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.     

Copper(II)-selective electrode using 2,2'-dithiodianiline as neutral carrier

Poly(vinyl chloride) membrane electrode, that is highly selective and sensitive to Cu(II) ions, was developed by using 2,2'-dithiodianiline and dibutyl phthalate as carrier and plasticizer, respectively. The electrode exhibits good potentiometric response for Cu(II) over a wide concentration range (5.0x10(-2)-7.0x10(-7) mol l(-1)) with Nernstian slope of 30+/-1 mV per decade. The response time of the electrode is 10 s and it has been used for a period of one month and exhibits good selectivity towards Cu(2+) in comparison to alkali, alkaline earth, transition and heavy metal ions, with no interference caused by Pb(2+), Cd(2+) and Fe(+2) which are known to interfere with many other copper electrodes.     

A 9,10-anthraquinone derivative having two propenyl arms as a neutral ionophore for highly selective and sensitive membrane sensors for copper(II) ion.

New polymeric membrane (PME) and coated graphite (CGE) copper(II)-selective electrodes based on 1-hydroxy-2-(prop-2'-enyl)-4-(prop-2'-enyloxy)-9,10-anthraquinone were prepared. The electrodes reveal linear emf-pCu2+ responses over wide concentration ranges (1.0 x 10(-5)-1.0 x 10(-1) M with a slope of 27.3 mV decade-1 for PME and 8.0 x 10(-8)-5.0 x 10(-2) M with a slope of 29.1 mV decade-1 for CGE) and very low limits of detection (8.0 x 10(-6) M for PME and 5.0 x 10(-8) M for CGE). The potentiometric response is independent of the pH of the test solution in the pH range 3.0-6.0. The proposed electrodes possess very good selectivities over a wide variety of other cations, including alkali, alkaline earth, transition and heavy metal ions, the selectivity coefficients for the CGE being much improved over those for the PME. The electrodes were used as indicator electrodes in the potentiometric titration of Cu2+ and in the recovery of copper ions from wastewater.     

Lead(II)-selective electrode based on phenyl disulfide.

A PVC membrane electrode for lead ions based on phenyl disulfide as the membrane carrier was developed. The electrode exhibits a good Nernstian slope of 29.3 +/- 0.7 mV/decade and a linear range of 2.0 x 10(-6)-1.0 x 10(-2) M for Pb(NO3)2. The limit of detection is 1.2 x 10(-6) M. It has a response time of 45 s and can be used for at least fifty days without any divergence in potential. The proposed membrane sensor revealed high selectivity for Pb2+ over a wide variety of other metal ions and could be used in the pH range of 3.5-6.3. The electrode was used as an indicator electrode in potentiometric titration of lead ions.     

A liquid-state copper(II) ion-selective electrode containing a complex of Cu(II) with salicylaniline

A new liquid-state ion-selective electrode based on a complex of Cu(II) with salicylaniline is described. The electrode shows linear dependence of potential on the activity of Cu(2+) in the range from 5 x 10(-6) to 0.1M, with a slope of 28.3 mV/pCu at 18 degrees . The electrode shows a better selectivity relative to Ag(I) and Hg(II) than other copper(II) ion-selective electrodes. The possibilities for using the electrode for determination of copper in the presence of interfering cations are described.     

Coated-wire silver ion-selective electrode based on silver complex of cyclam.

A coated-wire ion-selective electrode (ISE) based on cyclam (1,4,8,11-tetraazacyclotetradecane) as a neutral carrier in a polyvinyl chloride (PVC) matrix was fabricated for the determination of Ag(I) ions. The coated-wire ISE exhibited a linear Nernstian response over the range 1 x 10(-1) to 1 x 10(-7) M with a slope of 59 +/- 2 mV per decade change and a detection limit of 5 x 10(-8) M. The ISE shows a greater preference for Ag over other cations with good precision. The electrode was selective towards Ag(I) ions in the presence of 13 different metal ions tested. The selectivity coefficients (K(ij)) were determined for Na(I), K(I), Mg(II), Ca(II), Ba(II), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pb(II) and Hg(II). The selectivity coefficients of these cations are in the range of 10(-4) to 10(-2). This ISE was used for the determination of free silver and total silver in electroplating bath solutions, additives and brighteners.     

