New Macrocyclic Diamides as Neutral Ionophores for Highly Selective and Sensitive PVC‐Membrane Electrodes for Be2+ Ion

Five recently synthesized macrocyclic diamides were investigated to characterize their ability as beryllium ion carriers in potentiometric PVC‐membrane electrodes. The electrodes based on 1,15‐diaza‐3,4;12,13‐dibenzo‐5,8,11‐trioxabicyclo[13,2,2] heptadecane‐2,14‐dione exhibited a Nernstian response for Be²⁺ ion over wide concentration ranges (from 3.0×10^?6 to 3.0×10^?2 M for polymeric membrane electrode, PME, and from 5.0×10^?7 to 2.0×10^?2 M for coated glassy carbon electrode, CGCE) and very low detection limits (2.0 ×10^?6 M for PME and 4.0×10^?7 M for (CGCE). The electrodes possess low resistances, fast responses, satisfactory reproducibilities and, most importantly, good selectivities relative to a variety of other common cations. The potentiometric response of the electrodes is independent of pH of test solution in the pH range of 4.0–7.5. The proposed sensors were used to determine beryllium ion in water samples.     

Novel Potentiometric PVC‐Membrane and Coated Graphite Sensors for Lanthanum(III)

Preliminary theoretical studies revealed the selective complexation of bis (2‐mercaptoanil) diacetyl (BMDA) with La³⁺ over several alkali, alkaline earth and heavy metal ions. Thus, novel PVC‐based membrane (PBM) and coated graphite membrane (CGM) sensors for La(III) based on BMDA were prepared. The electrodes display Nernstian behavior over wide concentration ranges (i.e., 1.0×10^?5–1.0×10^?1 M for PBM and 1.0×10^?6–1.0×10^?1 M for CGM). The potential response of sensors was pH independent in the range of 4.0–8.0. The sensors possess satisfactory reproducibility, fast response time (<15 s), and specially excellent discriminating ability for La³⁺ ions with respect to most of the cations. The membrane sensor was used as an indicator electrode in potentiometric titration of lanthanum ions with EDTA. The coated graphite membrane electrode was applied in determination of fluoride ions in mouth wash preparations.     

Highly Selective Chromium(III) PVC‐Membrane Electrodes Based on Some Recently Synthesized Schiff's Bases

Three recently synthesized Schiff's bases were studied to characterize their ability as Cr³⁺ ion carrier in PVC‐membrane electrodes. The polymeric membrane (PME) and coated glassy carbon (CGCE) electrodes based on 2‐hydroxybenzaldehyde‐O,O′‐(1,2‐dioxetane‐1,2‐diyl) oxime (L1) exhibited Nernstian responses for Cr³⁺ ion over wide concentration ranges (1.5×10^?6–8.0×10^?3 M for PME and 4.0×10^?7–3.0×10^?3 M for CGCE) and very low limits of detection (1.0×10^?6 M for PME and 2.0×10^?7 M for CGCE). The proposed potentiometric sensors manifest advantages of relatively fast response and, most importantly, good selectivities relative to a wide variety of other cations. The selectivity behavior of the proposed Cr³⁺ ion‐selective electrodes revealed a considerable improvement compared to the best previously PVC‐membrane electrodes for chromium(III) ion. The potentiometric responses of the electrodes are independent of pH of the test solution in the pH range 3.0–6.0. The electrodes were successfully applied to determine chromium(III) in water samples.     

