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1.
A strontium Schiff's base complex (SS) can be used as a suitable ionophore to prepare a sulfate-selective PVC-based membrane electrode. The use of oleic acid (OA) and hexadecyltrimethylammonium bromide (HTAB), as additives, and nitrobenzen (NB), dibutyl phthalate (DBP) and benzyl acetate (BA) as solvent mediators, were investigated. The best performance was observed with a membrane composition PVC: NB: SS: HTAB of 30%: 62%: 5%: 3% ratio. The resulting sensor works well over a wide concentration range (1.0 x 10(-2)-1.0 x 10(-6) M) with a Nernstian slope of -29.2 mV per decade of sulfate activity over a pH range 4.0-7.0. The limit of detection of the electrode is 5 x 10(-7) M. The proposed sensor shows excellent discriminating ability toward SO4(2-) ions with regard to many anions. It has a fast response time of about 15 s. The membrane electrode was used to the determination of zinc in zinc sulfate tablets. The sensor was also used as an indicator electrode in the potentiometric titration of SO4(2-) against barium ion.  相似文献   

2.
Tripodal cadmium complex of hydrotris(3‐phenyl‐5‐methylpyrazolyl)borate (I1) and macrocyclic ligand 5,7 : 12,14 : 19,21 : 26,28‐Bzo4‐[28]‐5,13,19,27‐tetraene‐8,11,22,25‐N4–1,4,15,18‐O4 (I2), have been synthesized and characterized by IR, 1H NMR, Mass and elemental analysis. Spectroscopic investigations indicate high affinity of these receptors for dihydrogen phosphate ion. Polyvinyl chloride (PVC) based membranes of (I1) and (I2) using hexadecyl trimethylammonium bromide (HTAB) as cation discriminator and dibutylpthalate (DBP), tributyl phosphate (TBP), dioctylsebacate (DOS), and o‐nitrophenyloctyl ether (o‐NPOE), as plasticizing solvent mediators were prepared and investigated as H2PO selective sensors. The best performance was shown by the membrane of composition (w/w) (I2) (5%):PVC (31%) : DBP (61.5%):HTAB (2.5%). This sensor works well over a wide concentration range 2.1×10?7 to 1.0×10?2 M with Nernstian compliance (59.0 mV decade?1 of activity) with a fast response time of 14 s and showed good selectivity for dihydrogen phosphate ion over a number of anions. The sensor exhibits good reproducibility (SD±0.3 mV) and could be used successfully for the determination of phosphate in soil water samples.  相似文献   

3.
In this paper, a novel membrane triiodide sensor based on a charge-transfer complex of (1,3-diphenyldihydro-1H-imidazole)-4,5-dionedioxime with iodine (CTCI) as a membrane carrier is introduced. The best performance was obtained with a membrane containing 30% polyvinylchloride (PVC), 63% dibutylphthalate (DBP), 5% CTCI, and 2% hexadecyltrimethylammonium bromide (HTAB). The electrode shows a Nernstian behavior (slope of 58.2 ± 0.3) over a very wide triiodide ion concentration range (5.0 × 10−8−1.0 × 10−2 M), and has a low detection limit (4.0 × 10−8 M). The potentiometric response of the sensor is independent of pH of the solution in the pH range 3.0–9.0. The proposed sensor has a very low response time (<12 s) and a good selectivity relative to a wide variety of common inorganic and organic anions, including iodide, bromide, chloride, nitrate, sulfate, thiocyanate, monohydrogen phosphate, and acetate. 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 its potentials. The electrode was successfully applied as an indicator electrode in the titration of triiodide with thiosulfate ion. The text was submitted by the authors in English.  相似文献   

4.
A [{hydrotris(3-phenyl-5-methyl-1-pyrazolyl)borate}(3-phenyl-5-methyl-pyrazole) nickel chloride] [TpPh,MeNi(Cl)PzPh,MeH] (I) has been synthesized and explored as ionophores for the preparation of a poly (vinyl chloride) (PVC) membrane sensor for azide and thiocyanate anions. The compounds [TpPh,MeNi(N3)PzPh,MeH] (II) and [TpPh,MeNi(SCN)PzPh,MeH] (III) were characterized by their crystal structures and proved to be bonded as monodentate through nitrogen atom of azide and thiocyanate anion. Potentiometric investigations also indicate high affinity of this receptor for thiocyanate and azide ions. PVC based membranes of I using as hexadecyltrimethylammonium bromide (HTAB) cation discriminator and o-nitrophenyloctyl ether (o-NPOE), dibutylphthalate (DBP), acetophenone (AP) and tributylphosphate (TBP) as plasticizing solvent mediators were prepared and investigated as SCN and N3 selective sensors. The best performance was shown by the membrane of thiocyanate with composition (w/w) of (I) (7%):PVC (31%):DBP (60%):HTAB (2%). This sensor works well over a wide concentration range 5.3 × 10−7 to 1.0 × 10−2 M with Nernstian compliance (59.2 mV decade−1 of activity) within pH range 2.5-9.0 with a response time of 11 s and showed good selectivity for thiocyanate ion over a number of anions. The sensor exhibits adequate life (3 months) and could be used successfully for the determination of thiocyanate content in human urine, saliva and river water samples. While the membrane of [TpPh,MeNi(Cl)PzPh,MeH] ionophore with composition (I) (6%):HTAB (4%):PVC (31%):TBP (59%) showed highest sensitivity and widest linear range for azide ion. These sensors exhibit the maximum working concentration range of 8.1 × 10−6 to 1.0 × 10−2 M with Nernstian slope of 59.3 mV decade−1 of activity. It can be applied for the monitoring of the azide ions concentration in aqueous black tea and orange juice samples.  相似文献   

