Potentiometric sensor for the high throughput determination of tetramisole hydrochloride

The electrochemical response characteristics of poly(vinyl)chloride (PVC) based membrane sensors for determination of tetramisole hydrochloride (TmCl) is described. The membranes of these electrodes consist of tetramisole-tetraphenyl borate (Tm-TPB), chlorophenyl borate (Tm-ClPB), and phosphotungstate (Tm(3)-PT) ion associations dispersed in a PVC matrix with dibutylpthalate as a plasticizer. The electrodes were fully characterized in terms of composition, life span, usable pH range, and working concentration range and ionic strength. The electrodes showed Nernstian response over the concentration ranges of 7.4 x 10(-7) to 1.0 x 10(-2) M, 1.7 x 10(-6) to 1.0 x 10(-2) M, and 5.6 x 10(-6) to 1.0 x 10(-2) M TmCl, respectively, and were applied to the potentiometric determination of tetramisole ion in pure solutions and pharmaceutical preparations. The potentiometric determination was also used in the determination of tetramisole in pharmaceutical preparations in four batches of different expiration dates. The electrodes exhibited good selectivity for TmCl with respect to a large number of excipients such as inorganic cations, organic cations, amino acids, and sugars. The solubility product of the ion-pair and the formation constant of the precipitation reaction leading to the ion-pair formation were determined conductometrically. The new potentiometric method offers the advantages of high-throughput determination, simplicity, accuracy, automation feasibility, and applicability to turbid and colored sample solutions.     

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.     

New conventional coated-wire ion-selective electrodes for flow-injection potentiometric determination of chlordiazepoxide.

New chlordiazepoxide hydrochloride (Ch-Cl) ion-selective electrodes (conventional type) based on ion associates, chlordiazepoxidium-phosphomolybdate (I) and chlordiazepoxidium-phosphotungstate (II), were prepared. The electrodes exhibited mean slopes of calibration graphs of 59.4 mV and 60.8 mV per decade of (Ch-Cl) concentration at 25 degrees C for electrodes (I) and (II), respectively. Both electrodes could be used within the concentration range 3.16 x 10(-6)-1 x 10(-2) M (Ch-Cl) within the pH range 2.0-4.5. The standard electrode potentials were determined at different temperatures and used to calculate the isothermal coefficients of the electrodes, which were 0.00139 and 0.00093 V degrees C(-1) for electrodes (I) and (II), respectively. The electrodes showed a very good selectivity for Ch-Cl with respect to the number of inorganic cations, amino acids and sugars. The electrodes were applied to the potentiometric determination of the chlordiazepoxide ion and its pharmaceutical preparation under batch and flow injection conditions. Also, chlordiazepoxide was determined by conductimetric titrations. Graphite, copper and silver coated wires were prepared and characterized as sensors for the drug under investigation.     

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.     

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.     

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.     

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.     

Construction and performance characterization of ion-selective electrodes for potentiometric determination of pseudoephedrine hydrochloride applying batch and flow injection analysis techniques

New pseudoephedrine selective electrodes have been constructed of the conventional polymer membrane type by incorporation of pseudoephedrine-phosphotungstate (PE-PT) or pseudoephedrine-silicotungstate (PE-SiT) ion-associates in a poly vinyl chloride (PVC) membrane plasticized with dibutyl phthalate (DBP). The electrodes were fully characterized in terms of the membrane composition, temperature, and pH. The electrodes exhibited mean slopes of calibration graphs of 57.09 and 56.10 mV concentration decade(-1) of PECl at 25 degrees C for (PE-PT) and (PE-SiT) electrodes, respectively. The electrodes showed fast, stable, and near-Nernstian response over the concentration ranges 6.31 x 10(-6)-1.00 x 10(-2) and 5.00 x 10(-5)-1.00x10(-2) M in the case of PE-PT applying batch and flow injection (FI) analysis, respectively, and 1.00 x 10(-5)-1.00 x 10(-2) and 5.00 x 10(-5)-1.00x10(-2) M in the case of PE-SiT for batch and FI analysis system, respectively. Detection limit was 5.01x 10(-6) M for PE-PT electrode and 6.31x10(-6) M for PE-SiT electrode. The electrodes were successfully applied for the potentiometric determination of pseudoephedrine hydrochloride (PECl) in pharmaceutical preparations with mean recovery 101.13 +/- 0.85% and 100.77+0.79% in case of PE-PT applying batch and flow injection systems, respectively, and 100.75+0.85% and 100.79 +/- 0.77% in case of PE-SiT for batch and flow injection systems, respectively. The electrodes exhibited good selectivity for PECl with respect to a large number of inorganic cations, sugars and amino acids.     

