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1.
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   

2.
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   

3.
A new solvent polymeric membrane (PME) and coated graphite (CGE) electrodes based on 3-amino-2-mercapto-3H-quinazolin-4-one as a suitable carrier for La(III) ion are described. The sensors exhibited a Nernstian response for La(III) ion over a wide concentration range (3.0 × 10?7 to 1.0 × 10?1 M for PME and 1.0 × 10?7 to 1.0 × 10?1 M for CGE) with a slope of 20.1 ± 0.3 (PME) and 23.4 ± 0.4 (CGE) mV decade?1. The lower detection limits by PME and CGE were 2.0 × 10?7 and 7.1 × 10?8 M, respectively. The potentiometric response of the proposed electrodes was independent of the pH of the test solution in the pH range 3.0–9.0 with a fast response time (<10 s). The applications of prepared sensors were demonstrated in the determination of lanthanum ions in spiked water sample and also utilized for indirect determination of fluoride content of two mouth wash preparation samples.  相似文献   

4.
Novel ligand 5,5?-((3-nitrophenyl)methylene)bis(2,6-diaminopyrimidin-4(3H)-one) (L) was synthesised and characterised. Preliminary studies on L have showed that it has more affinity towards the Ni2+ ion. Thus, the L was used as the electroactive material in the fabrication of poly(vinyl chloride) (PVC)-based membrane sensors such as coated graphite electrode (CGE) and coated pyrolytic graphite electrode (CPGE). Several polymeric membranes were fabricated by incorporating L as ionophore, NaTPB as anion excluders and BA, 1-CN, DBP, DOP and o-NPOE as solvent mediators and their effect on potentiometric response studied. Comparative electroanalytical studies performed on the CGE and CPGE depict that the CPGE with optimised membrane composition of L:PVC:o-NPOE:NaTPB in the ratio of 7:33:58:2 (w/w, mg) exhibited the best response in terms of wide working concentration range from 2.0 × 10?8 to 1.0 × 10?1 mol L?1, (3.64 µg L?1 –18.2 g L?1) lower detection limit of 8.1 × 109 mol L?1 (1.47 µg L?1) with Nernstian compliance of 29.4 ± 0.2 mV decade?1 of activity of Ni2+ ion in the pH range of 3.5–9.0. The sensor can work satisfactorily in water–acetonitrile and water–methanol mixtures. It can tolerate 30% acetonitrile and 20% methanol content in the mixtures. The sensor showed fast response time of 8 s and could be used successfully for a period of 4 months. The sensor reflects its utility in the quantification of Ni2+ ion in real samples and has been successfully employed as an indicator electrode in the potentiometric titration of Ni2+ ion with EDTA.  相似文献   

5.
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   

6.
A novel thia-aza substituted macrocyclic diamide 7,10,13-triaza-1-thia-4,16-dioxa-20,24-dimethyl-2,3;17,18-dibenzo-cyclooctadecane-6,14-dione (L) was synthesized and stability of its complexes with several alkaline earth, transition and heavy metal ions were studied conductometrically in methanol solution. The resulting 1:1 Ag+L complex found to be the most stable one among all cation complexes studied. The optimized structures of the ligand and its Ag+ complex were also investigated. Based on the preliminary results thus obtained, L was used as an excellent sensing material to prepare polymeric membrane (PME) and coated graphite (CGE) silver-selective electrodes. The electrodes revealed a Nernstian behavior over wide Ag+ ion concentration ranges (i.e., 2.0 × 10?6–1.0 × 10?2 M for PME and 5.0 × 10?7–1.0 × 10?2 M for CGE). The potentiometric responses were independent of pH of the test solution in the range 2.9–6.8. The electrodes possessed advantages of low resistance, relatively fast response time, long lifetimes and, especially, good selectivity relative to a wide variety of other cations. The electrodes were used, as indicator electrodes, in the potentiometric titration of silver ion and in the determination of Ag+ ion in waste water, photographic emulsion, radiographic and photographic films and dental amalgams.  相似文献   

7.
《Electroanalysis》2004,16(16):1336-1342
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.  相似文献   

8.
《Analytical letters》2012,45(15):2444-2459
Abstract

Polymeric membrane electrodes (PMEs) and coated graphite electrodes (CGEs) containing 1,3,4-trisubstituted-2-azetidinone derivatives as ion carriers are reported here for bismuth(III) ion selectivity. These electrodes exhibited Nernstian response for Bi3+ ions over a wide concentration range (5.0 × 10?7 M to 1.0 × 10?1 M for CGE) with a lower detection limit of 3.98 × 10?7 M (for CGE) and wide pH range (1.3–5.0). Compared to polymeric membrane electrode, the coated graphite electrode has shown better selectivity for Bi3+ ions with respect to common metal ions. Proposed electrodes have been used for the estimation of Bi3+ ions in pharmaceutical and glass samples.  相似文献   

