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1.
The two macrocyclic pendant ligands 3,4,5:12,13,14-dipyridine-2,6,11,15-tetramethyl-1,7,10,16-tetramethylacrylate-1,4,7,10,13,16-hexaazacyclooctadeca-3,13-di ene (L1) and 3,4,5:12,13,14-dipyridine-2,6,11,15-tetramethyl-1,7,10,16-tetra(2-cyano ethane)-1,4,7,10,13,16-hexaazacyclooctadeca-3,13-diene (L2) have been synthesized and explored as neutral ionophores for preparing poly(vinylchloride) (PVC) based membrane sensors selective to Tb(III) ions. Effects of various plasticizers and anion excluders were studied in detail and improved performance was observed. The best performance was obtained for the membrane sensor having a composition of L1: PVC:1-CN:NaTPB in the ratio of 6: 32: 58: 4 (w/w; mg). The performance of the membrane based on L1 was compared with polymeric membrane electrode (PME) as well as with coated graphite electrode (CGE). The electrodes exhibit Nernstian slope for Tb3+ ions with limits of detection of 3.4 × 10−8 mol L−1 for PME and 5.7 × 10−9 mol L−1 for CGE. The response time for PME and CGE was found to be 10 s and 8 s, respectively. The potentiometric responses are independent of the pH of the test solution in the pH range 3.0-7.5 for PME and 2.0-8.5 for CGE. The CGE has found to work satisfactorily in partially non-aqueous media upto 30% (v/v) content of methanol, ethanol and 20% (v/v) content of acetonitrile and could be used for a period of 5 months. The CGE was used as indicator electrode in the potentiometric titration of Tb3+ ions with EDTA and in determination of fluoride ions in various samples. It can also be used in direct determination of Tb3+ ions in tap water and various binary mixtures with quantitative results.  相似文献   

2.
《Electroanalysis》2004,16(12):1002-1008
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.  相似文献   

3.
Poly(vinylchloride) (PVC) based membranes of macrocycles 2,3,4:9,10,11-dipyridine-1,3,5,8,10,12-hexaazacyclotetradeca-2,9-diene (L1) and 2,3,4:9,10,11-dipyridine-1,5,8,12-tetramethylacrylate-1,3,5,8,10,12-hexaazacyclotetradeca-2,9-diene (L2) with NaTPB and KTpClPB as anion excluders and dibutylphthalate (DBP), benzyl acetate (BA), dioctylphthalate (DOP), o-nitrophenyloctyl ether (o-NPOE) and tri-n-butylphosphate (TBP) as plasticizing solvent mediators were prepared and investigated as Co2+ selective electrodes. The best performance was observed with the membranes having the composition L2:PVC:TBP:NaTPB in the ratio of 6:39:53:2 (w/w; mg). The performance of the membrane based on L2 was compared with polymeric membrane electrode (PME) and coated graphite electrode (CGE). The PME exhibits detection limit of 4.7 × 10−8 M with a Nernstian slope of 29.7 mV decade−1 of activity between pH 2.5 and 8.5 whereas CGE exhibits the detection limit of 6.8 × 10−9 M with a Nernstian slope of 29.5 mV decade−1 of activity between pH 2.0 and 9.0. The response time for PME and CGE was found to be 11 and 8 s, respectively. The CGE has been found to work satisfactorily in partially non-aqueous media up to 35% (v/v) content of methanol, ethanol and 25% (v/v) content of acetonitrile and could be used for a period of 4 months. The CGE was successfully applied for the determination of Co2+ in real and pharmaceutical samples and as an indicator electrode in potentiometric titration of cobalt ion.  相似文献   