Copper(II) modified carbon paste electrodes based on self-assembled mercapto compounds-gold-nanoparticle

Three mercapto compounds [2-mercapto-5-(1-methyl-5-nitroimidazole-2-yl)-1,3,4-thiadiazole] (MMNIT), [2-mercapto-5-(5-nitrofuran-2-yl)-1,3,4-thiadiazole] (MNFT) and [2-mercapto-5-(5-nitrothiophen-2-yl)-1,3,4-thidiazole] (MNTT) were used for self-assembled-gold nanoparticle (SAGNP) modified carbon paste electrodes. The electrodes were applied as indicator electrodes for potentiometric determination of Cu(II) ion. The prepared electrodes exhibit a Nernstian slope of 31.0+/-0.5 mV per decade for Cu(II) ion over a wide concentration range of 7.9x10(-9)-3.2x10(-2), 7.9x10(-9)-7.9x10(-4), and 2.8x10(-8)-7.9x10(-3) mol L(-1) for MMNIT, MNFT and, MNTT, respectively. The detection limits of electrodes were 3.5 (+/-0.2)x10(-9), 4.1x10(-9), and 4.1x10(-8) mol L(-1) of copper ion, respectively. The potentiometric responses of electrodes based on MMNIT, MNFT, and MNTT are independent of the pH of test solution in the pH range 2.0-5.5, 2.5-7.0, and 2.0-6.5, respectively. They have quick response with response time of about 5 s. The proposed electrodes show fairly good selectivity over some alkali, alkaline earth, transition and heavy metal ions. Finally, the proposed electrodes were successfully employed to detect Cu(II) ion in hair and water samples.     

Amineptine Plastic Membrane Electrode Based on its Ion Associate with Tetraphenylborate and Phosphomolybdic Acid

New amineptine hydrochloride (Am-Cl) ion-selective electrodes (conventional type) based on amineptinium-tetraphenylborate (I) and amineptinium-phosphomolybdate (II) were prepared. The electrodes exhibited mean slopes of calibration graphs of 57.9?mV and 53.8?mV per decade of (Am-Cl) concentration at 25?°C for electrodes (I) and (II), respectively. The electrodes can be used within the concentration range 3.16×10^?5?10^?2?M (Am-Cl) at a pH range of 2.0–3.9 for both electrodes. The standard electrode potentials were determined at different temperatures and used to calculate the isothermal coefficients of the electrodes, which were 0.00172?V?°C^?1 and 0.00091 V?°C^?1 for (I) and (II) electrodes, respectively. The electrodes showed a very good selectivity for (Am-Cl) with respect to a number of inorganic cations and sugars. The standard addition method is successfully applied to determine (Am-Cl) in pure solutions and in amineptine-containing tablets.     

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.     

A Potentiometric Sensor for Determination of Doxycycline Hydrochloride in Pharmaceutical Preparation and Biological Fluids