9.
Three types of ion‐selective electrodes: PVC membrane, modified carbon paste (CPE), and coated graphite electrodes (CGE) have been constructed for determining paroxetine hydrochloride (Prx). The electrodes are based on the ion pair of paroxetine with sodium tetraphenylborate (NaTPB) using dibutyl phthalate as plasticizing solvent. Fast, stable and potentiometric response was obtained over the concentration range of 1.1×10?5–1×10?2 mol L?1 with low detection limit of 6.9×10?6 mol L?1 and slope of a 56.7±0.3mV decade?1 for PVC membrane electrode, the concentration range of 2×10?5–1×10?2 mol L?1 with low detection limit of 1.2×10?5 mol L?1 and slope of a 57.7±0.6 mV decade?1 for CPE, and the concentration range of 2×10?5–1×10?2 mol L?1 with low detection limit of 8.9×10?6 mol L?1 and slope of a 56.1±0.1 mV decade?1 for CGE. The proposed electrodes display good selectivity for paroxetine with respect to a number of common inorganic and organic species. The electrodes were successfully applied to the potentiometric determination of paroxetine hydrochloride in its pure state, its pharmaceutical preparation, human urine and plasma.  相似文献   

10.
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.  相似文献   

11.
Novel 5-amino-1,3,4-thiadiazole-2-thiol unit based macrocyclic ionophore 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonaazatetracyclo[14.2.1.14,7.110,13]henicosa-4(20),10(21),16(19)-triene-6,12,18-trithione (M1), was synthesized and characterized. Preliminary studies on M1 have showed that it has more the affinity toward Cd2+ ion. Thus, the macrocyclic ionophore (M1) was used as electroactive material in the fabrication of PVC-membrane electrodes such as polymeric membrane electrode (PME), coated graphite electrode (CGE) and coated pyrolytic graphite electrode (CPGE) were prepared and its performance characteristic were compared with. The electroanalytical studies performed on PME, CGE and CPGE revealed that CPGE having membrane composition M1:PVC:1-CN:NaTPB in the ratio of 7:37:54:2 exhibits the best potentiometric characteristics in terms of detection limit of 7.58 × 10−9 mol L−1, Nernstian slope of 29.6 mV decade−1 of activity. The sensor was found to be independent of pH in the range 2.5–8.5. The sensor showed a fast response time of 10 s and could be used over a period of 4 months without any significant divergence in its potentiometric characteristics. The sensor has been employed for monitoring of the Cd2+ ion in real samples and also used as an indicator electrode in the potentiometric titration of Cd2+ ion with EDTA.  相似文献   

12.
《Analytical letters》2012,45(14):2727-2742
Abstract

This report describes an attempt to develop potentiometric Mg2+ sensors based on a liquid polymeric membrane. Membrane incorporating 4,5-Bis(benzoylthio)-1,3- dithiole-2-thione (Bz2dmit) as ionophore, with composition Bz2 dmit:NaTPB:NB:PVC in the ratio 2.5:2.5:65:30 (w/w), exhibits the best result for potentiometric sensing of Mg2+ ions. The proposed electrode, based on Bz2 dmitwith nitrobenzene (NB) as a solvent mediator in a polyvinyl chloride (PVC) membrane matrix, exhibited a near-Nernstian response to Mg2+ in the concentration range of 1.0 × 10?5 to 1.0 × 10?1 M, with a slope of 29.2 mV per decade of activity of Mg2+. The lower limit of detection was 1.0 × 10?5 M. This sensor showed high selectivity with respect to alkaline, alkaline earth, transition, and heavy metal ions, except for Sr2+, and could be used over a pH range of 3.5–9.0. It can be used for at least 2 mo without considerable divergence in potentials and has a relatively fast response of <10 s. It was applied successfully as an indicator electrode in potentiometric titration of Mg2+ ions with EDTA.  相似文献   

13.
A new triiodide ion-selective electrode based on charge-transfer complex of iodine with 1,4,8,11-tetraazacyclotetracdecane as membrane carrier was prepared. The best performance of electrode observed with the membrane having the ligand–PVC–NPOE–NaTPB composition 3.0:33:66:0.5 mg which worked well over a wide concentration range 2.8 × 10?6–1.4 × 10?1 M with a Nernstian slope of 59.6 ± 0.3 mV per decade and a detection limit of 1.2 × 10?6 M. This electrode showed a response time of 25 s and was used over a period of 2 months. The electrode exhibits an anti-Hofmeister selectivity sequence with a performance for triiodide at pH 1.5–10.2. The response mechanism of the electrode was investigated by UV–Vis spectroscopic technique. The electrode was successfully applied as an indicator electrode in the potentiometric titration of ascorbic acid and hydroquinone in drugs.  相似文献   