Highly Selective Nd(III) Sensors: Novel Macrocyclic Compounds for Potentiometric Determination of Neodymium

Conductometric studies on the complexation properties of two newly synthesized lariat ethers viz 1,5‐di(cyanoethane)‐2,4 : 7,8 : 13,14‐tribenzo‐1,5‐diaza‐9,12‐dioxacyclopentadeca‐2,7,13‐triene (L₁) and 1,5‐di(cyanoethane)‐2,3,4‐pyridine‐7,8 : 13,14‐dibenzo‐1,3,5‐triaza‐9,12‐dioxa cyclopentadeca‐2,7,13‐triene (L₂) towards various metal ions in acetonitrile solutions revealed the formation of 1 : 1 ligand metal complexation. These compounds were explored as neutral ionophores for the fabrication of Nd³⁺ selective and sensitive membrane coated graphite electrodes (CGEs). Among all the electrodes prepared, CGEs with membrane composition L₁(5%) : NaTPB(3%) : NPOE (57%) : PVC (35%) and L₂(5%) : NaTPB(3%) : NPOE (53%) : PVC (39%) showed best performance. Both the electrodes showed Nernstian response towards Nd³⁺ ions over a wide concentration range with detection limits 3.8×10^?8 mol L^?1 and 1.6×10^?8 mol L^?1 respectively. These electrodes showed a fast response time of <15 s and could be used over a period of three months without significant divergence in their characteristics. The proposed electrodes revealed very good selectivity for Nd³⁺ ions over several ions. However, higher concentration of Co²⁺, La³⁺, Pr³⁺ and Yb³⁺ caused some interference. The potentiometric response of these electrodes was excellent in the range of pH 3.5 to 7.6 and they could tolerate up to 20% (v/v) nonaqueous media in the test solutions. These electrodes were used successfully as indicator electrode in the potentiometric titration of Nd³⁺ against EDTA and also in the quantitative determination of Nd³⁺ ions from binary mixtures and water samples.     

Highly Selective and Sensitive Perchlorate Sensors Based on Some Recently Synthesized Ni(II)‐Hexaazacyclotetradecane Complexes

Three nickel(II)‐hexaazacyclotetradecane complexes were studied to characterize their abilities as perchlorate ion carrier in PVC membrane electrodes. The electrodes based on these complexes exhibit Nernstian responses for ClO over very wide concentration ranges (1.0×10^?1 ?5.0×10^?7 M) with detection limits of 2.0×10^?7 ?5.0×10^?7 M (20–50 ng/mL). The sensors show very good selectivity for ClO ion in comparison with the most common organic and inorganic anions. The responses of the proposed electrodes are independent of pH in the range of 3.5–11.0. The perchlorate selective membranes show fast response time (<10 s) and can be used for 4–12 weeks without any major deviation. The sensors were successfully used to determine the perchlorate ion in water, wastewater and human urine samples.     

[Cu(L)](NO3)2 (L=4,7‐Bis(3‐aminopropyl)‐1‐thia‐4,7‐diazacyclononane) as a Suitable Ionophore for Construction of Thiocyanate‐Selective Electrodes and Their Use in Determination of Urinary and Salivary Thiocyanate Concentration

The construction, performance characteristics, and application of polymeric membrane (PME) and coated graphite (CGE) thiocyanate‐selective electrodes are reported. The electrodes were prepared by incorporating the complex [Cu(L)](NO₃)₂ (L=4,7‐bis(3‐aminopropyl)‐1‐thia‐4,7‐diazacyclononane) into a plasiticized poly(vinyl chloride) membrane. The influence of membrane composition, pH of test solution, and foreign ions were investigated. The electrodes reveal Nernstian behavior over a wide SCN^? ion concentration range (1.0×10^?6–1.0×10^?1 M for PME and 5.0×10^?7–1.0×10^?2 M for CGE) and show fast dynamic response times of 15 s and lower. The proposed sensors show high selectivity towards thiocyanate over several common organic and inorganic anions. They were successfully applied to the direct determination of thiocyanate in urine and saliva of smokers and nonsmokers, and as an indicator electrode in titration of Ag⁺ ions with thiocyanate.     

