Lead-selective poly(vinyl chloride) membrane electrodes based on acyclic dibenzopolyether diamides

Lipophilic acyclic dibenzopolyether diamides, 12 kinds, have been designed to prepare solvent polymeric membrane ion-selective electrodes (ISEs) for Pb(2+). The ionophores include 1,5-bis[2-(N,N-dialkylcarbamoylmethoxy)phenoxy]-3-oxapentanes1-4, 1,5-bis[2-(N,N-dialkylcarbamoylpentadecyloxy)phenoxy]-3-oxapentanes 5-8, and 1,2-bis[2-(2'-N,N-dialkylcarbamoylpentadecyloxy)phenoxy]ethanes 9-12. Linear response concentration range of the ISE based on 9 is 3 x 10(-2) - 1 x 10(-6) M of Pb(2+) (average slope = 28.5 mV decade(-1)). Potentiometric selectivities of the ISEs based on 1-12 for Pb(2+) over other heavy metal cations, alkali metal cations, and alkaline earth metal cations have been assessed. These ISEs exhibit remarkably high selectivities for Pb(2+) relative to heavy metal cations, such as Cu(2+), Fe(2+), and Ni(2+), the selectivity coefficients (K(Pot)(Pb,Cu)) being 5 x 10(-5) - 6 x 10(-5) for 1-4 and ca. 6 x 10(-4) for 9. For the Pb(2+) selectivities over alkali metal cations, such as Na(+) and K(+), 9 which has an ethylene glycol spacer and a N,N-diethyl group is superior to other dibenzopolyether diamide ionophores 1-8 and 10-12.     

Lead-selective membrane electrodes based on dithiophenediazacrown ether derivatives

Three double-armed diazacrown ethers with two thiophene side groups, 7,16-dithenyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (DTDC), 7,16-dithenoyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (DTODC), and 7,16-di-(2-thiopheneacetyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (DTAODC), have been synthesized and used as novel neutral lead(II) ionophores in ion selective electrode applications. The relationship between the molecular structure of these ionophores and electrochemical properties (linear range, response time, selectivity) of the membrane electrode is discussed. The optimum conditions for the preparation of the electrodes are described. The optimized dithenoyldiazacrown had a detection limit of pPb = 5.7, and Nernstian range with slope 29.2 mV decade⁻¹ from pPb = 5.0 to 2.7. Mercury and silver ions are the major interferences. These electrodes are applied to potentiometric titrations of lead(II) ions and show promise for the determination of lead ions in water samples.     

Lead-selective electrodes based on lead(IV) oxide

Lead(IV) oxide electrodes are shown to give near-theoretical calibration slopes for lead(II) ions over the range 10^?3–10^?5 mol l^?1, and to have near-theoretical standard potentials in different acidic media. They are compared with lead sulphide-silver sulphide membrane electrodes and shown to be more tolerant of acidity and copper(II), mercury(II) and iron(III) ions. Iron(II) and manganese(II), however, interfere significantly. Some of the advantages of the lead(IV) oxide electrode are brought out in the determination of the solubility product of lead sulphate; implications for constructing phosphate- and sulphate-sensitive electrodes are mentioned.     

Ion-selectivity of plasticizers in poly(vinyl chloride) membrane electrodes

Electrode membranes were presented which contained only PVC and a plasticizer. The plasticizers studied were tris(2-ethylhexyl)phosphate, 2-nitrophenyl octyl ether and bis(1-butylpentyl)adipate. The response and selectivity of these ligand-free PVC electrodes towards alkali and alkaline earth cations are reported.     

邻菲咯啉冠醚衍生物为载体的伯胺药物电极及机理研究

合成了邻菲咯啉-18-冠-6等四种含邻菲咯啉结构的冠醚化合物, 并用作载体制备伯胺电极, 以苄胺为模型化合物, 研究了电极特性, 并制备了测试美西律药物的选择性电极。研究了实验条件对电极性能的影响。用正交多项式回归法优化电极的膜组成。苄胺电极的线性范围1.0×10^-5~0.1mol/L, 斜率55.6mV/pc, 检测下限2.0×10^-6mol/L。美西律电极的线性范围6.0×10^-6~0.1mol/L, 检测下限8.0×10^-7mol, 斜率58.0mV/pc。同时研究了冠醚推动伯胺穿透大块液膜的传输行为。     

