Ho3+ carbon paste sensor based on multi-walled carbon nanotubes: Applied for determination of holmium content in biological and environmental samples

For the first time a novel multi-walled carbon nanotubes (MWCNTs) modified Ho³⁺ carbon paste sensor is introduced. The electrode with a composition containing 20% paraffin oil, 60% graphite powder, 15% N-(1-thia-2-ylmethylene)-1,3-benzothiazole-2-amine (TBA) as an ionophore, and 5% MWCNTs, exhibits a stable potential response to Ho³⁺ ions with a nice Nernstian behavior (19.3 ± 0.3 mV decade^? 1) in a wide dynamic linear concentration range of Ho³⁺ ions (1 × 10^? 8–1.0 × 10^? 2 M). In the absence of MWCNTs, sensitivity of the Ho³⁺ sensor was relatively poor. The proposed modified Ho³⁺ sensor shows very low detection limit (7.0 × 10^? 9 M) and a fast response time (13 s). It has a long life time (more than 2 months) and its response is independent of pH in the range of 3.8–7.5. In term of selectivity, Ho³⁺ sensor has a good selectivity over all lanthanide members and common alkali and alkaline earth metal ions. The Ho³⁺ sensor was applied for the determination of Ho³⁺ ion concentration in water, holmium alloys and synthetic human serum.     

Quantitative monitoring of terbium ion by a Tb3+ selective electrode based on a new Schiff's base

Solution study showed N,N′-bis(5-nitrosalicylidene)-2-aminobenzylamin (L) trends toward Tb³⁺ ion. Then, it was used as a suitable ionophore in construction of terbium ion selective electrode. The electrode with composition of 30% PVC, 65% solvent mediator (NB), 3% ionophore (L) and 2% anionic additive (NaTPB) shows the best potentiometric response characteristics. It displays a Nernstian behavior (20.1 mV decade^?1) over the concentration range 1.0 × 10^? 6 to 1.0 × 10^? 2 mol L^?1. The detection limit of the electrode is 6.3 × 10^? 7 mol L^?1. It has a very short response time (~ 10 s) and a useful working pH range of 2.6–9.4 for at least 2 months. The proposed membrane sensor shows excellent discriminating ability towards Tb³⁺ ions with regard to several alkali, alkaline earth, transition and heavy metal ions. To investigate the analytical applicability of the sensor, it was successfully applied to the determination of terbium in certified reference material.     

Selective recognition of Pr3 + based on fluorescence enhancement sensor

(E)-2-(1-(4-hydroxy-2-oxo-2H-chromen-3-yl)ethylidene)hydrazinecarbothioamide (L) has been used to detect trace amounts of praseodymium ion in acetonitrile–water solution (MeCN/H₂O) by fluorescence spectroscopy. The fluorescent probe undergoes fluorescent emission intensity enhancement upon binding to Pr^3 + ions in MeCN/H₂O (9/1:v/v) solution. The fluorescence enhancement of L is attributed to a 1:1 complex formation between L and Pr^3 +, which has been utilized as the basis for selective detection of Pr^3 +. The sensor can be applied to the quantification of praseodymium ion with a linear range of 1.6 × 10^? 7 to 1.0 × 10^? 5 M. The limit of detection was 8.3 × 10^? 8 M. The sensor exhibits high selectivity toward praseodymium ions in comparison with common metal ions. The proposed fluorescent sensor was successfully used for determination of Pr^3 + in water samples.     