Novel Copper(II)‐Selective Membrane Electrode Based on a New Synthesized Schiff Base

A PVC membrane electrode for copper(II) ion based on a recently synthesized Schiff base as a suitable ion carrier was constructed. The electrode exhibits a Nernstian slope of 28.3 ± 0.6 mV per decade of Cu²⁺ over a wide concentration range of 7.0 × 10^?6‐2.6 × 10^?2 M with a detection limit of 5.0 × 10^?6M in the pH range of 4.2–5.8. The response time is about 10s and it can be used for at least 1 month without any considerable divergence in potential. It was successfully applied as an indicator electrode in the potentiometric titration of copper ions.     

Polymeric Membrane Lanthanum(III)‐Selective Electrode Based on N,N′‐Adipylbis(5‐phenylazo salicylaldehyde hydrazone)

A recently synthesized azao‐containing Schiff's base N,N′‐adipylbis(5‐phenylazo salicylaldehyde hydrazone) was used as a suitable neutral ion carrier in construction of a highly selective La³⁺‐PVC membrane electrode. The electrode exhibits a Nernstian response with a slope of 19.4 mV decade^?1 over a wide concentration range (1.0×10^?6–1.0×10^?2 M) and a limit of detection of 4.0×10^?7 M (0.05 ppm). The electrode possesses a fast response time of ca. 10 s and can be used for at least 3 months without observing any deviation. The proposed electrode revealed excellent selectivity for La³⁺ over a wide variety of alkali, alkaline earth, transition and heavy metal ions and could be used in a pH range of 4.0–8.0. The practical utility of the electrode has been demonstrated by its use as an indicator electrode in the potentiometric titration of La³⁺ ions with EDTA and in determination of F^? ion in some pharmaceutical preparations.     

Highly Selective and Sensitive Tin(II) Membrane Electrode Based on a New Synthesized Schiff's Base

Studies on complex formation of tris(3‐(2‐hydroxybenzophenone)propyl)amine (THPA) with a number of metal ions in acetonitrile solution revealed the occurrence of a selective 1 : 1 complexation of the proposed ligand with Sn²⁺ ion. Consequently, THPA was used as a suitable neutral ionophore for the preparation of a polymeric membrane‐selective electrode. The electrode exhibits a Nernstian behavior with a slope of 29.4±0.3 mV per decade and a detection limit of 2.0×10^?7 M. It also showed a good selectivity for Sn²⁺ ions in comparison with some of group A and B metal ions over a wide concentration range of 5.0×10^?7–1.0×10^?1 M. Improved selectivity was achieved compared to the best selectivity recently reported by other authors for tin(II). The electrode was successfully applied to the determination of Sn²⁺ ion in waste water and various canned products.     

Thermal Studies of New Lead(II) Coated‐Wire Membrane Electrodes

Five plastic membrane Pb²⁺‐selective electrodes were prepared based on 1,4‐bis(N‐tosyl‐o‐aminophenoxy)butane I , 1,4‐bis(N‐allyl‐N‐tosyl‐o‐aminophenoxy)butane II , 1,4‐bis(N‐benzyl‐N‐tosyl‐o‐aminophenoxy)butane III , 1,4‐bis[N‐(o‐allyloxybenzyl)‐N‐tosyl‐o‐aminophenoxy]butane IV , and 1,4‐bis(N‐octyl‐N‐tosyl‐o‐aminophenoxy)butane V as neutral carriers. The electrodes exhibited nearly Nernstian responses over the concentration ranges, 2.5×10^?4–4.0×10^?2, 2.5×10^?5–4.0×10^?2, 7.9×10^?5–4.0×10^?2, 2.2×10^?5–4.0×10^?2, and 1.9×10^?4–4.0×10^?2 M for electrodes composed with the ionophores I–V , respectively. All electrodes showed pH range of about 4.0 to 11.5 and working temperature range of 22 to 70 °C with isothermal temperature coefficients of 1.19×10^?3, 1.16×10^?3, 1.16×10^?3, 1.00×10^?3 , and 1.32×10^?3 V/°C for electrodes I–V respectively.     

