Highly selective PVC-membrane electrodes based on Co(II)-Salen for determination of nitrite ion.

A cobalt(II) derivative was used as a suitable ionophore for the preparation of a polymeric membrane nitrite-selective electrode. The electrode reveals a Nemstian behavior over a very wide NO2- ion concentration range (1.0 x 10(-6)-1.0 x 10(-1) M) and a very low detection limit (5.0 x 10(-7) M). The potentiometric response is independent of the pH of solution in the pH range 4.0-9.5. The electrode shows advantages such as low resistance, fast response and, most importantly, good selectivity relative to a wide variety of inorganic and organic anions. In fact, the selectivity behavior of the proposed NO2- ion-selective electrode shows great improvements compared to the previously reported electrodes for nitrite ion. The proposed electrodes could be used for at least 2 months without any significant changes in potentials. The electrode was successfully applied to the determination of nitrate ion concentrations in sausage and milk samples.     

Thiocyanate-selective electrode based on unsymmetrical benzoN(4) nickel(II) macrocyclic complexes

Unsymmetrical benzoN(4) nickel(II) macrocyclic complexes have been explored as an ionophore for preparing PVC-based membrane electrodes selective to SCN(-). The resulting electrode exhibited the best working concentration range (1.4x10(-7)-0.1 M) with a Nernstian slope of (-59.7+/-0.9 mV per decade) in the wide pH range of 3.5-10.5. The proposed electrode has a very fast response time (5 s) and high selectivity for thiocyanate over variety of anions. This sensor was successfully applied as an indicator electrode to potentiometric titration of thiocyanate ion with AgNO(3) and for direct determination of the amount of thiocyanate in urine and saliva samples in order to distinguish between smokers and nonsmokers.     

Novel Nitrite Membrane Sensor Based on Cobalt(II) Salophen for Selective Monitoring of Nitrite Ions in Biological Samples

A novel PVC-based membrane sensor based on the Co(II)-salophen complex (CSC) is described. The electrode revealed a Nernstian response over a wide nitrite ion concentration range (1.0×10^–6–1.0×10^–1M). The detection limit of the sensor is 8.0×10^–7M. The best performance was obtained with a membrane composition of 33% PVC, 61% ortho-nitrophenyloctyl ether, 3% cobalt(II)-salophen, and 3% hexadecyltrimethylammonium bromide. The potentiometric response of the sensor is independent of the pH of solution in the pH range 4.5–11.9. The electrode exhibits a very fast response time and good selectivity over a variety of common inorganic and organic anions, including fluoride, bromide, iodide, sulfite, nitrate, thiocyanate, thriiodide and perchlorate. The selectivity behavior of the proposed sensor shows substantial improvements compared to the previously reported electrodes for nitrite ion. The membrane sensor can be used for at least 2 months without any divergence in potential. The electrode was successfully applied to the monitoring of nitrite ion in water, sausage, flour, wheat, cheese and milk.     

Potentiometric anion selectivity of polymer-membrane electrodes based on cobalt, chromium, and aluminum salens

Metallo-salens of cobalt(II) (Co-Sal), chromium(III) (Cr-Sal), and aluminum(III) (Al-Sal) are used as the active ionophores within plasticized poly(vinyl chloride) membranes. It is shown that central metal-ion plays a critical role in directing the ionophore selectivity. Polymer-membrane electrodes based on Co-Sal, Cr-Sal, and Al-Sal are demonstrated to exhibit enhanced responses and selectivity toward nitrite/thiocyanate, thiocyanate, and fluoride anions, respectively. The improved anion selectivity of the three ionophore systems is shown to deviate significantly from the classical Hofmeister pattern that is based only on ion lipophilicity. For example, optimized membrane electrodes for nitrite ion based on Co-Sal exhibit logK(Nitrite,Anion)(pot) values of -5.22, -4.66, -4.48, -2.5 towards bromide, perchlorate, nitrate, and iodide anions, respectively. Optimized membrane electrodes based on Co-Sal and Cr-Sal show near-Nernstian responses towards nitrite (-57.9+/-0.9 mV/decade) and thiocyanate (-56.9+/-0.8 mV/decade), respectively, with fast response and recovery times. In contrast, Al-Sal based membrane electrodes respond to fluoride ion in a super-Nernstian (-70+/-3 mV/decade) and nearly an irreversible mode. The operative response mechanism of Co-Sal, Cr-Sal, and Al-Sal membrane electrodes is examined using the effect of added ionic sites on the potentiometric response characteristics. It is demonstrated that addition of lipophilic anionic sites to membrane electrodes based on the utilized metallo-salens enhances the selectivity towards the primary ion, while addition of cationic sites resulted in Hofmeister selectivity patterns suggesting that the operative response mechanism is of the charged carrier type. Electron spin resonance (ESR) data indicates that Co(II) metal-ion center of Co-Sal ionophore undergoes oxidation to Co(III). This process leads to formation of a charged anion-carrier that is consistent with the response behavior obtained for Co-Sal based membrane electrodes.     