4.
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.  相似文献   

5.
Plasticized membranes using 2,3,4:12,13,14-dipyridine-1,3,5,8,11,13,15,18-octaazacycloicosa-2,12-diene (L1) and 2,3,4:12,13,14-dipyridine-1,5,8,11,15,18-hexamethylacrylate-1,3,5,8,11,13,15,18-octaazacycloicosa-2,12-diene (L2) have been prepared and explored as Ce(III) selective sensors. Effect of various plasticizers viz. dibutylphthalate (DBP), tri-n-butylphthalate (TBP), o-nitrophenyloctylether (o-NPOE), dioctylphthalate (DOP), benzylacetate (BA) and anion excluders, sodium tetraphenylborate (NaTPB) and potassium tetrakis p-(chlorophenyl) borate was studied in detail and improved performance was observed. Optimum performance was observed for the membrane sensor having a composition of L2:PVC:o-NPOE:KTpClPB in the ratio of 6:34:58:2 (w/w, mg). The performance of the membrane based on L2 was compared with polymeric membrane electrode (PME) as well as with coated graphite electrode (CGE). The electrodes exhibit Nernstian slope for Ce(III) ions with limits of detection of 8.3 × 10−8 mol L−1 for PME and 7.7 × 10−9 mol L−1 for CGE. The response time for PME and CGE was found to be 12 s and 10 s respectively. The potentiometric responses are independent of the pH of the test solution in the pH range 3.5-7.5 for PME and 2.5-8.5 for CGE. The CGE could be used for a period of 5 months. The practical utility of the CGE has been demonstrated by its usage as an indicator electrode in potentiometric titration of oxalate and fluoride ions with Ce(III) solution. The proposed electrode was also successfully applied to the determination of fluoride ions in mouthwash solution and oxalate ions in real samples.  相似文献   

6.
Novel Zn2+ ion‐selective PVC based coated graphite electrodes were fabricated using the ionophores N‐((1H‐indol‐3‐yl)methylene)thiazol‐2‐amine (I1), N‐((1H‐indol‐3‐yl)methyl)‐thiazol‐2‐amine (I2) and 1‐((1H‐indol‐3‐yl)methylene)urea (I3). Their potentiometric performance was examined in dependence of the addition of plasticizers and anion excluders and compared. It is found that the coated graphite electrode with the composition I1:KTpClPB:o‐NPOE:PVC=9 : 1.5 : 51 : 38.5 is the best with respect to the wide working concentration range (4.2×10?8–1.0×10?1 mol L?1), low detection limit (1.6×10?8 mol L?1) and wide pH range of 3.0–8.0. The proposed electrode was successfully applied to quantify Zn2+ in various environmental, biological and medicinal plant samples and used as indicator electrode.  相似文献   

7.
Two chemosensors 4H‐1‐benzopyran‐3‐carboxaldehyde, 4‐oxo‐, 3‐(2‐phenylhydrazone), [I1] and 4H‐1‐benzopyran‐3‐carboxaldehyde, 4‐oxo‐, 3‐[2‐(2,4‐dinitrophenyl)hydrazone], [I2] with hydrazone‐NH group as binding site have been shown excellent selectivity for arsenite ion. It is confirmed by the UV‐vis titration that I2 is more selective than I1. The performance of the coated graphite electrode (CGE) was found to be better than polymeric membrane electrode (PME) in terms of linear range of 4.89×10?7–1.0×10?1 mol L?1, low detection limit of 8.31×10?8 mol L?1 and short response time. The proposed sensors were also used to determine the arsenite ion in different water samples.  相似文献   

8.
《Electroanalysis》2004,16(4):282-288
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.  相似文献   