Mixed Aza‐Thioether Crowns Containing a 1,10‐Phenanthroline Sub‐Unit as Neutral Ionophores for Silver Ion

Three different recently synthesized aza‐thioether crowns containing a 1,10‐phenanthroline sub‐unit (L1–L3) and a corresponding acyclic ligand (L4) were studied to characterize their abilities as silver ion ionophores in PVC‐membrane electrodes. Novel conventional silver‐selective electrodes with internal reference solution (CONISE) and coated graphite‐solid contact electrodes (SCISE) were prepared based on one of the 15‐membered crowns containing two donating S atoms and two phenanthroline‐N atoms (L1). The electrodes reveal a Nernstian behavior over wide Ag⁺ ion concentration ranges (1.0×10^?5?1.0×10^?1 M for CONISE and 5.0×10^?8?4.0×10^?2 M for SCISE) and very low limits of detection (8.0×10^?6 M for CONISE and 3.0×10^?8 M for SCISE). The potentiometric response is independent from pH of the solution in the pH range 3.0–8.0. The electrodes manifest advantages of low resistance, very fast response and, most importantly, good selectivities relative to a wide variety of other cations. The electrodes can be used for at least 2 months (for CONISE) and 4 months for (SCISE) without any appreciable divergence in potentials. The electrodes were used as an indicator electrode in the potentiometric titration of Ag⁺ ion and in the determination of silver in photographic emulsions and in radiographic and photographic films.     

Highly Selective and Sensitive Copper(II) Membrane Sensors Based on 6‐Methyl‐4‐(1‐phenylmethylidene)amino‐3‐thioxo‐1,2,4‐triazin‐5‐one as a New Neutral Ionophore

A new Cu(II) ion‐selective PVC membrane sensor based on 6‐methyl‐4‐(1‐phenylmethylidene)amino‐3‐thioxo‐1,2,4‐triazin‐5‐one (MATTO) as an excellent sensing material was developed. The electrode exhibits a Nernstian slope of 29.2±0.4 mV per decade over a very wide concentration range between 1.0×10^?1 and 1.0×10^?6 M, with a detection limit of 4.8×10^?7 M (30.5 ng/mL). The sensor possesses the advantages of short conditioning time, fast response time (<10 s), and especially, very good selectivity towards transition and heavy metal, and some mono, di and trivalent cations. The proposed electrode was successfully applied to the determination of copper in wastewater of copper electroplating samples and as an indicator electrode in potentiometric titration of Cu(II) ions with EDTA.     

Zn(II)‐Selective Membrane Electrode Based on Tetraazamacrocycle [Bzo2Me2Ph2(16)hexaeneN4]

A PVC membrane electrode using [Bzo₂Me₂Ph₂(16)hexaeneN₄] ( I ) as ionophore, oleic acid as lipophilic additive and o‐nitrophenyloctyl ether as plasticizer has been investigated as Zn(II)‐selective electrode. The membrane incorporating 34.9% (w/w) PVC, 2.3% I , 4.7% OA and 58.1% o‐NPOE gave linear response over the concentration range 2.82×10^?6?1.0×10^?1 M with a Nernstian slope of 28.5±0.2 mV/decade of concentration with a detection limit of 2.24×10^?6 M (0.146 ppm) and showed a response time of less than 10 s and could be used in pH range 2.5–8.5. High selectivity was obtained over a wide variety of metal ions. The proposed electrode was successfully used as an indicator electrode in potentiometric titration of zinc ions with EDTA and for determination of zinc in real samples.     