This article focused on the construction and characteristics of novelty and sensitivity of modified carbon paste electrodes for determination of doxycycline hydrochloride (DC.HCl) in urine, serum and pharmaceutical preparations. It was based on the incorporation of α-cyclodextrine (α-CD) and multi-walled carbon nanotube (MWCNT) ionophores which improved the characteristics of the electrodes with tricresylphosphate (TCP) (electrode I) and o-nitrophenyloctylether (o-NPOE) (electrode II) as plasticizers, respectively. The constructed electrodes, at optimum paste composition, exhibited good Nernstian response for determination of doxycycline hydrochloride over a linear concentration range from 1.0 × 10^–7 to 1.0 × 10^–2 and 1.22 × 10^–7 to 1.0 × 10^–2 mol L^–1 with detection limit of 1.0 × 10–7 and 1.22 ×10^–7 mol L^–1 and with slope values of (58.7 ± 0.2) mV decade–1 and (58.0 ± 0.6) mV decade–1, for modified carbon paste electrodes (MCPEs; electrodes I and II), respectively. The results showed fast dynamic response time (about 6–7 s) and long lifetime in the range from 4 to 5 months where the response of the electrodes was not affected by pH variation within the range from 2 to 8 and 2 to 7.5 for electrodes I and II, respectively. Electrodes I and II showed high selectivity for doxycycline hydrochloride with respect to a large number of interfering species including foreign inorganic, organic species, excipients and the fillers added to the pharmaceutical preparation. The constructed electrodes were successfully applied for determination of DC.HCl in pure form, its pharmaceutical preparations and biological fluids (urine and serum) using standard addition, calibration curves and potentiometric titration methods. The results obtained using these potentiometric electrodes were comparable with those obtained using official method. The results were satisfactory with excellent percentage recovery comparable or better than those obtained by other routine methods.

     

Quantitative analysis of methacycline hydrochloride by direct potentiometry using the internal solid contact sensor.

An internal solid contact sensor (ISCS) for the determination of methacycline hydrochloride (MC.Cl), Pt/PPy/PVC(MC-PT), is described, based on the use of conducting poly(pyrrole) (PPy) as solid contact material and MC-phosphotungstate (PT) as the ion exchanger and dibutyl phthalate (DBP) as the plasticizer. A direct potentiometric method for the quantitative analysis of MC.Cl is also described. Under the condition of pH 2.7, the linear concentration range, slope (25 degrees C) and detection limit of the sensor are 6.4 x 1.0(-6) - 3.0 x 1.0(-3) M, 52.4 +/- 0.2 mV/decade and 4.4 x 1.0(-6) M, respectively. The response time is <5 s. The determinations of MC.Cl in tablets were carried out by direct potentiometry. The average recovery and relative standard deviation are 100.1 and 0.7% (n = 4), respectively.     

Bis(2-mercaptobenzoxazolato)mercury(II) and bis(2-pyridinethiolato)mercury(II) complexes as carriers for thiocyanate selective electrodes

Highly selective poly(vinyl chloride) (PVC) membrane electrodes based on bis(2-mercaptobenzoxazolato)mercury(II) [Hg(MBO)₂] and bis(2-pyridinethiolato)mercury(II) [Hg(PT)₂] complexes as new carriers for thiocyanate-selective electrodes are reported. The electrodes were prepared by coating the membrane solution containing PVC, plasticizer, carriers and additives on the surface of graphite electrodes. Influence of the membrane composition, pH and possible interfering anions were investigated on the response properties of the electrodes. Both sensors exhibited Nernstian responses towards thiocyanate over a wide concentration range of 1×10⁻⁶ to 0.1 M, with slopes of 60.6±0.8 and 57.5±1.2 mV per decade of thiocyanate concentration for Hg(MBO)₂ and Hg(PT)₂ carriers, respectively, over a wide pH range of 3-11. The limit of detection for both electrodes was ∼6×10⁻⁷ M. The sensors have response times of ≤5 s and can be used for at least 2 months without any considerable divergence in their potential response. The proposed electrodes show fairly good discrimination of thiocyanate over several inorganic and organic anions. The electrodes were successfully applied to direct determination of thiocyanate in saliva and as indicator electrodes in precipitation titrations.     

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.     