Comparative evaluation of Dy(III) selective poly(vinyl) chloride based membrane electrodes of macrocyclic tetraimine Schiff's bases

Three different derivatives of macrocyclic tetraimine Schiff's base have been synthesized and explored as a neutral ionophores for preparing poly(vinyl chloride) based membrane sensors selective to Dy³⁺. The addition of sodium tetraphenyl borate and various plasticizers, viz., o-NPOE, DBP, DBBP, DOP and CN has been found to substantially improve the performance of the sensors. The best performance was obtained with the sensor no. 1 having membrane of Schiff's base (SL-1) with composition (w/w) SL-1 (4.5%): PVC (30.5%): o-NPOE (59.5%): NaTPB (5.5%). This sensor exhibits Nernstian response with slope 19.4 mV/decade of activity in the concentration range of  10⁻⁸ to 1.0 × 10⁻² M Dy³⁺, performs satisfactorily over wide pH range of (2.8-7.2) with a fast response time (10 s). The sensor was also found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of acetonitrile, methanol or ethanol. The proposed sensor can be used over a period of 1.5 months without significant drift in potentials. The sensor has been also utilized for the determination of Dy³⁺ level in different soil samples.     

Response of poly(vinyl chloride) electrodes based on the neutral carrier 1,4,7,10-tetraoxacyclododecane

Ion-selective electrodes based on the neutral carrier, 12-crown-4, in a poly(vinyl chloride) matrix were found to respond ideally, or almost ideally, to potassium, sodium, barium, strontium, magnesium, cobalt(II), nickel(II) and aluminum ions. The electrode showed good selectivity for Al³⁺ over Co²⁺ and Mg²⁺, and for Co²⁺ over Mg²⁺. Little selectivity was found for the other ions tested.     

Mercury(II) ion-selective electrodes based on heterocyclic systems

Mercury ion-selective electrodes (ISEs) were prepared with a polymeric membrane based on heterocyclic systems: 2-methylsulfanyl-4-(4-nitro-phenyl)-l-p-tolyl-1H-imidazole (I) and 2,4-diphenyl-l-p-tolyl-1H-imidazole (II) as the ionophores. Several ISEs were conditioned and tested for the selection of common ions. The electrodes based on these ionophores showed a good potentiometric response for Hg2+ ions over a wide concentration range of 5.0 x 10(5-) - 1.0 x 10(-1)M with near-Nernstian slopes. Stable potentiometric signals were obtained within a short time period of 20 s. The detection limits, the working pH range of the electrodes were 1.0 x 10(-5) M and 1.6-4.4 respectively. The electrodes showed better selectivity for Hg2+ ions over many of the alkali, alkaline-earth and heavy metal ions. Also sharp end points were obtained when these sensors were used as indicator electrodes for the potentiometric titration of Hg2+ ions with iodide ions.     

Potassium-selective PVC membrane electrodes based on bis- and poly(crown ether)s

Potassium-selective PVC membrane electrodes based on bis- and poly (crown ether)s containing benzo-15-crown-5 moiety as neutral carrier were prepared and selectivity coefficients for various monovalent ions were measured in order to elucidate the effect of complexing property of these crown ether derivatives on the electrode response. In the preference for potassium over sodium of the electrodes, these bis- and poly (crown ether)s were found to exceed the corresponding monocyclic crown ether considerably, which reflects the easy complexation of stable 2:1 complexes of crown ether ring and ion, derived from the cooperative effect of two adjacent crown ether rings.     

A chlorate ion-selective electrode based on a poly(vinyl chloride)-matrix membrane

An electrode has been prepared, consisting of a PVC membrane containing Corning 477316 nitrate liquid ion-exchanger in the chlorate form, which responds to chlorate ions. It has a faster response (1-2 sec) and lower limit of detection (3 x 10(-5)M) than the nitrate electrode for chlorate determination. Selectivity coefficients for the electrode towards several other ions have been measured.     