Investigation of Silver(I) Ion Sensing Property of Ruthenium(II) Thiosemicarbazone Complex Using Coated Graphite and Polymeric Membrane Electrodes

A ruthenium(II) complex [Ru(PPh₃)₂(pytsc)₂] {Hpytsc = pyridine‐2‐carbaldehydethiosemicarbazone, (C₅H₅N)C²(H)=N³‐N²(H)‐C¹(=S)N¹H} has been used as an ion carrier for the selective determination of silver(I) ions in solution. Silver(I) ion‐selective coated graphite based (CGE) and PVC polymeric membrane based (PME) electrodes exhibit Nernstian slope for silver(I) ions over a wide concentration range from 1.0 × 10⁻¹ M to 5.0 × 10⁻⁶ M (with CGE) and 1.0 × 10⁻¹ M to 2.0 × 10⁻⁵ M (with PME). The working pH range of these electrodes has been found to be from 1.2 to 7.2 for CGE and 2.2 to 6.5 for PME. The proposed CGE sensor exhibits better analytical features like sensitivity and selectivity towards different secondary ions in comparison to the corresponding PME with no interference from mercury(II) ions . These electrodes also act as indicator electrodes in potentiometric titration and have been successfully used for the determination of silver content in solution of real samples (1 gm dissolved in 100 mL of dilute nitric acid) such as silver ornaments and thin silver foils. Silver content determined by the use of ion selective electrode was found to vary in the concentration range from 1.20 x 10⁻² M to 7.45 x 10⁻² M and results were found to be comparable with those obtained from the traditional volumetric method of analysis. It is the first report of a metal‐ligand complex used as an ion carrier in ion selective electrode, which is selective for a metal ion other than the one used in the complex.     

Electroanalytical Studies on Cobalt(II) Ion‐Selective Sensor of Polymeric Membrane Electrode and Coated Graphite Electrode Based on N2O2 Salen Ligands

Poly(vinyl chloride)‐based membranes of salen ligands, 2‐((E)‐((1R,2S)‐2‐((E)‐5‐tert‐butyl‐2‐hydroxybenzylideneamino)cyclohexylimino)methyl)‐4‐tert‐butyl phenol (S₁) and 2‐((E)‐((1R,2S)‐2‐((E)‐3,5‐di‐tert‐butyl‐2‐hydroxybenzylideneamino)cyclohexylimino)methyl)‐4,6‐di‐tert‐butylphenol (S₂) were fabricated and explored as cobalt(II) selective electrodes. The performance of the polymeric membrane electrode (PME) and coated graphite electrode (CGE) were compared and it was observed that CGE showed a wide working concentration range of 1.1×10^?8 to 1.0×10^?1 mol L^?1 with a limit of detection of 7.0×10^?9 mol L^?1 exhibiting the Nernstian slope 29.6 mV/decade of activity in the pH range 3.0–9.0. It was used for the determination of cobalt(II) ions in water, soil, beer, pharmaceutical samples and medicinal plants and would be used as an indicator electrode in potentiometric titration with EDTA.     

Comparative Studies of Tridentate Sulfur and Nitrogen‐Containing Ligands as Ionophores for Construction of Cadmium Ion‐Selective Membrane Sensors

New polymeric membrane cadmium‐ion selective sensors have been prepared by incorporating nitrogen and sulfur containing tridentate ligands as the ionophores into the plasticized PVC membranes. Poly(vinyl chloride) (PVC) based membranes of potassium hydrotris[N‐(2,6‐xylyl)thioimdazolyl) borate] (KTt^2,6‐xylyl) and potassium hydrotris(3‐phenyl‐5‐methylpyrazolyl) borate (KTp^Ph,Me) with sodium tetraphenyl borate (NaTPB) as an anionic excluder and dibutylphthalate (DBP), tributylphthalate (TBP), dioctylsebacate (DOS), and o‐nitrophenyloctyl ether (o‐NPOE) as plasticizing solvent mediators were investigated in different compositions. KTt^2,6‐xylyl was found to be a selective and sensitive ion carrier for Cd(II) membrane sensor. A membrane composed of KTt^2,6‐xylyl:NaTPB:PVC:DBP with the % mole ratio 2.3 : 1.1 : 34.8 : 61.8 (w/w) works well over a very wide concentration range (7.8×10^?8–1.0×10^?2 M) with a Nernstian slope of 29.4±0.2 mV/decades of activity between pH values of 3.5 to 9.0 with a detection limit of 4.37×10^?8 M. The sensor displays very good discrimination toward Cd(II) ions with regard to most common cations. The proposed sensor shows a short response time for whole concentration range (ca. 8 s). The effects of the cationic (tetrabutylammonium chloride, TBC), anionic (sodium dodecyl sulfate, SDS) and nonionic (Triton X‐100) surfactants were investigated on the potentiometric properties of proposed cadmium‐selective sensor. The proposed sensor based on KTt^2,6‐xylyl ionophore has also been used for the direct determination of cadmium ions in different water samples and human urine samples.     

