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.     

Potentiometric Membrane Electrode for Cr(III) Ion Based on a New Aryl Amide Bifunctional Bridging Ligand as a Neutral Carrier

A novel Cr(III) ion‐selective electrode is constructed by incorporating a new aryl amide bifunctional bridging ligand, 2,2′‐bis{[(2″‐benzylaminoformyl)phenxoyl]methyl}‐diethylether (BBPMD) as a neutral carrier into the PVC matrix. The proposed electrode, with optimum membrane composition, exhibits an excellent near‐Nernstian response for Cr³⁺ ion ranging from 2.8 × 10^?6 to 1.0 × 10^?1 mol/L with a detection limit of 8.6 × 10^?7 mol/L and a slope of 19.5 ± 0.2 mV/dec in pH 3.0 nitrate buffer solution at 25 °C. It has an appropriate response time, suitable reproducibility, and good selectivity towards Cr³⁺ ion. The operational pH range of the proposed electrode is 2.5–6.5. The response mechanism was discussed in view of UV‐vis spectroscopy and the A. C. impedance technique. The excellent analytical features of the proposed electrode could lead to its successful application as an indicator electrode in potentiometric titration of Cr³⁺ ion and in the direct determination of Cr³⁺ ion in tea leaves and coffee samples.     

Be(II) Graphite Coated Membrane Sensor Based on a Recently Synthesized Benzo‐9‐Crown‐3 Derivative

A highly sensitive and selective membrane electrode with 9‐crown‐3 derivative (CD) as ionophore, potassium tetrakis‐(p‐chlorophenyl) borate as anionic additive (KTB), acetophenone (AP) as solvent mediator was prepared and investigated as a Be(II) sensor. The best performance was observed with the membrane having the percent ratio 30% PVC: 8% CD: 6% KTB: 56% Acetophenone. The poly(vinyl chloride) PVC membrane containing 9‐crown‐3 derivative (CD) directly coated on a graphite electrode, shows a Nernstian response for Be(II) ions over a very wide concentration range (1.0×10^?1?1.0×10^?7 M) with a detection limit of 8.0×10^?8 M (ca. 0.72 ng/mL). It has a fast response time of ca. 20 s and can be used for at least 10 weeks without any major deviation in potential. The proposed sensor exhibits very good selectivity with respect to common alkali, alkaline earth, transition and heavy metal ions. The proposed sensor was used as end point indicator electrode in the titration of Be(II) ions with EDTA. It was also applied to determination of Be(II) in real sample.     

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 and Sensitive Membrane Sensors for Copper(II) Ion Based on a New Benzo‐Substituted Macrocyclic Diamide 6,7,8,9,10‐Hexahydro‐2H‐1,13,4,7,10‐benzodioxatriazacyclopentadecine‐3,11(4H,12H)‐dione

Novel PVC membrane (PME) and coated graphite (CGE) Cu²⁺‐selective electrodes based on 5,6,7,8,9,10‐hexahydro‐2H‐1,13,4,7,10‐benzodioxatriazacyclopentadecine‐3,11(4H,12H)‐dione are prepared. The electrodes reveal a Nernstian behavior over wide Cu²⁺ ion concentration ranges (1.0×10^?7–1.0×10^?1 M for PME and 1.0×10^?8–1.0×10^?1 M for CGE) with very low limits of detection (7.8×10^?8 M for PME and 9.1×10^?9 M for CGE). The potentiometric responses are independent of the pH of the test solutions in the pH range 2.7–6.2. The proposed electrodes possess very good selectivities for Cu²⁺ over a wide variety of the cations including alkali, alkaline earth, transitions and heavy metal ions. The practical utility of the proposed electrodes have been demonstrated by their use in the study of interactions between copper ions and human growth hormone (hGH) in biological systems, potentiometric titration of copper with EDTA and determination of copper content of a sheep blood serum sample and some other real samples.     