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.     

Poly(vinyl chloride)-based macrocyclic membrane sensors for magnesium

Poly(vinyl chloride)-based membranes of macrocycles 4,11-dimethyl-2,4,9,11-tetraethyl-1,5,8,12-tetraaza cyclotetradeca-1,8-diene (I) and 4,11-dioxa-2,9-dimethyl-1,5,8,12-tetraaza cyclotetradeca-1,8-diene (II) with sodium tetraphenyl borate (STB) as an anion excluder and dibutyl phthalate (DBP), dioctyl phthalate (DOP), dibutylbutyl phosphonate (DBBP) and 1-chloronaphthalene (CN) as plasticizing solvent mediators were prepared and investigated as magnesium selective electrodes. The best performance was observed having the composition (II)-PVC-STB-DBP in the ratio 2:10:1:7, which works well over a wide concentration range (1.9x10(-6) to 1.0x10(-1) M) with a Nernstian slope of 29 mV per decade of activity between pH 2.5 and 6.5. These electrodes have been found to be chemically inert showing a fast response time of 15 s and were used over a period of 3 months with good reproducibility (S=+/-0.2 mV). The selectivity coefficient values for mono-, di- and trivalent cations indicate excellent selectivity for Mg(2+) over a large number of cations. The electrodes have also been used successfully in partially non-aqueous medium and as an indicator electrode in the potentiometric titration of Mg(2+) with EDTA. Anions such as Cl(-) and SO(4)(2-) do not interfere in the working of the electrode. The practical utility of the membrane sensor has also been observed in solutions contaminated with detergents (cetyltrimethyl ammonium bromide and sodium dodecyl sulphate). Above all, the membrane sensor has been very successfully used to analyse some babyfood products and soft drinks for the determination of Mg(2+).     

New cadmium(II)-selective electrode based on a tetraazacyclohexadeca macrocyclic ionophore.

A poly(vinyl chloride)-based membrane of 3,4:11,12-dibenzo-1,6,9,14-tetraazacyclohexadecane with sodium tetraphenyl borate (NaTPB) as an anion excluder and dibutylphthalate (DBP), dibutyl(butyl)phosphonate (DBBP), tris(2-ethylhexyl)phosphate (TEHP) and tributyl phosphate (TBP) as a plasticizing solvent mediator was prepared and investigated as a Cd2+-selective electrode. The best performance was observed with the membrane having a ligand-PVC-DBP-NaTPB composition of 2:25:60:1, which worked well over a wide concentration range (1.6 x 10(-6) - 1.0 x 10(-1) M) with a Nernstian slope of 29.5 mV per decade of activity between pH 2.0 - 6.0. This electrode showed a fast response time of 13 s and was used over a period of 4 months with good reproducibility (S = 0.4 mV). The selectivity coefficient for mono-, di- and trivalent cations indicated excellent selectivity for Cd2+ ions over a large number of cations. Anions such as NO3- and SO4(2-) , did not interfere. The membrane sensor has been successfully used to determine Cd2+ in real samples.     

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.     

A new lead(II)-selective PVC-coated graphite rod electrode based on a Schiff base complex.

A new lead(II)-selective electrode has been developed based on bis(acetylacetone)-p-phenylenediamine-lead(II) [LPb(NO3)2]H2O complex ionophore as a sensing material, dioctylphthalate (DOP) as a solvent mediator and PVC as a matrix. This electrode exhibits a linear Nernstian response over the concentration range of 1 x 10(-5)-1 x 10(-1) mol l(-1) of Pb(II) cation, with a cationic calibration slope of 30.0 +/- 0.2 mV/concentration decade and a detection limit of 2 x 10(-6) mol l(-1) (0.40 ppm). It has a fast response time and can be used for a period of 2 months without any divergence in potentials. The proposed electrode reveals a good selectivity for Pb(II) over a wide variety of other tested cations and could be used in the pH range of 4-8. It was successfully used for direct determination of Pb(II) concentration in some samples. The obtained results show a good agreement with those obtained by an atomic absorption spectrometric method. The average recovery obtained is 96.5 +/- 0.5% with standard deviation of 1.2% (n = 8).     