A Highly Selective and Sensitive Barium(II)‐Selective PVC Membrane Based on Dimethyl 1‐Acetyl‐8‐oxo‐2,8‐dihydro‐ 1H‐pyra‐zolo[5,1‐a]isoindole‐2,3‐dicarboxylate

A poly(vinyl chloride)‐based membrane of dimethyl 1‐acetyl‐8‐oxo‐2,8‐dihydro‐1H‐pyra‐zolo[5,1‐a]isoindole‐2,3‐dicarboxylate as a neutral carrier with sodium tetraphenylborate (NaTPB) as an anion excluder and 2‐nitrophenyl octyl ether (NPOE) as plasticizer was prepared and investigated as a Ba(II)‐selective electrode. The electrode exhibits a Nernstian slope of 29.7±0.4 mV per decade over a wide concentration range (1.0×10^?6 to 1.0×10^?1 M) with a detection limit of 7.6×10^?7 M between pH 3.0 and 11.0. The response time of the sensor is about 10 s and it can be used over a period of 2 months without any divergence in potential. The proposed membrane sensor revealed good selectivity for Ba(II) over a wide variety of other metal ions. It was successfully used in direct determination of barium ions in industrial wastewater samples.     

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.     

Aluminum(III)‐selective PVC Membrane Electrode Based on Salicylaldehyde Salicyloyl Hydrazone

A highly selective PVC membrane electrode for Al³⁺ based on salicylaldehyde salicyloyl hydrazone as a neutral carrier has been prepared and studied. The sensor exhibits a good response for Al³⁺ over a linear range of 9.0 × 10^‐6 to 1.0 × 10^‐1 mol/L, with a Nernstian slope of 20.0 ± 0.2 mV/decade and detection limit of 7.0 × 10^‐6 mol/L. Selectivity coefficients determined by the method of separate solution indicate high selectivity for Al³⁺. The response mechanism was discussed in view of UV‐Vis spectroscopy technique and the A.C. impedance technique. It was used as an indicator electrode in potentiometric titration of Al3+ with EDTA and in the determination of Al³⁺ in real samples. The electrode has a relatively fast response time, long life time and satisfactory stability.     

Ruthenium(III) Schiff's Base Complex as Novel Chloride Selective Membrane Sensor

A novel chloride PVC‐based membrane sensor based on a ruthenium(III) Schiff's base complex, as an excellent neutral carrier, has been developed. The ruthenium complex, in combination with a ketonic plasticizer and a cationic additive led to ISEs with fundamental characteristics, such as slope sensitivity, short response times and selectivity coefficients, which were sufficient for practical applications. The sensor with composition of 30% PVC, 62% benzyl acetate, 5% ruthenium(III) Schiff's base complex and 3% hexadecyltrimethyl ammonium bromide displays near‐Nernstian behavior in a wide concentration range (1.0×10^?1–3.0×10^?6 M with slope of ?54.5±0.5) with a detection limit of 2.0×10^?6 M (71.0 ng per mL). The response of the electrode is independent on pH in the range of 4.0–10.0 and can it be used for at least ten weeks. The proposed electrode shows a very short response time (<20 s) in whole concentration range. The sensor displays high selectivity toward chloride ions over several organic and inorganic anions. It was successfully applied for the determination of chloride in serum samples. It was also used as an indicator electrode in the potentiometric titration of chloride ions with silver nitrate solution.