Binuclear Schiff base complex of manganese(III) as a neutral carrier for a highly selective iodide electrode.

A new highly selective iodide electrode incorporating a binuclear manganese(III) complex, bis(salicylaldehyde-aminopropanol)dichloroaceticdimanganese(III) [Mn(III)(2)-BSAPDCA], as a neutral carrier is described. The electrode displays an anti-Hofmeister selectivity sequence: iodide > perchlorate > salicylate > thiocyanate > nitrate > bromide > nitrite > chloride > sulfate. The excellent selectivity for iodide is related to a direct interaction between the central Mn(III) atom and iodide and a steric effect associated with the structure of the carrier, which is supported by UV spectroscopy and AC impedance techniques. The electrode exhibits a near-Nernstian potentiometric linear response range to iodide from 1.0 x 10(-1) to 2.0 x 10(-5) mol/L with a detection limit of 8.0 x 10(-6) mol/L and a slope of -60.3 mV/decade in pH 3.0 of phosphate buffer solutions at 20 degrees C. From a comparison of the potentiometric response characteristics between a binuclear manganese(III) complex, Mn(III)(2)-BSAPDCA, and a mononuclear manganese(III) complex, Mn(III)-BSAPB, an enhanced response towards iodide from a binuclear metallic complex-based electrode was observed. The electrode, based on binuclear manganese(III) complex, was successfully applied to the determination of inorganic total iodine in iodized table salt with satisfactory results.     

Thiocyanate ion-selective PVC membrane electrode based on N,N'-ethylene-bis(4-methylsalicylidineiminato)nickel(II).

A highly selective poly(vinyl chloride) (PVC) membrane electrode based on an N,N'-ethylene-bis(4-methyl-salicylidineiminato) nickel(II) [Ni(EBMSI)] complex as a carrier for a thiocyanate-selective electrode is reported. The influences of the membrane composition, pH and possible interfering anions were investigated based on the response properties of the electrode. The electrode exhibited a good Nernstian slope of -58.9 +/- 0.7 mV decade(-1), over a wide pH range of 3.5 - 8.5 and a linear range of 1.0 x 10(-6) - 1.0 x 10(-1) M for thiocyanate. The detection limit of electrode was 3.1 x 10(-7) M SCN(-). The selectivity coefficients determined by a fixed interference method (FIM) indicate that a good discriminating ability towards the SCN- ion compared to other anions. The proposed sensor had a fast response time of about 5 - 15 s and could be used for at least 3 months without any considerable divergence in the potential. It was applied as an indicator electrode in the titration of thiocyanate with Ag+ and in the potentiometric determination of thiocyanate in saliva and urine samples.     

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.     