Fabrication of a PVC membrane samarium(III) sensor based on N,N′,N″-tris(4-pyridyl)trimesic amide as a selectophore

A new ion-selective electrode for Sm^3 + ion is described based on the incorporation of N,N′,N″-tris(4-pyridyl)trimesic amide (TPTA) in a poly(vinylchloride) (PVC) matrix. The membrane sensor comprises nitrobenzene (NB) as a plasticizer, and oleic acid (OA) as an anionic additive. The sensor with the optimized composition shows a Nernstian potential response of 19.8 ± 0.5 mV decade^? 1 over a wide concentration range of 1.0 × 10^? 2 and 1 × 10^? 6 mol L^? 1, with a lower detection limit of 4.7 × 10^? 7 mol L^? 1 and satisfactor applicable pH range of 3.6–9.2. Having a short response time of less than 10 s and a very good selectivity towards the Sm^3 + over a wide variety of interfering cations (e.g. alkali, alkaline earth, transition and heavy metal ions) the sensor seemed to be a promising analytical tool for determination of the Sm^3 +. Hence, it was used as an indicator electrode in the potentiometric titration of samarium ion with EDTA. It was also applied to the direct samarium recovery in binary mixtures.     

Highly selective determination of perchlorate by a novel potentiometric sensor based on a synthesized complex of copper

In this paper, a highly selective poly (vinyl chloride) (PVC) membrane electrode based on (1, 9-dibenzyl-1, 3, 7, 9, 11, 15-hexaaza cyclohexa decane) copper(II) perchlorate; [Cu((benzyl)₂[16]aneN₆)](ClO₄)₂; as a synthesized ionophore, for perchlorate-selective electrode is reported. The influence of membrane composition, pH and possible interfering anions were investigated on the response properties of the electrode. The sensor responds to perchlorate ion in linear range from 1.0 × 10^? 6 to 1.0 × 10^? 1 M with a slope ? 59.4 ± 0.3 mV per decade. The limit of detection of the electrode was 4.0 × 10^? 7 M ClO₄^–. Selectivity coefficients indicate a good discriminating ability towards ClO₄^– ion in comparison to other anions. The proposed sensor has a fast response time of about 7 s and can be used for at least 2 months without any considerable divergence in potential. Due to importance of analysis of perchlorate in water samples, this selective electrode was applied as potentiometric sensor in determination of perchlorate ion in real samples.     

Dysprosium selective potentiometric membrane sensor

A novel Dy(III) ion-selective PVC membrane sensor was made using a new synthesized organic compound, 3,4-diamino-N′-((pyridin-2-yl)methylene)benzohydrazide (L) as an excellent sensing element. The electrode showed a Nernstian slope of 19.8 ± 0.6 mV per decade in a wide concentration range of 1.0 × 10^? 6–1.0 × 10^? 2 mol L^? 1, a detection limit of 5.5 × 10^? 7 mol L^? 1, a short conditioning time, a fast response time (< 10 s), and high selectivity towards Dy(III) ion in contrast to other cations. The proposed sensor was successfully used as an indicator electrode in the potentiometric titration of Dy(III) ions with EDTA. The membrane sensor was also applied to the F^– ion indirect determination of some mouth washing solutions and to the Dy^3 + determination in binary mixtures.     

A novel lutetium(III) PVC membrane sensor based on a new symmetric S–N Schiff's base for Lu(III) analysis in real sample

A novel Lu(III) PVC membrane sensor has been constructed based on a new synthesized symmetric S–N Schiff's base, namely N-[(Z)-1-(2-thienyl)methylidene]-N-[4-(4-{[(Z)-1-(2-thienyl) methylidene]amino}benzyl)phenyl] amine (TBPA). The electrode showed a Nernstian slope of 19.8 ± 0.5 mV per decade across a wide concentration range of 1.0 × 10^? 6 to 1.0 × 10^? 2 mol L^? 1 with a detection limit of 7.2 × 10^? 7 mol L^? 1. The proposed sensor showed high selectivity toward Lu(III) ion in comparison with common alkaline, alkaline earth, transition, and heavy metals specially lanthanide ions, and could be used over a pH range of 2.7–10.6. It can be used for at least 2 months without any considerable divergency in potentials and it has a relatively fast response time of < 10 s. The sensor was effectively used as an indicator electrode in the potentiometric titration of Lu(III) ions with EDTA. The constructed sensor accuracy was investigated by the monitoring of Lu(III) ion in mixtures of two and three different ions.     