Synthesis of N'-(1-pyridin-2-ylmethylene)-2-furohydrazide and its application in construction of a highly selective PVC-based membrane sensor for La(III) ions.

A highly La(III) ion-selective PVC membrane sensor based on N'-(1-pyridin-2-ylmethylene)-2-furohydrazide (NPYFH) as an excellent sensing material was successfully developed. The electrode shows a good selectivity for La(III) ion with respect to most common cations including alkali, alkaline earth, transition and heavy metal ions. The proposed sensor exhibits a wide linear response with slope of 19.2 +/- 0.6 mV per decade over the concentration range of 1.0 x 10(-6) - 1.0 x 10(-1) M, and a detection limit of 7.0 x 10(-7) M of La(III) ions. The sensor response is independent of pH in the range of 3.5-10.0. The proposed electrode was applied as an indicator electrode in potentiometric titration of La(III) ion with EDTA.     

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.     

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.     

Aluminium(III)-selective electrode based on a newly synthesized tetradentate Schiff base

A PVC membrane electrode for aluminium ion based on bis(5-phenyl azo salicylaldehyde) 2,3-naphthalene diimine (5PHAZOSALNPHN) as an ion carrier was developed. The electrode exhibits a Nernstian slope of 19.3+/-0.8 mV per decade and a linear range of 5.0x10(-6)-1.0x10(-2) M for Al(NO(3))(3). The limit of detection is 2.5x10(-6) M. It has a fast response time of about 10 s and can be used for at least 10 weeks without observing any deviation. The proposed membrane sensor revealed good selectivity for Al(3+) over a wide variety of other metal ions and could be used in pH range of 2.9-5.0. It was used as an indicator electrode in potentiometric titration of aluminium ion.     

A comparative study of four 20-membered N2S4-crown ethers as ionophores for polymeric membrane silver

Four 20-membered N2S4-monoazathiacrown ethers have been synthesized and explored as neutral ionophores for Ag+-selective electrodes.Potentiometric responses reveal that the flexibility of the ligands has great effect on the selectivity and sensitivity to Ag+ions.The electrode based on ionophore 9,10,20,25-tetrahydro-5H,12H-tribenzo[b,n,r][1,7,10,16,4,13]tetrathiadiaza cycloicosine6,13-(7H,14H)-dione(C)with 2-nitrophenyl octyl ether(ο-NPOE)as solvent in a poly(vinyl chloride)(PVC)membrane matrix shows a measuring range of 1.0 × 10-6 to 1.0 × 10-3 mol/L with a Nemstian slope of 54.9 ± 0.3 mV/decade.This electrode has high selectivity for Ag+with negligible interference from many other cations and can be used in a wide pH range of 3.6-9.2.     

A highly selective and sensitive thorium(IV) PVC membrane electrode based on a dithio-tetraaza macrocyclic compound.

A poly(vinyl chloride)-based membrane composed of dithio-tetraaza macrocyclic compound as a neutral carrier with sodium tetraphenylborate (NaTPB) as an anion excluder and nitrobenzene (NB) as plasticizer was prepared and investigated as a Th(IV)-selective electrode. The electrode exhibits a Nernstian slope of 14.2 +/- 0.3 mV per decade over a wide concentration range (1.0 x 10(-6) to 1.0 x 10(-1) M) with a detection limit of 8.0 x 10(-7) M between pH 3.5 and 9.5. The response time of the sensor is about 10 s and it can be used over a period of 5 months without any divergence in potential. The proposed membrane sensor revealed a good selectivity for Th(IV) over a wide variety of other metal ions and proved to be a better electrode in many respects than those reported in the literature. It was successfully applied as an electrode indicator as well as in the direct determination of thorium ions in standard and real samples.     