Papaverine PVC membrane ion-selective electrodes based on its ion-exchangers with tetraphenylborate and tetrathiocyanate anions

The construction and general performance of novel potentiometric membrane ion selective electrodes for determination of papaverine hydrochloride has been described. They are based on the formation of the ion association complexes of papaverine (PA) with tetraphenylborate (TPB)(I) or tetrathiocyanate (TTC)(II) counter anions as electro-active material dispersed in a PVC matrix. The electrodes show fast, stable, near Nernstian response for 1 x 10(-2) to 6 x 10(-5) M and 1 x 10(-2) to 1 x 10(-5) M for PA-TPB and PA-TTC respectively at 25 degrees C over the pH range of 3-5.0 with a cationic slope of approximately 56.5 +/- 0.5 mV/decade for both sensors respectively. The lower detection limit is 4 x 10(-5) and 8 x 10(-6) M for PA- I and PA-II respectively with fast response time ranging from 20-45 sec. Selectivity coefficients for PA relative to a number of interfering substances were investigated. There is a negligible interference from the studied cations, anions, and pharmaceutical excipients. The determination of 4.0- 3000.0 microg/ml of PA in aqueous solutions shows an average recovery of 99.1% and a mean relative standard deviation of 1.4 at 100microg/ml. The direct determination of PA in some formulations (Vasorin injection) gave results that compare favorably with those obtained using the British Pharmacopoeia method. Potentiometric titration of PA with sodium tetraphenylborate and potassium thiocyanate as titrants utilizing the papaverine electrode as an end point indicator electrode has been carried out.     

Bis-dimethylaminobenzaldehyde Schiff-base cobalt(II) complex as a neutral carrier for a highly selective iodide electrode.

A new solvent polymeric membrane electrode based on N,N'-bis-(dimethylaminobenzaldehyde)-glycine cobalt(II) [Co(II)-BDMABG] as a neutral carrier is described, which displays a preferential potentiometric response to iodide ion and an anti-Hofmeister selectivity sequence in the following order: I- > ClO4- > Sal- > SCN- > NO2- > Br- > NO3- > Cl- > SO3(2-) > SO4(2-). The electrode exhibits a near-Nernstian potential linear range of 9.0 x 10(-7)-1.0 x 10(-1) M with a detection limit of 6.8 x 10(-7) M and a slope of -53.0 mV/decade in pH 2.0 of a phosphate buffer solution at 20 degrees C. The response mechanism is discussed in view of the A.C. impedance technique and the UV spectroscopy technique. The electrode was successfully applied to the determination of iodide in Jialing River and Spring in Jinyun Mountains with satisfactory results.     

Tetrakis(4-N,N-dimethylaminobenzene)porphyrinato]manganese(III) acetate as a novel carrier for a selective iodide PVC membrane electrode.

[5,10,15,20-Tetrakis(4-N,N-dimethylaminobenzene)porphyrinato]Mn(III) acetate (MnTDPAc) was applied as an ionophore for an iodide-selective PVC membrane electrode. The influences of the membrane composition, pH of the test solution and foreign ions on the electrode performance were investigated. The sensor exhibited not only excellent selectivity to iodide ion compared to Cl- and lipophilic anions such as ClO4- and salicylate, but also a Nernstian response with a slope of -59.4 +/- 1.2 mV per decade for iodide ions over a wide concentration range from 1.0 x 10(-2) to 7.5 x 10(-6) M at 25 degrees C. The potentiometric response was independent of the pH of the solution in the pH range of 2 - 8. The electrode could be used for at least 2 months without any considerable divergence in the potential. Good selectivity for iodide ion, a very short response time, simple preparation and relatively long-term stability were the silent characteristics of this electrode. It was successfully used as an indicator electrode in the potentiometric titration of iodide ions, and also in the determination of iodide from seawater samples and drug formulations.     

Mercury(II) ion-selective electrodes based on p-tert-butyl calix[4]crowns with imine units.

A PVC membrane incorporating p-tert-butyl calix[4]crown with imine units as an ionophore was prepared and used in an ion-selective electrode for the determination of mercury(II) ions. An electrode based on this ionophore showed a good potentiometric response for mercury(II) ions over a wide concentration range of 5.0 x 10(-5) - 1.0 x 10(-1) M with a near-Nernstian slope of 27.3 mV per decade. The detection limit of the electrode was 2.24 x 10(-5) M and the electrode worked well in the pH range of 1.3 - 4.0. The electrode showed a short response time of less than 20 s. The electrode also showed better selectivity for mercury(II) ions over many of the alkali (Na+, -1.69; K+, -1.54), alkaline-earth (Ca2+, -3.30; Ba2+, -3.32), and heavy metal ions (Co2+, -3.67; Ni2+, -3.43; Pb2+, -3.31; Fe3+, -1.82). Ag+ ion was found to be the strongest interfering ion. Also, sharp end points were obtained when the sensor was used as an indicator electrode for the potentiometric titration of mercury(II) ions with iodide and dichromate ions.     