A comparative study on fabrication of Mn2 + selective polymeric membrane electrode and coated graphite electrode

Poly(vinyl chloride)-based membranes of two ligands 2,4-bis(2-acetoxybenzylamino)-6-phenyl-1,3,5-triazine (L₁) and N2,N4-di(cyanoethyl)-2,4-bis(2-acetoxybenzylamino)-6-phenyl-1,3,5-triazine (L₂) were fabricated and explored as Mn^2 + ion selective electrodes. The performance of the polymeric membranes electrodes of ionophores with different plasticizers (dibutylphthalate, benzoic acid, o-nitrophenyloctyl ether, 1-chloronapthalene and tri-n-butylphosphate) and anion excluders (sodium tetraphenylborate and potassium tetrakis p-(chloro phenyl)borate) was looked in to and the better results were obtained with the membrane having composition L₂: NaTPB: DBP: PVC as 6: 3: 56: 35 (w/w; mg). The coated graphite electrode (CGE) with same composition was also fabricated and investigated as Mn^2 + selective electrode. It was found that CGE showed better response characteristics than PME. The potentiometric response of CGE was independent of pH in the range 3.0–9.0 exhibiting the Nernstian slope 29.5 ± 0.3 mV decade^? 1 of activity and working concentration range 4.1 × 10^? 7–1.0 × 10^? 1 mol L^? 1 with a limit of detection 6.7 × 10^? 8 mol L^? 1. The electrode showed a fast response time of 12 s with a shelf life of 105 days. The proposed CGE could be successfully used for the determination of Mn^2 + ions in different water, soil, vegetables and medicinal plants also used as an indicator electrode in potentiometric titration with EDTA.     

Praseodymium analysis in aqueous solution by Pr3+–PVC membrane sensor based on N,N′-bis(4-hydroxysalicylidene)-1-3-phenylenediamine

A new Pr³⁺ poly vinyl chloride PVC membrane sensor based on a membrane containing 3% N,N′-bis(4-hydroxysalicylidene)-1-3-phenylenediamine (HSPDA) as an ionophore, 2% sodium tetraphenyl borate (NaTPB) as an anionic additive, 65% benzyl acetate (BA) as solvent mediator and 30% poly(vinyl chloride) was prepared. This sensor responds to praseodymium ion in a wide linear dynamic range of 1.0 × 10^?6 to 1.0 × 10^?2 mol L^?1 with Nernstian slope of 19.8 ± 0.4 mV per decade and a detection limit of 5.7 × 10^?7 mol L^? 1 in pH range of 3.1 to 9.8. It has a fast response time of ~5 s in the whole concentration range, and can be used for at least 2 months without any considerable divergences in the potentials. The proposed sensor displays an excellent selectivity for Pr³⁺ ions with respect to a large number of alkali, alkaline earth, transition and heavy metal ions. The developed sensor was successfully applied as an indicator electrode in Pr³⁺ ion potentiometric titration with EDTA, and in direct determination of fluoride ion in two mouth wash samples.     

Potentiometric detection of silver (I) ion based on carbon paste electrode modified with diazo-thiophenol-functionalized nanoporous silica gel

For the first time, triazene compound functionalized silica gel was incorporated into carbon paste electrode for the potentiometric detection of silver (I) ion. A novel diazo-thiophenol-functionalized silica gel (DTPSG) was synthesized, and the presence of DTPSG acted as not only a paste binder, but also a reactive material. The electrode with optimum composition, exhibited an excellent Nernstian response to Ag⁺ ion ranging from 1.0 × 10^? 6 to 1.0 × 10^? 1 M with a detection limit of 9.5 × 10^? 7 M and a slope of 60.4 ± 0.2 mV dec^? 1 over a wide pH range (4.0–9.0) with a fast response time (50 s) at 25 °C. The electrode also showed a long-time stability, high selectivity and reproducibility. The response mechanism of the proposed electrode was investigated by using AC impedance. Moreover, the electrode was successfully applied for the determination of silver ions in radiology films, and for potentiometric titration of the mixture solution of Cl^? and Br^? ions.     