Electrically controlled separation of maleic acid and fumaric acid through a poly(vinyl alcohol)/poly(acrylic acid) composite membrane

The separation of maleic acid (MA) from a mixture of MA and fumaric acid (FA) was studied using an electrically activated polyelectrolyte gel membrane. The membrane was prepared through the iterative freezing-thawing of an aqueous solution containing poly(vinyl alcohol) and poly(acrylic acid). The separation of MA from an equimolar mixture (5 mM) of MA and FA using the membrane was performed under different conditions of pH (1–8) and electric fields (2–6 V). It was found that MA was separated from the mixture at pH 2 under an applied electric field of greater than 2 V because only the COOH groups of MA were dissociated at pH 2 and the MA⁻ ions were transported through the membrane toward the electrode opposite in sign to their charge.     

Plastic reference electrodes and plastic potentiometric cells with dispersion cast poly(3,4-ethylenedioxythiophene) and poly(vinyl chloride) based membranes

A simple procedure of preparing low cost, planar and disposable reference electrodes for potentiometric applications is presented. This method is essentially the same as used for obtaining all-plastic ion-selective electrodes and thus promising for simple fabrication of complete cells. Commercially available aqueous dispersion of poly(3,4-ethylenedioxythiophene) doped by poly(4-styrenesulfonate) ions (PEDOT-PSS, Baytron P) is simply cast on a non-conducting plastic support (transparent foil for laser printers). This layer is covered by a non-selective poly(vinyl chloride) based membrane containing solid AgCl and KCl, added to obtain a stable potential. The conducting polymer layer plays a double role, of electrical contact and ion-to-electron transducer, enhancing the potential stability. The reference electrodes obtained exhibit independence of the kind and concentration of electrolyte applied as well as very low sensitivity to interferences: redox reactants and H+ ions; they are also characterized by both potential stability and low polarisability, sufficient for potentiometric applications. Cells of plastic electrodes (indicator and reference ones) are tested using an arrangement with Pb2+ or Ca2+ selective sensors. Potentiometric characteristic of such cells is satisfactory, well comparable with that using a classical electrode arrangement.     

Highly selective thiocyanate poly(vinyl chloride) membrane electrode based on a cadmium-Schiff's base complex

A PVC membrane electrode based on a cadmium-salen (N,N'-bis-salicylidene-1,2-ethylenediamine) complex as an anion carrier is described. The electrode has an anti-Hofmeister selectivity sequence with a preference for thiocyanate at pH 1.5-11.0. It has a linear response to thiocyanate from 1.0 x 10(-6) to 1.0 x 10(-1) mol L(-1) with a slope of 59.1 +/- 0.2 mV per decade, and a detection limit of 7 x 10(-7) mol L(-1). This electrode has high selectivity for thiocyanate relative to many common organic and inorganic anions. The proposed sensor has a fast response time of approximately 15 s. It was applied to the determination of thiocyanate in a milk sample.     

Selective thiocyanate poly(vinyl chloride) membrane based on a 1,8-dibenzyl-1,3,6,8,10,13-hexaazacyclotetradecane-Ni(II) perchlorate

A highly selective poly(vinyl chloride) (PVC) membrane electrode based on 1,8-dibenzyl-1,3,6,8,10,13-hexaazacyclotetradecane-Ni(II) as a membrane carrier with unique selectivity toward thiocyanate is reported. The influence of membrane composition, pH and foreign anions were investigated. The sensor exhibits a Nernstian response for thiocyanate over a wide concentration range of 3.3×10⁻⁶ to 0.10 M, with a slope 58.4±0.3 mV per decade. The limit of detection is 3.0×10⁻⁶ M SCN⁻. The sensor has a response time of <20 s and can be used for at least 2 months without any considerable divergence in potential. The proposed electrode shows fairly a good discriminating ability towards SCN⁻ ion in comparison to other anions. It was successfully applied to direct determination of thiocyanate in urine and saliva and it was also used as an indicator electrode in titration of thiocyanate with Ag⁺ ions.     

New chemical hydrogels based on poly(vinyl alcohol)

The syntheses of two new types of chemical hydrogels based on poly(vinyl alcohol), PVA, are reported. Common to both synthetic routes is the preparation of a telechelic PVA (tel-PVA) obtained by periodate splitting of the vicinal diol units present in few percent along the chain. tel-PVA was then used as crosslinking agent with chitosan and PVA in two simple reactions in aqueous phase such as reductive alkylation of chitosan and acetalyzation of PVA. Both reactions yielded firm wall-to-wall networks showing marked differences in their swelling capability. © 1996 John Wiley & Sons, Inc.