Highly selective iodide membrane electrode based on a cerium salen.

A highly selective PVC membrane electrode based on a cerium-salen complex was prepared. The sensor displays an anti-Hofmeister selectivity sequence with a preference for iodide ion over many common organic and inorganic anions. The proposed electrode exhibits a near-Nernstian behavior over a wide concentration range (5.0 x 10(-2) - 8.0 x 10(-6) M) with a slope of 57.5 mV per decade, and a detection limit of 6.0 x 10(-6) M. The electrode has a very fast response time and can be used in the pH range of 3.0 - 1 1.0. It was applied, as an indicator electrode, in potentiometric titration of Ag+ ions.     

Salicylate ion-selective electrode based on new tetranuclear copper complexes of O-vannlin-methionine as neutral carriers.

A new salicylate-selective PVC membrane electrode based on a new Schiff base tetranuclear copper complex of O-vannlin-methionine (Cu(II)(4)-TVM) as a neutral carrier is described. This electrode displays a preferential potentiometric response to salicylate and an anti-Hofmeister selectivity sequence in the following order: Sal(-) > ClO(4)(-) > SCN(-) > I(-) > NO(2)(-) > NO(3)(-) > Br(-) > Cl(-) > SO(3)(2-) > SO(4)(2-) > H(2)PO(4)(-). The electrode exhibits near-Nernstian potential linear range of 1.5 x 10(-6)-1.0 x 10(-1) M with a detection limit of 8.0 x 10(-7) M and a slope of -56.3 mV/decade in pH 3.0-8.0 of phosphorate buffer solution at 20 degrees C. Thanks to the tetranuclear copper(II) in the carrier, the electrode has the advantages of simplicity, fast response, fair stability and reproducibility and low detection limit. The response mechanism to the electrodes is discussed by the a.c. impedance technique and the UV spectroscopy technique. The electrode can be applied to analyses of medicine and the results obtained are in fair agreement with the results given by a standard method.     

Sulfite-sensitive solvent/polymeric-membrane electrode based on bis(diethyldithiocarbamato)mercury(II)

A new solvent/polymeric-membrane electrode which exhibits significant potentiometric response toward sulfite ion in the 1 × 10_?6?1 × 10^?3 M range is described. The membrane is prepared by incorporation of neutral bis(diethyldithiocarbamato)mercury (II) in a thin film of plasticized poly (vinyl chloride). In sharp contrast to classical Hofmeister behavior, the resulting membrane displays little or no response to a wide range of anions (log K^pot_i,j ? ?4, i being sulfite) including sulfate, nitrate, nitrite, chloride, perchlorate, salicylate, and alkylsulfonates. Bromide and thiocyanate are moderate interferents, while significant response to iodide, thiosulfate, and sulfide is observed. These selectivity data, along with other response characteristics of the membrane, are used to postulate the mechanism by which the electrode responds to sulfite. Preliminary studies demonstrate that the electrode can be used in conjunction with an outer gas-permeable membrane for highly selective detection of total sulfite species in the form of sulfur dioxide.     

