution. The range of concentration of the test solution for the Nernstian behaviour lies between 10^?4 and 10^?1M. With a dissimilar metal ion in test solution the metal soap liquid membrane electrode indicates deviations from Nernst's equation depending on the nature of the metal ion, suggesting different selectivities for different ions. The selectivity ratios are therefore calculated.     

An evaluation of solvent mediators for ion-selective electrode membranes based on calcium bis(dialkylphosphate) sensors trapped in poly(vinyl chloride) matrices

This study on several alkan-1-ols, di-n-octylphenyl phosphorate and di-n-nonyl phthalate as solvent materials in ion-selective electrode membranes based on calcium bis(dialkylphosphate) sensors trapped in a PVC matrix indicates that the best electrodes are made with di-n-octylphenyl phosphonate. These are selective for calcium. The liquid alcohols readily exude from the PVC matrix, and solid alcohols are completely unsuitable for membrane fabrication. However, despite a tendency to be exuded, decan-1-ol gives acceptable electrodes responsive to bivalent cations if calcium bis (di-2-ethylhexylphosphate) is used as sensor. Several selectivity coefficients, k(caj), greater than unity were found, but though such values for j = Na or K do not involve complete loss of selectivity towards calcium, a value of K(CaCu) = 13 for a membrane with di-n-nonyl phthalate as mediator and calcium bis(di-n-decylphosphate) as sensor indicates greater selectivity for copper than for calcium.     

A Selective Film Based on Poly(3‐octylthiophene) Doped with Dihydroxyanthraquinone Sulfonate

A stable film of poly(3‐octylthiophene)–dihydroxyanthraquinone sulfonate has been synthesized electrochemically in non‐aqueous solution. The incorporation of dihydroxyanthraquinone sulfonate as an anionic complexing ligand into poly(3‐octylthiophene) film during electropolymerization was achieved and copper ions were accumulated by reduction on the electrode surface. The presence of dihydroxyanthraquinone sulfonate during the electrochemical polymerization of 3‐octylthiophene is shown to impact the sensitivity and the stability of the organic conducting film electrode response. The electroanalysis of copper(II) ions using conducting polymer electrode was achieved by differential pulse anodic stripping voltammetry with remarkable selectivity. The analytical performance was evaluated and linear calibration graphs were obtained in the concentration range of 50–400 ng mL^?1 copper(II) ion for 240 seconds accumulation time and the limit of detection was found to be 7.8 ng mL^?1. To check the selectivity of the proposed stripping voltammetric method for copper(II) ion, various metal ions as potential interferents were tested. The developed method was applied to copper(II) determination in certified reference material, NWRI‐TMDA‐61, trace elements in fortified water.     

Electrochemical charactreistics of membranes based on Mn(III) tetraphenylporphyrin

Anion-selective electrodes with polymer membranes based on manganese(III) tetraphenylporphyrin (TPP) complexes with various axial ligands (chloride, perchlorate, nitrate, and rhodanide) were studied. The electrodes showed high (compared with other anions) selectivity toward the salicylate anion in a wide range of concentrations at different pH values. The selectivity coefficients of membrane electrodes $K_{Sal^ - /X^{n - } }^{sel} $ were determined by the bi-ionic potential method. A selectivity series was obtained based on $K_{Sal^ - /X^{n - } }^{sel} $ , which differs from Hofmeister series for classical anion exchangers. The possibility of using these electrodes in clinical practice for determining salicylate ions in human blood was shown.     

Anion-selective properties of alkali metal-free lead phosphate glasses containing silver chloride and their application in an ion-selective electrode

Alkali-free lead phosphate glasses containing silver chloride have been developed for anion responsive sensors. From measurements of the final glass compositions by electron probe microanalysis, it became clear that some of chloride ions in the glass bulk were not volatilized during the glass melting process. Compared with phosphate glasses containing silver oxide, the new glass electrodes containing silver chloride could respond more rapidly, although the response behaviour for anionic species were similar. From the electrode potential vs. time curve for the anionic species, the potential rapidly reached equilibrium when these concentrations varied from 10^?5 to 10^?2 M. The response times, t₉₅, to thiocyanate of the new glass electrode and the phosphate glass electrode containing silver oxide were 30 and 110 s, respectively. Moreover, the response time required for an initial potential change with a concentration jump of thiocyanate with the new glass electrode was found to be independent of the membrane thickness within about 2 mm and of the measuring temperature between 15 and 40°C. It is concluded that the diffusion process of species such as silver ion in the glass bulk does not take part in the initial part of the response behaviour.     

Potentiometric detection of organic acids in liquid chromatography using polymeric liquid membrane electrodes incorporating macrocyclic hexaamines

Potentiometric detection employing coated-wire electrodes was applied to the determination of organic acids in liquid chromatography (LC). Poly(vinyl chloride)-based liquid membranes, incorporating lipophilic macrocyclic hexaamines as neutral ionophores were used as electrode coatings. The selectivity and sensitivity of the macrocycle-based electrodes were found to be superior to an electrode based on a lipophilic anion exchanger (a quaternary ammonium salt). Sensitive detection was obtained for the di- and tricarboxylic acids tartaric, malonic, malic, citric, fumaric, succinic, pyruvic, 2-oxoglutaric and maleic acids after separation in reversed-phase LC. Detection limits (signal/4sigmanoise=3) of 6 pmol for malonic acid and 2 pmol for maleic acid were attained. The detection was explained using a molecular recognition model. The hexaamine-based potentiometric electrodes had a 1-s response time at 1 ml min(-1) flow-rates. They were stable for at least 4 months, with an intra-electrode variation of 3.2% (n=5).