Gadolinium(III) ion selective sensor using a new synthesized Schiff's base as a sensing material

According to a solution study which showed a selective complexation between N,N′-bis(methylsalicylidene)-2-aminobenzylamine (MSAB) and gadolinium ions, MSAB was used as a sensing element in construction of a gadolinium(III) ion selective electrode. Acetophenon (AP) was used as solvent mediator and sodium tetraphenyl borate (NaTPB) as an anion excluder. The electrode showed a good selectivity towards Gd(III) ions over a wide variety of cations tested. The constructed sensor displayed a Nernstian behavior (19.7 ± 0.3 mV/decade) in the concentration range of 1.0 × 10^? 6 to 1.0 × 10^? 2 mol L^? 1 with detection limit of 5.0 × 10^? 7 mol L^? 1 and a short response time (< 10 s). The working pH range of the electrode was 3.5–10.1 and lifetime of the sensor was at least 10 weeks. Analysis of certified reference materials confirmed the accuracy of the proposed sensor. The electrode was successfully applied as an indicator electrode in gadolinium titration with EDTA.     

Potentiometric sensor for the indomethacin determination

A potentiometric indomethacin-selective sensor based on Rhodamine B indomethacinate ion-pair (IP) as a membrane carrier is reported. Influences of the membrane composition, pH, and possible interfering ions were investigated on the response properties of the electrode. The sensor exhibits significantly enhanced response toward indomethacinate ions over the concentration range 1 × 10^? 4 mol L^? 1 to 5 × 10^? 2 mol L^? 1 with a lower detection limit (LDL) of 3 × 10^? 5 mol L^? 1 and a slope of ? 60 mV decade^? 1. Fast and stable response, good reproducibility, long-term stability, applicability over a pH range of 6–10 is demonstrated. The proposed electrode shows good discrimination of indomethacin from several inorganic and organic ions. The proposed sensor has been applied for the direct potentiometric determination of indomethacin in pharmaceutical preparations.     

An optical chemical sensor for thorium (IV) determination based on thorin

A selective method for the determination of thorium (IV) using an optical sensor is described. The sensing membrane is prepared by immobilization of thorin–methyltrioctylammonium ion pair on triacetylcellulose polymer. The sensor produced a linear response for thorium (IV) concentration in the range of 6.46 × 10^?6 to 9.91 × 10^?5 mol L^?1 with detection limit of 1.85 × 10^?6 mol L^?1. The regeneration of optode was accomplished completely at a short time (less than 20 s) with 0.1 mol L^?1 of oxalate ion solution. The relative standard deviation for ten replicate measurements of 2.15 × 10^?5 and 8.62 × 10^?5 mol L^?1 of thorium was 2.71 and 1.65%, respectively. The optode membrane exhibits good selectivity for thorium (IV) over several other ionic species and are comparable to those obtained in case of spectrophotometric determination of thorium using thorin in solution. A good agreement with the ICP-MS and spiked method was achieved when the proposed optode was applied to the determination of thorium (IV) in dust and water samples.     

Design of an efficient uranyl ion optical sensor based on 1′-2,2′-(1,2-phenylene)bis(ethene-2,1-diyl)dinaphthalen-2-ol

A new optical uranyl (IV) selective sensor by incorporation of 1,1′-2,2′-(1,2-phenylene)bis(ethene-2,1-diyl)dinaphthalen-2-ol (PBED), dibutyl phthalate (DBP) and sodium tetraphenylborate (Na-TPB) in the plasticized poly vinyl chloride membrane matrices has been constructed. In the proposed optode, PBED functions as both ionophore and chromoionophore while DBP has synergistic effect on the complexation of uranyl ion (UO₂²⁺) by PBED. Following the optimization of influences of variables, the proposed sensor due to its high stability, reproducibility and relatively long lifetime has good selectivity and sensitivity for uranyl ion over a large number of alkali, alkaline earth, transition, and heavy metal ions. The response of the proposed optode is linear over the concentration range of 3.99 × 10^? 6 up to 8.06 × 10^? 5 mol L^? 1 of UO₂²⁺ within a detection limit of 9.99 × 10^? 7 mol L^? 1 and response time less than 10 min. The proposed optical sensor was applied successfully for the determination and evaluation of UO₂²⁺ ion content in water samples.     