Fabrication of PVC based membrane using nickel porphyrazine as ionophore in the screening of thiocyanate ion in aqueous and real samples

The [Ni[(TAP)(SBn)8]] complex (I), i.e. ([2,3,7,8,12,13,17,18-octakis(benzylthio)-5,10,15,20-tetraazaporphyrin])nickel(II), has been explored as an ionophore for fabrication of the PVC based membrane electrodes used in the screening of thiocyanate anion (SCN-). The membrane having [Ni[(TAP)(SBn)8]] complex (I) as an electroactive material and dioctylphthalate (DOP) as plasticizer in the PVC matrix with the percentage ratio 5 : 158 : 200 (I : DOP : PVC, % w/w) exhibited a linear response in the concentration range 7.0 x 10(-6)-1.0 x 10(-1) M of SCN- with a sub-Nernstian slope 32.5 +/- 0.2 mV/decade of activity and a fast response time of 10 +/- 2 s. The sensor works well in the pH range 3.0 - 9.5 and could be satisfactorily used in presence of 50 % (v/v) methanol, ethanol and acetone, and is selective for SCN- over a large number of anions with slight interference from iodide (I-) and azide (N3-) if present at a level >or = 1.0 x 10(-5) M. Described electrode works well over a period of six months. The sensor can be successfully applied for the screening of SCN- in both aqueous and real samples and also as indicator electrodes in precipitation titrations.     

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.     

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.     

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.     

Highly Selective and Sensitive Triiodide PVC‐Membrane Electrode Based on a New Charge‐Transfer Complex of Bis(2,4‐Dimethoxybenzaldehyde)butane‐2,3‐Dihydrazone with Iodine

In this work, a highly selective membrane triiodide sensor based on a new charge‐transfer complex of bis(2,4‐dimethoxybenzaldehyde)butane‐2,3‐dihydrazone with iodine (Iodide Charge Transfer complex: ICT) as membrane carrier is introduced. The influences of five different solvent mediators on sensitivity and selectivity of the proposed sensor were considered. The best performance was obtained with the membrane composition containing 30% poly (vinyl chloride), 63% DBP, 5% ICT and 2% HTAB. The electrode shows a Nernstian behavior over a very wide triiodide ion concentration range (1.0 × 10^?7‐1.0 × 10^?2 M), and a detection limit value of 8.0 × 10^?8 M. The effect of pH on the potentiometric response of the sensor was also studied, and it was found that the response of the electrode is independent of the pH of the solution in the pH range of 4.0–10. The proposed sensor has a very fast response time (< 12 s), and good selectivities relative to a wide variety of common inorganic and organic anions, including iodide, acetate, bromide, chloride, fluoride, nitrite, nitrate, sulfite, sulfate, cyanide and thiocyanate. In fact the selectivity behavior of the proposed triiodide ion‐selective electrode shows great improvements compared to the previously reported electrodes for triiodide ion. The proposed membrane sensor can be used for at least 6 months without any divergence in the potentials. The electrode was successfully applied as an indicator electrode in the titration of triiodide with thiosulfate ion.     

Ion-selective electrodes for potentiometric determination of ranitidine hydrochloride, applying batch and flow injection analysis techniques.

New ranitidine hydrochloride (RaCl)-selective electrodes of the conventional polymer membrane type are described. They are based on incorporation of ranitidine-tetraphenylborate (Ra-TPB) ion-pair or ranitidine-phosphotungstate (RaPT) ion-associate in a poly(vinyl chloride) (PVC) membrane plasticized with dioctylphthalate (DOP) or dibutylphthalate (DBP). The electrodes are fully characterized in terms of the membrane composition, solution temperature, and pH. The sensors showed fast and stable responses. Nernstian response was found over the concentration range of 2.0 x 10(-5) M to 1.0 x 10(-2) M and 1.0 x 10(-5) M to 1.0 x 10(-2) M in the case of Ra-TPB electrode and over the range of 1.03 x 10(-5) M to 1.00 x 10(-2) M and 1.0 x 10(-5) M to 1.0 x 10(-2) M in the case of Ra-PT electrode for batch and FIA systems, respectively. The electrodes exhibit good selectivity for RaCl with respect to a large number of common ions, sugars, amino acids, and components other than ranitidine hydrochloride of the investigated mixed drugs. The electrodes have been applied to the potentiometric determination of RaCl in pure solutions and in pharmaceutical preparations under batch and flow injection conditions with a lower detection limit of 1.26 x 10(-5) M and 5.62 x 10(-6) M at 25 +/- 1 degrees C. An average recovery of 100.91% and 100.42% with a relative standard deviation of 0.72% and 0.53% has been achieved.