9.
A highly selective poly(vinyl chloride) (PVC) membrane electrode based on Co(III)-Schiff base [Co(5-NO2- Salen)(PBu3)]ClO4•H2O (where 5-NO2-SalenH=bis(5-nitrosalycilaldehyde)ethylenediamine) as a new carrier for construction of perchlorate-selective electrode by incorporating the membrane ingredients on the surface of a graphite electrodes has been reported. The proposed electrode possesses a very wide Nernestian potential linear range to perchlorate from 1.0×10-6 to 5.0×10-1 mol•L-1 with a slope of (59.4±0.9) mV per decade of perchlorate concentration with a low detection limit of 5.0×10-7 mol•L-1 and good perchlorate selectivity over the wide variety of other anions. The developed electrode has an especially fast response (<5 s) and a wide pH independent range (3.0—12.0) in comparison with recent reported electrodes and can be used for at least 2 months without any considerable divergence in their potential response. This electrode was used for the determination of perchlorate in river water, drinking water, sludgy water and human urine with satisfactory results without complicated and time consuming pretreatment.  相似文献   

10.
The 3‐amion‐5‐mercapto‐1,2,4‐triazole cobalt(II) [Co(II)AMETR] was used as a new carrier for preparing polymeric membrane selective sensor which exhibited high affinity for iodide ion. The effects of membrane composition, pH, the influence of lipophilic ion additives and plasticizer on the response characteristics of the sensor were investigated. The sensor showed a near Nernstian slope of ?56.6 mV/decade for I? ion over a wide concentration range from 8.5×10?7 to 1.0×10?1 M with a low detection limit of 5.1×10?7 M. The sensor has a fast response time and could be used over a wide pH range of 2–8. The response mechanism is discussed in view of the AC impedance technique. The sensor was successfully applied to direct determination of iodide content in environmental water samples and mouth wash samples.  相似文献   

11.
《Electroanalysis》2006,18(22):2174-2179
A new modified carbon paste electrode (CPE) based on a recently synthesized ligand of Ethyl‐2‐(benzoylamino)‐3‐(2‐hydroxy‐4‐methoxyphenyl)‐2‐propenoate (EBHMP) as a suitable carrier for Hg2+ ion was described. The electrode exhibit a super Nernstian slope of 48.5±1.0 mV per decade for Hg2+ ion over a wide concentration range from 3.0×10?7–3.1×10?2 M. The lower detection limits are 1.0×10?7 M Hg2+. The electrode has a fast response time (ca. 5 s), a satisfactory reproducibility and relatively long life time. The proposed sensor shows a fairly good selectivity toward Hg2+ ion in comparison to other common cations. The potentiometric responses are independent of the pH of the test solution in the pH range 1.0–4.0. The proposed electrode was used as an indicator electrode in potentiometric titration of mercuric ion with standard solution of EDTA. The direct determination of mercury in spiked wastewater and an amalgam sample gave results that compare favorably with those obtained by the cold vapor atomic absorption spectrometric method.  相似文献   

12.
An all solid‐state Ag(I) ion‐selective electrode has been prepared by simply immersing a glassy carbon rod coated with PVCAc, which contained plasticizer and additive but no ionophore, into the AgNO3 solution. The response of the electrode was linear with a Nernstian slope of 60.25 mV/decade within the concentration range from 1×10?1 to 1×10?5 M and with a detection limit of 4.25×10?6 M. The stability as an effect of various cations was defined. The electrode is suitable for use in high acidic solutions (pH<1 to 7) and has successfully been applied for the determination of silver(I) concentrations in different samples.  相似文献   

13.
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.  相似文献   

14.
《Analytical letters》2012,45(14):2859-2871
ABSTRACT

A polymer coated graphite rod ion selective electrode for saccharin was constructed and evaluated for the determination of saccharin in artificial table top sweeteners. The polymer consists of a thin film of silsesquioxane 3-n-propylpyridinium chloride. The electrode response was based on the ion pair formed between saccharinate and the 3-n-propylpyridinium cation from the silsequioxane polymer. The electrode exhibits a Nernstian response for saccharin concentrations between 6.9×10-6 and 5.3×10-3 mol L-1 and a detection limit of 5.5×10-6 mol L-1. The electrode response for saccharin was fast (10-20 s) and the potential independent of pH in the range of 3 to 7. The selectivity coefficients K A, B pot for several anions usually present in commercial table top sweeteners were determined following the IUPAC recommendations. The potentiometric method with the ion selective electrode was validated by the HPLC reference method, through t8543226 determination of saccharin in commercial samples of table top sweeteners. The ion selective electrode is proved suitable for the routine quality control of table top sweeteners by potentiometry.  相似文献   