Nickel analysis in real samples by Ni2 + selective PVC membrane electrode based on a new Schiff base

A newly synthesized Schiff base 3-aminoacetophenonesemicarbazone (AAS) has been used for the preparation of Ni^2 + selective PVC membrane electrode. The proposed electrode exhibits a Nernstian response over the nickel concentration range of 1.0 × 10^? 7 to 1.0 × 10^? 2 mol L^? 1 with a slope of 30.0 ± 0.3 mV/decade of concentration. The limit of detection as determined from the intersection linear segment of the calibration plot is 5.1 × 10^? 8 mol L^? 1. The electrode shows good selectivity towards nickel with respect to several alkali, alkaline earth, transition and heavy metal ions. The response time of the electrode is very fast (≥ 10 s) and can be used for 17 weeks in the pH range of 2.0–9.8. The electrode can also be used in partially non-aqueous media having up to 20% (v/v) methanol, ethanol or acetone content with no significant change in the value of slope or working concentration range. To investigate the analytical applicability of the electrode, it was successfully applied as an indicator electrode in Ni^2 + ion potentiometric titration with EDTA, and in direct determination of nickel(II) in real samples.     

Fabrication of an iron(III) PVC-membrane sensor based on bis-benzilthiocarbohydrazide as a selective sensing material

The construction, performance characteristics, and application of a novel iron(III) membrane sensor based on a new bis-benzilthiocarbohydrazide (BBTC) are reported in this paper. The sensor is prepared by incorporating of BBTC, nitrobenzene (NB), and sodium tetraphenyl borate (NaTPB) into a plasticized poly(vinyl chloride) membrane. The electrode reveals a Nernstian behavior over a wide iron ion concentration range (1.0 × 10^? 2–1.0 × 10^? 7 mol L^? 1), and relatively low detection limit (8.6 × 10^? 8 mol L^? 1). The potentiometric response is independent on the pH of the solution in the range of 1.6–4.3. The electrode shows a very short response time (< 10 s). The proposed electrode can be used for at least nine weeks without any considerable divergence in potentials. It exhibits very good selectivity relative to a wide variety of alkali, alkaline earth, transition and heavy metal ions. In fact, the selectivity of the proposed sensor shows great improvements compared to the previously reported electrodes for the iron ion. Also, the sensors accuracy was investigated in two ways: (i) with the potentiometric titration of a Fe(III) solution with EDTA and (ii) with the Fe(III) monitoring in river and wastewater samples.     

Simultaneous determination of phenylhydrazine and hydrazine by a nanostructured electrochemical sensor

In the present paper, the use of a nanostructured electrochemical sensor was described for simultaneous determination of phenylhydrazine (PhH) and hydrazine (HZ). This electrochemical sensor was prepared by a simple and rapid method by modification of carbon paste electrode with a derivative of hydroquinone and TiO₂ nanoparticles. The modified electrode showed an excellent character for electrocatalytic oxidation of PhH. Using differential pulse voltammetry, a highly selective and simultaneous determination of PhH and HZ has been explored at the modified electrode. Differential pulse voltammetry peak currents of PhH and HZ increased linearly with their concentration at the ranges of 2.0 × 10^? 6 to 1.0 × 10^? 3 M and 7.5 × 10^? 5–1.0 × 10^? 3 M, respectively and the detection limits for PhH and HZ were 7.5 × 10^? 7 M and 9.0 × 10^? 6 M, respectively.     