A mercury(II) ion-selective electrode based on N,N-dimethylformamide-salicylacylhydrazone as a neutral carrier.

A new PVC membrane mercury(II) ion electrode based on N,N-dimethylformamide-salicylacylhydrazone (DMFAS) as an ionophore is described, which shows excellent potentiometric response characteristics and displays a linear log[Hg(2+)] versus EMF response over a wide concentration range between 6.2 x 10(-7) and 8.0 x 10(-2) M with a Nerstian slope of 29.6 mV per decade and a detection limit of 5.0 x 10(-7) M. The response time for the electrode is less than 30 s and the electrode can be used for more than 2 months with less than a 2 mV observed divergence in a potentials. The proposed electrode exhibits very good selectivity for mercury(II) ions over many cations in a wide pH range (pH 1 - 4). The electrode was also applied to the determination of a mercury(II) ion in vegetables and in Azolla filiculoides.     

A 15-crown-5-functionalized carbosilane dendrimer as ionophore for ammonium selective electrodes

The synthesis of CH(2)CHCH(2)OCH(2)[15-crown-5] (III) is achieved by the treatment of HOCH(2)- [15-crown-5] (I) with equimolar amounts of CH(2)CHCH(2)Br (II) in the presence of KOH. The hydrosilylation of III with Si(CH(2)CH(2)CH(2)SiMe(2)H)(4) (IV) in the presence of the Karstedt catalyst affords the crown ether end-capped carbosilane dendrimer Si(CH(2)CH(2)CH(2)Si-Me(2)CH(2)CH(2)CH(2)OCH(2)[15-crown-5])(4) (V). PVC-based membranes of V as ionophore with sodium tetraphenyl borate (NaTPB) as anion excluder and dioctyl phthalate (DOP), diphenyl ether (DPE), dibutyl amine (DBA) and dibutyl phthalate (DBP) as plasticizing solvent mediators were prepared and investigated as NH(4)(+)-selective electrode. The response of the electrode was linear with a Nernstian slope of 53.3mV/decade over an NH(4)(+) ion concentration range of 7.60x10(-6) to 1.0x10(-1)M and a detection limit of 3.9x10(-6)M. The response time to achieve a steady potential for NH(4)(+) ions was between 6 and 10s, and the electrode is suitable for use within the pH range of 2.2-8.5. The selectivity relative to alkali, alkaline earth, and transition heavy metal ions is good. The newly developed ionophore showed higher NH(4)(+) selectivity over K(+) ( [Formula: see text] ) and Na(+) ( [Formula: see text] ). The electrode could be used for at least 45 days without considerable alteration in its potential. The electrode also shows a better working concentration range and slope in comparison to other NH(4)(+)-selective electrodes reported in literature.     

Triethylene glycol ether end-grafted carbosilane dendrimer: a potential ionophore for potassium ion recognition.

The performance of a newly synthesized carbosilane dendrimer bearing four triethylene glycol ether (TEG) units, Si(CH2CH2CH2Si(Me)2CH2CH2CH2(OCH2CH2)3Me)4 (1), as ionophores in ion-selective electrodes has been investigated. Optimization of the plasticized polyvinyl chloride membrane composition has produced electrodes that exhibit a Nernstian response for potassium ions. The best general characteristics exhibited by the electrodes were found when the membrane composition ratio of DPE:1:NaTPB:PVC 60:3:2:35 (wt%) was used. The response of the electrode was linear with a Nernstian slope of 58.3 mV/decade over the K+ ion concentration range of 1.9x10(-7) to 1.0x10(-1) M with a detection limit of 3.1x10(-7) M. The response time to achieve a 95% steady potential for the K+ concentration ranging from 1.0x10(-1) to 1.0x10(-8) M was less than 10 s, and it was found that the electrode is suitable for use within a pH range of 5.5-8.5. The selectivity coefficients (log KPotK+,Mn+)), which were determined by the fixed interference method, showed good selectivity for K+ against most of the interfering cations. The influence of this selective ion-binding behavior using electrospray ionization time-of-flight (ESI-TOF) mass spectrometric studies is discussed.