15.
Molecularly imprinted polymers (MIP) were used as potentiometric sensors for the selective recognition and determination of chlormequat (CMQ). They were produced after radical polymerization of 4‐vinyl pyridine (4‐VP) or methacrylic acid (MAA) monomers in the presence of a cross‐linker. CMQ was used as template. Similar non‐imprinted (NI) polymers (NIP) were produced by removing the template from reaction media. The effect of kind and amount of MIP or NIP sensors on the potentiometric behavior was investigated. Main analytical features were evaluated in steady and flow modes of operation. The sensor MIP/4‐VP exhibited the best performance, presenting fast near‐Nernstian response for CMQ over the concentration range 6.2×10−6–1.0×10−2 mol L−1 with detection limits of 4.1×10−6 mol L−1. The sensor was independent from the pH of test solutions in the range 5–10. Potentiometric selectivity coefficients of the proposed sensors were evaluated over several inorganic and organic cations. Results pointed out a good selectivity to CMQ. The sensor was applied to the potentiometric determination of CMQ in commercial phytopharmaceuticals and spiked water samples. Recoveries ranged 96 to 108.5%.  相似文献   

16.
Preliminary studies on the two Schiff bases N2‐((3H‐indol‐3‐yl)methylene)‐6‐phenyl‐1,3,5‐triazine‐2,4‐diamine (L1) and N2,N4‐bis((3H‐indol‐3‐yl)methylene)‐6‐phenyl‐1,3,5‐triazine‐2,4‐diamine (L2) have shown that they can act as Sm3+ selective electrodes. The performances of a polymeric membrane electrode and a coated graphite electrode based on L2 were compared and the CGE proved to be better, as it shows a low detection limit of 1.8×10?8 mol L?1, a Nernstian slope of 19.6±0.4 mV decade?1 of activity with a response time of 11 s in the pH range of 3.0–9.0. The CGE was used to determine Sm3+ in medicinal plants and soil samples. It was also used to determine fluoride ions in mouthwash samples and in toothpaste.  相似文献   

17.
In this article a new coated platinum Cu2+ ion selective electrode based on 2-((2-(2-(2-(2-hydroxy-5-methoxybenzylideneamino)phenyl)disufanyl)phenylimino) methyl)-4-methoxyphenol Schiff base (L1) as a new ionophore is described. This sensor has a wide linear range of concentration (1.2 × 10−7-1.0 × 10−1 mol L−1) and a low detection limit of 9.8 × 10−8 mol L−1of Cu(NO3)2. It has a Nernstian response with slope of 29.54 ± 1.62 mV decade−1 and it is applicable in the pH range of 4.0-6.0 without any divergence in potentioal. The coated electrode has a short response time of approximately 9 s and is stable at least for 3.5 months. The electrode shows a good selectivity for Cu2+ ion toward a wide variety of metal ions. The proposed sensor was successfully applied for the determination of Cu2+ ion in different real and environmental samples and as indicator electrode for potentiometric titration of Cu2+ ion with EDTA.  相似文献   

18.
《Electroanalysis》2003,15(2):139-144
A highly selective and sensitive membrane electrode based on vanadyl salen complex (VS), which responds to monohydrogenphosphate (MHP) ions is described. The response of the sensor is Nernstian over the wide concentration range (1.0×10?1 ? 5.0×10?6 M) of MHP. The sensitivity of the electrode is high enough to permit the detection of as little as 0.6 μg/mL of MHP without any significant interference from high levels of other anions. The potentiometric selectivity coefficient data revealed negligible interference from 11 common anions. The electrode has a fast response time (<25 s), good slope stability at pH 8.2 for a period of at least eight weeks. It was successfully applied for the direct determination of monohydrogenphosphate in fertilizer and, as indicator electrode, in potentiometric titration of HPO42? ion with barium chloride.  相似文献   