A New Pentadentate S‐N Schiffs' Base as a Novel Ionophore in Construction of a Novel Gd(III) Membrane Sensor

We found that bis(thiophenal) pyridine‐2,6‐diamine (BPD) can be used as an excellent ion carrier to prepare a gadolinium‐selective PVC‐based membrane sensor. The use of oleic acid (OA) and potassium tetrakis(p‐chlorophenyl borate)(KTKpClPB), as anionic additives, and dibutyl phthalate (DBP), acetophenone (AP) and nitrobenzene (NB), as plasticizing solvent mediators was investigated. The best performance was observed with a membrane having the composition of 30% PVC; 62% BA; 5% BPD; and 3% KTKpClPB. The resulting sensor works well over a relatively wide concentration range (1.0×10^?6–1.0×10^?1 M) with a Nernstian slope of 19.4±0.4 mV per decade of gadolinium activity over a wide pH range (3.5–8.0). The limit of detection of the sensor is 7.0×10^?7 M (ca. 110 ng mL^?1). The proposed electrode shows excellent discriminating ability toward gadolinium ions with regard to common alkali, alkaline earth, transition, heavy metal ions, and specially, lanthanide ions. The proposed sensor was applied as an indicator electrode for titration of gadolinium ions with EDTA.     

Crown Ethers Bearing 18C6 Unit; Sensory Molecules for Fabricating PVC Membrane Lead Ion‐selective Electrodes

Crown ethers bearing 18C6 unit 18‐crown‐6 (18C6), dicyclohexyl18‐crown‐6 (DC18C6) and dibenzo18‐crown‐6 (DB18C6) have been examined as ion sensing materials for fabricating lead ion‐selective potentiometric sensors. Best performance of the electrode based upon 18C6 ionophore was achieved by using a membrane including 9% ionophore, 30% polyvinyl chloride (PVC), 2% oleic acid and 59% dibutylphthalate (DBP). The optimum composition for the sensors based on DC18C6 and DB18C6 was provided by the compositions: 9% DC18C6, 30% PVC, 1.5% sodium tetraphenyl borate (NaTBP), 59.5% DBP; and 5.9% DB18C6, 29.7% PVC, 2.5% NaTBP and 61.9% DBP, respectively. The linear response range of the electrode based on 18C6 (1 × 10^‐6‐1 × 10^‐3 M) differs from that presented by the DC18C6‐ and DB18C6‐based electrodes (1 × 10^‐5‐1 × 10^‐2 M). All the sensors were shown rapid response time (<12 s). The detection limit of the electrodes varies as 5.6 × 10^‐7, 6.3 × 10^‐6 and 7.1 × 10^‐6 M, for 18C6‐, DC18C6‐ and DB18C6‐based electrodes, respectively. The selectivity of the electrodes towards lead ions over some mono‐, di‐ and trivalent metal ions was evaluated. The lifetime of the electrode based on DC18C6 or DB18C6 ionophores was found to be more than three months, while it was shorter for 18C6‐based electrode. The application of the electrodes in aqueous samples was assessed.     

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.     

Etilefrine Plastic Membrane Electrodes Based on Individual and Mixed Ion-exchangers of Etilefrinium Phosphotungstate and Tetraphenylborate.

Abstract

Etilefrine hydrochloride (EfCl) selective PVC membrane electrodes based on Etilefrinium phosphotungstate (I), Etilefrinium tetraphenylborate (II) and a mixture of both (III) were prepared, The electrodes exhibited near Nernstian response over the concentration ranges 5.0 × 10^?6 - 1.0 × 10^?1, 6.3 × 10^?6 - 1.0 × 10^?1 and 6.3 × 10^?5 - 1.0 × 10^?1 M EfCl for electrodes I, II and III, respectively. The working pH ranges of electrodes I, II and III were 10 - 8.0, 10 - 7.5 and 10 - 7.5 and their isothermal coefficients were 0.00150, 0.00088 and 0.00072 V/°C, respectively. The electrodes showed good selectivity to EfCl with respect to many inorganic cations, sugars and amino acids. The standard additions method was used to determine EfCl in pure solutions and in pharmaceutical preparations.     