Application of 1-ethyl-3-(2,5-dihydro-4-(3,5-dimethyl-1H-pyrazol-4-yl)-5-oxo-1H-pyrazol-3-yl)thiourea as sensing material for construction of Tm3+-PVC membrane sensor

A thulium(III) membrane sensor was made using 2% sodium tetraphenyl borate (NaTPB), 65% dibutylphthalate (DBP), 30% poly(vinyl chloride) (PVC) and 3% 1-ethyl-3-(2,5-dihydro-4-(3,5-dimethyl-1H-pyrazol-4-yl)-5-oxo-1H-pyrazol-3-yl)thiourea (ET) as an ionophore. Conductometric study shows selectivity of the Et toward Tm³⁺ ions. Nernstian response of 19.6 ± 0.4 mV per decade of thulium concentration was observed, and the electrode worked well in concentration range of 1.0 × 10^? 6 to 1.0 × 10^? 2 mol L^? 1 with a lower detection limit (LDL) of 7.2 × 10^? 7 mol L^? 1, in a pH range of 4.3–10.4. The selectivity of the sensor over alkaline, alkaline earth, transition and heavy metal ions was also found to be in a satisfactory range. To check the analytical applicability of the proposed Tm³⁺ sensor, it was successfully used as an indicator electrode in analysis of thulium in certified reference materials.     

Modified carbon paste electrodes for Cu(II) determination

A new Cu²⁺ carbon paste electrode (CPE) using 2,2′-(1E,1′E)-1,1′-(2,2′-azanediylbis (ethane-2,1-diyl)bis(azan-1-yl-1-ylidene))bis(ethan-1-yl-1-ylidene)diphenol (ADEZEDP) has been prepared. The influence of variables including sodium tetraphenylborate (NaTPB), ionophore, and amount of multiwalled carbon nanotubes (MWCNT), CdO nanowires, CdS nanoparticles and palladium nanoparticles loaded on ADEZEDP and Nujol on the electrodes response were studied and optimized. At optimum values of all variables, for each nanomaterial the electrode response was linear in concentration range of 1.0 × 10^? 8 to 1.0 × 10^? 1 mol L^? 1 for ADEZEDP with Nernstian slope. The good performance of electrode viz. Wide applicable pH range (2.0–5.0), fast response time (≈ 6 s), and adequate life time (3 months) indicate the utility of the proposed electrodes for evaluation of Cu²⁺ ion content in various situations. Finally, these electrodes have been successfully applied for the determination of Cu²⁺ ions content in various real samples. The selectivity of proposed electrode was evaluated by separation solution method and fixed interference method.     

Neutral N,N′-bis(2-pyridinecarboxamide)-1,2-ethane as sensing material for determination of lutetium(III) ions in biological and environmental samples

The biological properties of the lutetium as well as other lanthanide ions, primarily based on their similarity to calcium, have been the bases for research into potential therapeutic applications of lanthanide series since the early part of the twentieth century. In this research, a Lu(III) potentiometric membrane sensor based on N,N′-bis(2-pyridinecarboxamide)-1,2-ethane (PCAE) is described. The sensor exhibits a Nernstian response over a concentration range of 1.0 × 10^? 6 mol L^? 1–1.0 × 10^? 1 mol L^? 1, with a detection limit of 6.0 × 10^? 7 mol L^? 1. The best performance was achieved with a membrane composition, consisting of 30% PVC, 63% o-nitrophenyl octyl ether (NPOE), 5% PCAE and 2% sodium tetraphenylborate (NaTPB). It was found that at the pH range of 4.0–9.0, the potential response of the sensor was not affected by the pH. Furthermore, the electrode presents satisfactory reproducibility, very fast response time (5 s) and relatively good discriminating ability for Lu(III) ions with respect to many common cations and other lanthanide ions. The sensor has been applied to the determination of Lu(III) in human serum and in some soil samples where domestic devices were stored.