19.
《Electroanalysis》2005,17(24):2246-2253
Coated‐wire (CW) and tubular (Tu) type membrane sensors for creatinine are developed. These consist of creatinine tungstophosphate(CTP), creatinine molybdophosphate (CMP) and creatinine picrolonate (CPC) ion‐pair complexes as electroactive materials dispersed in plasticized poly(vinyl chloride) matrix membranes. Electrochemical evaluation of these sensors under static (batch) mode of operation reveals near‐Nernstian response with slopes of 62.9, 58.1, and 55.2 mV decade?1 over the concentration range 1×10?2–5.0×10?6, 1×10?2–7.5×10?5, and 1×10?2?3.1×10?5 mol L?1. The lower detection limits are 0.39, 3.49, and 2.20 μg mL?1 creatinine with CTP, CMP and CPC membrane based sensors plasticized with o‐NPOE, respectively. Tubular and coated wire CTP membrane sensors are incorporated in flow‐through cells and used as detectors for flow injection analysis (FIA) of creatinine. The intrinsic characteristics of the detectors under hydrodynamic mode of operation in a low dispersion manifold are determined and compared with data obtained under static mode of operation. With 10?2 mol L?1 phosphate buffer of pH 4.5 as a carrier solution, the tubular and coated wire CTP detectors exhibit rapid response of 58.9 and 50.7 mV decade?1 over the concentration range 1×10?2–1×10?5 mol L?1 and detection limits of 0.39 μg mL?1 and 0.85 μg mL?1, respectively. Validation of the assay methods with the proposed sensors by measuring the lower detection limit, range, accuracy, precision, repeatability and between‐day‐variability reveals good performance characteristics confirming applicability for continuous determination of creatinine. The sensors are used for determining creatinine in human blood serum at an input rate of 40 samples per hour. No interferences are caused by creatine, most common anions, cations and organic species normally present in biological fluids. The results favorably compare with data obtained using the standard spectrophotometric method.  相似文献   

20.
Highly selective all solid state electrochemical sensor based on a synthesized compound i.e. 2‐(1‐(2‐((3‐(2‐hydroxyphenyl)‐1H‐pyrozol‐1‐yl)methyl)benzyl)‐1H‐pyrazol‐3‐yl)phenol (I) as an ionophore has been prepared and investigated for the selective quantification of chromium(III) ions. The effect of various plasticizers, viz. dibutyl phosphonate (DBP), dibutyl(butyl) phosphonate (DBBP), nitrophenyl octyl ether (NPOE), tris‐(2‐ethylhexyl)phosphonate (TEP), tri‐butyl phosphonate (TBP), dioctyl phthalate (DOP), dioctyl sebacate (DOS), benzyl acetate (BA) and acetophenone (AP) along with anion excluders NaTPB (sodium tetraphenyl borate) and KClTPB (potassium(tetrakis‐4‐chlorophenyl)borate was also studied. The optimum composition of the best performing membrane contained (I):KClTPB:NPOE:PVC in the ratio 15 : 3 : 40 : 42 w/w. The sensor exhibited near Nernstian slope of 20.1±0.2 mV/decade of activity in the working concentration range of 1.2×10?7–1.0×10?1 M, and in a pH range of 3.8–4.5. The sensor exhibited a fast response time of 10 s and could be used for about 5 months without any considerable divergence in potentials. The proposed sensor showed very good selectivity over most of the common cations including Na+, Li+, K+, Cu2+, Sr2+, Ni2+, Co2+, Ba2+, Hg2+, Pb2+, Zn2+, Cs+, Mg2+, Cd2+, Al3+, Fe3+and La3+. The activity of Cr(III) ions was successfully determined in the industrial waste samples by using this sensor.  相似文献   

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