Amide and Acyl‐Hydrazine Functionalized Calix[4]arenes as Carriers for Hydrogen Phosphate Selective Electrodes

Anion‐selective solvent polymeric membrane based on hydrogen bond‐forming, neutral ionophores with amide or acyl‐hydrazine groups are described. The use of the two calix[4]arenes results in anion‐selective electrodes with a selectivity for phosphate. The electrodes of the optimum characteristic have the composition of 1 wt% ionophore, 66 wt% o‐NPOE, 33 wt% poly (vinyl chloride) (PVC) and TDMACl (15 or 30 mol% relative to the ionophore 1 and 2 , respectively). The optimized membrane electrodes show Nernstian responses towards monohydrogen phosphate (?29.1 and ?29.3 mV/decade) based on ionophore 1 and 2 , respectively, in a wide concentration range (1.0×10^?5 to 1.0×10^?2 or 1.0×10^?5 to 1.0×10^?1 M). The selectivity coefficients are determined with the fixed interference method and the activity ratio method. The electrodes display an anti‐Hofmeister series selectivity pattern and highly selective for HPO₄^2? over Cl^?, Br^?, CH₃COO^?, NO₃^? and SO₄^2?. The lifetime of the electrodes is at least 1 month and their response time is found to be 25 s. The proposed sensors could be put to analytical use both by direct potentiometry as well as potentiometric titration.     

Novel Potentiometric Sensors for Determination of Melatonin and Oxomemazine in Biological Samples and in Pharmaceutical Formulations

Simple, selective and accurate sensors were developed for the determination of melatonin and oxomemazine in biological samples (urine) and in pharmaceutical preparations. Potentiometric measurements were based on bismus tetraiodate‐drug ion‐pair as novel electroactive materials incorporating a plasticized PVC membrane with o‐nitrophenyl octyl ether or dioctyl phthalate. Each sensor was conditioned for at least two days in 0.1 M drug solution before use. It exhibited fast and stable Nernstian response for melatonin and oxomemazine over the concentration range of 1.0×10^?6–1.0×10^?2 M and 1.0×10^?5–1.0×10^?2 M, pH range of 3.0–6.5 and 3.5–6.0 for melatonin and oxomemazine sensors, respectively. Results with an average recovery not more than 101 % and a mean standard deviation less than 1.0 % of the nominal were obtained for the four sensors. The sensors showed reasonable selectivity towards investigated drugs in presence of many cations.     

A Copper(II) Ion‐Selective Potentiometric Sensor Based on N,N′,N″,N′′′‐Tetrakis(2‐pyridylmethyl)‐1,4,8,11‐tetraazacyclotetradecane in PVC Matrix

The simple PVC‐based membrane containing N,N′,N″,N′′′‐tetrakis(2‐pyridylmethyl)‐1,4,8,11‐tetraazacyclotetradecane (tpmc) as an ionophore and dibutyl phthalate as a plasticizer, directly coated on a glassy carbon electrode was examined as a new sensor for Cu²⁺ ions. The potential response was linear within the concentration range of 1.0×10^?1–1.0×10^?6 M with a Nernstian slope of 28.8 mV/decade and detection limit of 7.0×10^?7 M. The electrode was used in aqueous solutions over a wide pH range (1.3–6). The sensor exhibited excellent selectivity for Cu²⁺ ion over a number of cations and was successfully used in its determination in real samples.     