Potentiometric batch and flow injection analysis of betaine hydrochloride

Novel PVC membrane electrodes for the determination of betaine ion based on the formation of betaine-tetraphenylborate (Be-TPB) and betaine-phosphotungstate (Be-PT) ion-exchangers as electroactive materials are described. The sensors show a fast, stable, near Nernstian response for 6.92 x 10(-6) to 7.94 x 10(-3) M and 1.0 x 10(-4) to 1.0 x 10(-2) M betaine hydrochloride (Be.Cl) in case of Be-TPB electrode applying batch and flow injection analysis (FIA), respectively, and 2.95 x 10(-5) to 2.26 x 10(-3) M and 3.16 x 10(-5) to 1.0 x 10(-2) M in case of Be-PT electrode for batch and FIA electrodes, respectively, at 25 degrees C over the pH range of 3.5-10 with a cationic slope of 60.2 and 59.1 mV decade(-1) and a fast potential response of < or =15 s. The lower detection limits are 7.94 x 10(-6) and 3.18 x 10(-5) M Be.Cl for Be-TPB and Be-PT electrodes, respectively. Selectivity coefficient data for some common inorganic cations, sugars, amino acids and the components other than betaine, of the mixed drug investigated show negligible interference. The electrodes have been applied to the direct potentiometric determination of betaine hydrochloride in water and in a pharmaceutical preparation under batch and FIA conditions. Potentiometric titrations of Be.Cl with NaTPB and PTA as titrants were monitored with the developed betaine electrodes as an end point indicator electrode. The determination of Be.Cl shows an average recovery of 100.8% with mean relative standard deviation of 0.61%. The effect of temperature on the electrodes was also studied.     

Tetrabenzyl pyrophosphate as a new class of neutral carrier responsive to lead ion

Tetrabenzyl pyrophosphate and diphenylphosphinic anhydride, with two phosphoryl groups (PO) as ligating sites, can be used as novel ionophores to make Pb(2+)-selective membrane electrodes. A good result was obtained with tetrabenzyl pyrophosphate, and the electrode based on this ionophore and bis(1-butylpentyl) adipate as a solvent mediator in a poly(vinyl chloride) membrane matrix exhibited a near-Nernstian response to Pb(2+) in the concentration range of 1x10(-5)-1x10(-2) M with a slope of 28.7 mV per concentration decade in a solution containing 0.1 M Mg(NO(3))(2). The limit of detection was 3x10(-6) M. The selectivity of this electrode to other metal cations was comparable to the best case in many Pb(2+)-selective electrodes so far developed. Addition of potassium tetrakis(p-chlorophenyl)borate (40 mol% relative to tetrabenzyl pyrophosphate) caused a drastic change in the response slope (53.3 mV per concentration decade), probably due to the formation of PbA(+), where A stands for anions present in the sample solution, and decreased significantly the electrode selectivity to other metal cations.     

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 and evaluation of tetrafluoroborate selective electrodes

Summary The construction and evaluation of three types of tetrafluoroborate electrodes without internal reference solution is described. Sensors for electrodes of Type A and Type B use tetraoctylammonium tetrafluoroborate as carrier and 2-nitrophenyloctylether and dibutylphthalate, respectively, as solvent mediators. Electrodes of Type C use the 92-05-02 Orion commercial sensor based on a complex of tris(1,10-phenanthroline)-Ni(II) dissolved in p-nitrocymene. Membranes were applied on a conductive support consisting of a mixture of graphite with a non-conductive epoxy resin. The three types of electrodes showed a similar behaviour with linear responses within the concentration range 10^–5–10^–1 mol/l in tetrafluoroborate, with slopes of 58 mV per decade when the pH of the solutions was between 3 and 11.5. Electrodes of Type A showed the lowest short term hysteresis after treatment with interfering species and offered the best reproducibility and lifetime. Therefore, they were used in the determination of tetrafluoroborate ion in plating baths by means of the sample addition method, giving results with an average spike recovery of 100.5% and a mean coefficient of variation of 1.0%.     

Ion-selective electrodes in organic analysis-determination of xanthate

A PVC membrane xanthate-selective electrode has been developed for the direct determination of xanthates of primary and secondary alcohols. The xanthate electrode is highly selective and exhibits a Nernstian response in the range 5.0 x 10(-2)-7.1 x 10(-5)M xanthate with a slope of 58.6 mV per concentration decade. The electrode has a wide working pH range (5.0-11.5), a fast response time (less than 30 sec) and is stable for at least two months.