14.
A polymeric membrane based Pb(II) selective potentiometric sensor was developed by using 1,3,7,9-tetraaza-2,8-dithia-4,10-dimethyl-6,12-diphenylcyclododeca-4,6,10,12-tetraene (TDDDCT) as an electroactive material along with anion excluder sodium tetraphenylborate (NaTPB) and plasticizer dioctylphthalate (DOP). The best performance in terms of slope, concentration range and response time was exhibited by the membrane having TDDDCT:PVC:DOP:NaTPB in the ratio 3:32:62:3 (w/w%). Potentiometric results show that the developed sensor works well in the concentration range 5.0 × 10?7–1.0 × 10?1 M with a near Nernstian slope of 29.5 (±0.5) mV decade?1. The detection limit is down to 2.5 × 10?7 M. The working pH range of this sensor is 2.8–7.0 and it works well in partially nonaqueous medium up to 25 % (v/v) methanol and ethanol. It exhibits a fast response time of 10 s. Selectivity coefficient values of various interfering ions were determined by the fixed interference method (FIM). The sensor reveals good selectivity for Pb(II) ions over other metal ions investigated. The developed sensor is used in the determination of lead in ‘Eveready battery waste’ and as an indicator electrode in the potentiometric titration of Pb(II) against EDTA.  相似文献   

15.
《Analytical letters》2012,45(1):141-153
Abstract

In this research, the construction and general performance characteristics of a sunset yellow sensor based on sunset yellow–cetyl pyridinum (SY-CPY) ion pair as an ion exchanger were described. A coated platinum wire electrode (CPE) was prepared and compared with coated graphite (CGE) and membrane electrode (PME). The CPE exhibited a rapid and Nernstian response (?29.77 ± 0.2 mV decade?1) to SY concentration range from 3.16 × 10?7 to 3.16 × 10?3 mol dm?3 within pH 4.5–9.5. Interfering effects of some foreign substances were reported. The optimized matrix was successfully applied to the determination of SY in artificial mixtures and commercial soft drinks. The results showed good agreements with the determination made by use of high-performance liquid chromatography.  相似文献   

16.
In this study, a potentiometric sensor based on a pencil graphite electrode (PGE) coated with polypyrrole doped with uranyl zinc acetate (termed PGE/PPy/U) have been prepared for potentiometric determination of uranyl in aqueous solutions. Electropolymerization reaction for preparing of U(VI) sensor electrode was carried via applying a constant current of 1.0 mA on PGA working electrode in a solution containing 8.0 mM pyrrole and 0.8 mM ZnUO2(CH3COO)4 salt. The constructed electrode displayed a linear and near Nernstian response (22.60 ± 0.40 mV/decade) to U(VI) ions in the concentration range of 1.0 × 10?6–1.0 × 10?2 M. A detection limit of 6.30 × 10?7 M and a fast response time (≤12 s) was observed during measurements. The working pH range of the electrode was 4.0–8.0 and lifetime of the sensor was at least 60 days. The electrode revealed good selectivity with respect to many cations including alkali, alkaline earth, transition and heavy metal ions. The introduced uranyl electrode was used for measurement of U(VI) ion in real samples without any serious inferences from other ions.  相似文献   

17.
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   

18.
The electrode characteristics and selectivities of PVC-based thiocyanate selective polymeric membrane electrode (PME) incorporating the newly synthesized zinc complex of 6,7:14,15-Bzo2-10,11-(4-methylbenzene)-[15]-6,8,12,14-tetraene-9,12-N2-1,5-O2 (I 1 ) and zinc complex of 6,7:14,15-Bzo2-10,11-(4-methylbenzene)-[15]-6,14-diene-9,12-dimethylacrylate-9,12-N2-1,5-O2 (I 2 ) are reported here. The best response was observed with the membrane having a composition of I2:PVC:o-NPOE:HTAB in the ratio of 6:33:59:2 (w/w; milligram). This electrode exhibited Nernstian slope for thiocyanate ions over working concentration range of 4.4 × 10−7 to 1.0 × 10−2 mol L−1 with detection limit of 2.2 × 10−7 mol L−1. The performance of this electrode was compared with coated graphite electrode (CGE), which showed better response characteristics w.r.t Nernstian slope 59.0 ± 0.2 mV decade−1 activity, wide concentration range of 8.9 × 10−8 to 1.0 × 10−2 mol L−1 and detection limit of 6.7 × 10−8 mol L−1. The response time for CGE and PME was found to be 8 and 10 s, respectively. The proposed electrode (CGE) was successfully applied to direct determination of thiocyanate in biological and environmental samples and also as indicator electrode in potentiometric titration of SCN ion.  相似文献   

19.
《Analytical letters》2012,45(3):571-583
Abstract

A fast potentiometric determination method has been reported for pentazocine in human plasma without complicated pretreatments using a coated-wire potentiometric selective electrode. The sensing membrane was made by incorporating of ion-association complexes of pentazocine cation and sodium tetraphenyl borate (NaTPB) in a polyvinyl chloride. The sensor exhibited fast, stable, and linear Nernstian response over the range of 5 × 10?5 to 0.1 mol L?1 pentazocine with a slope of 57.8 mV per decade and with detection limit of 3.2 × 10?5 mol L?1. The proposed sensor has been used for determination of pentazocine in human plasma and urine.  相似文献   

20.
《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   

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