Comparative Study of Lead(II) Selective Poly(vinyl chloride) Membrane Electrodes Based on Podand Derivatives as Ionophores

The two podand chelates based on diethylsulfide, 1,5‐bis(2′‐hydroxy‐4′‐nitrophenoxy)‐3‐thiapentane (L₁) and 1,5‐bis(8′‐oxybenzopyridine)‐3‐thia pentane (L₂), have been synthesized and explored as neutral ionophores for preparing poly(vinyl chloride) based membrane electrodes selective to Pb²⁺. The addition of anionic additives and various plasticizers has been found to substantially improve the performance of the electrode. The best performance was obtained with the electrode No. 1 having a membrane of ionophore (L₁) with the composition PVC:o‐NPOE:ionophore (L₁):NaTFPB (%w/w) of 33 : 62 : 3 : 2. The electrode exhibits Nernstian response with a slope of 31.57±0.3 mV decade^?1 of activity in the concentration range from 2.0×10^?9 to 1.0×10^?1 M Pb²⁺, performs satisfactorily over a wide pH range (1.6–7.0), with a fast response time (5 s).     

Novel Cesium‐Selective Electrodes Based on Lipophilic 1,3‐Bisbridged Cofacial‐calix[6]crowns

Five bisbridged calix[6]crowns have been investigated as Cs⁺ ionophore in PVC membrane electrodes. As ionophores, three 1,3‐bisbridged calix[6]crown‐4‐ethers( I–III ), 1,3‐bisbridged calix[6]crown‐5‐ether( IV ), and 1,3‐bisbridged calix[6]crown‐6‐ether( V ) have been evaluated. The membranes all give good Nernstian response in the concentration range from 1×10^?7 to 1×10^?1 M of cesium ion. The best detection limits (?log aequation/tex2gif-inf-1.gif=7.08–7.36) are obtained for electrode membranes containing 1,3‐bisbridged cofacial‐calix[6]crown‐4‐ethers( I‐III ), and the values are the lowest compared with those reported previously. The highest selectivity coefficients [ 3.74(Cs/K), 2.63(Cs/Rb)] are obtained for the membrane of 1,3‐bisbridged calix[6]crown‐4‐ether( II ), and these values are also the highest compared with previous reports for Cs⁺‐ISEs. The highest selectivity towards cesium ion is attributed to the geometrically cofacial positions of two crown‐ethers in calix[6]crowns in order to provide the complex of cesium ion and eight oxygens of cofacial crowns.     

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.     

A New Chromium(III) Microelectrode Based on Self‐Assembled Diethylenetriamminepentaacetic Acid‐Poly(fuchsin basic) Modified Electrode

A new selective, sensitive, and rapid response microelectrode for microamount chromium(III) determination was developed. For the electrode preparation, fuchsin basic was electropolymerized onto a carbon microdisk electrode, and then diethylenetriamminepentaacetic acid (DTPA) was self‐assembled on the electrode surface by the reaction between DTPA and poly(fuchsin basic). The determination conditions were optimized. The electrode showed a linear response to Cr³⁺ ions in the concentration range of 1.0×10^?6?1.0×10^?4 M and exhibits a super‐Nernstian slope of 32.5±0.4 mV per decade. The detection limit is 3.6×10^?7 M. The response time of the electrode is less than 10 s, and it can be used for at least 2 months with limited considerable divergences in its potentials. The proposed electrode was applied for monitoring the chromium ion level in wastewater of chromate industries.     

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.     

[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.     

The synthesis of bis(benzo-crown ether)s and their incorporation into potassium-selective PVC membrane electrodes

Five bis(benzo-15-crown-5) derivatives connected with different bridge chains were synthesized as neutral carriers in K⁺-selective electrodes. Potassium ion-selective PVC membrane electrodes based on these bis(crown ether)s were prepared using dibutyl phthalate (DBP) and dioctyl phthalate (DOP) as plasticizers of the PVC membrane. The selectivity coefficients (K _M ⁿ⁺:K _K+) for various alkali and alkaline-earth metal ions were measured. The electrodes based on the bis(crown ether)s are more selective for K⁺ than those based on monomeric crown ethers. The selectivity of one of the prepared potassium selective electrodes was higher than that of the electrode based on valinomycin and three of them were stable over a wide pH range.     

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.