5.
Poly(vinyl chloride) (PVC) based membranes of zinc-phthalocyanine (ZPC) with hexadecyltrimethylammonium bromide (HTAB) as a cation excluder, and dibutyl phthalate (DBP) and benzyl acetate (BA) as plasticizing solvent mediators were prepared and investigated as a SO4(2-) selective electrode. The best performance was observed with a membrane having a composition of ZPC-PVC-HTAB-BA in a ratio of 5%:32%:3%:60%, which works well over a wide concentration range (1.0 x 10(-2) - 1.0 x 10(-6) M) with a Nemstian slope of -29.2 mV per decade of activity, between the pH values of 2.0 to 7.0. This sensor shows a very fast response time of 10 s, and can be used over a period of 2 months with good reproducibility. The proposed sensor displays excellent selectivity for SO4(2-) over a large number of common inorganic anions. The sensor has been successfully applied for the direct and indirect determination of sulfate and zinc in zinc sulfate tablets, respectively. It was also used as an indicator electrode in the potentiometric titration of sulfate ions with barium ions.  相似文献   

6.
In this paper, a new PVC-based liquid-membrane anion-selective electrode based on a copper(II) of N,N'-bis(salicylidene)-1,2-bis(p-aminophenoxy)ethane tetradentate complex (Cu(II)BBAP) is described, which displays a preferential potentiometric response to iodide ion at pH 2.0 and an anti-Hofmeister selectivity sequence: I->SCN->ClO4->NO2->H2PO4->NO3->SO4(2-)>Br->Cl-. The electrode exhibits a near-Nernstian potential linear range of 8.2x10(-7)-1.0x10(-1) M with a detection limit of 5.3x10(-7) M and a slope of -58.8 mV per decade. The A.C. impedance technique and the UV/Vis spectroscopy technique were used to analyze the response mechanism. The electrode could be applied to determine iodide in medicine analysis, and the obtained results were fairly satisfactory.  相似文献   

7.
The [Ni[(TAP)(SBn)8]] complex (I), i.e. ([2,3,7,8,12,13,17,18-octakis(benzylthio)-5,10,15,20-tetraazaporphyrin])nickel(II), has been explored as an ionophore for fabrication of the PVC based membrane electrodes used in the screening of thiocyanate anion (SCN-). The membrane having [Ni[(TAP)(SBn)8]] complex (I) as an electroactive material and dioctylphthalate (DOP) as plasticizer in the PVC matrix with the percentage ratio 5 : 158 : 200 (I : DOP : PVC, % w/w) exhibited a linear response in the concentration range 7.0 x 10(-6)-1.0 x 10(-1) M of SCN- with a sub-Nernstian slope 32.5 +/- 0.2 mV/decade of activity and a fast response time of 10 +/- 2 s. The sensor works well in the pH range 3.0 - 9.5 and could be satisfactorily used in presence of 50 % (v/v) methanol, ethanol and acetone, and is selective for SCN- over a large number of anions with slight interference from iodide (I-) and azide (N3-) if present at a level >or = 1.0 x 10(-5) M. Described electrode works well over a period of six months. The sensor can be successfully applied for the screening of SCN- in both aqueous and real samples and also as indicator electrodes in precipitation titrations.  相似文献   

8.
This is a first promethium(145) ion-selective sensor based on the comparative study of two Schiff base ligands (X(1) and X(2)) as neutral ionophores. Effect of various plasticizers: 2-nitrophenyloctylether (o-NPOE), dibutyl phosphonate (DBP), dioctylphthalate (DOP), tri-(2-ethylhexyl) phosphate (TEHP), dibutyl butylphosphonate (DBBP), chloronaphthalene (CN) and anion excluders: potassium tetrakis (p-chloropheny1) borate (KTpClPB), sodiumtetraphenylborate (NaTPB) and oleic acid (OA) have been studied. The membrane with a composition of ionophore (X(1)/X(2)):KTpClPB:PVC:o-NPOE (w/w, %) in the ratio of 5:5:30:60 exhibited best performance. The best responsive membrane sensors (8 and 21) exhibited working concentration range of 4.5×10(-7)-1.0×10(-2) M and 3.5×10(-6)-1.0×10(-2) M with a detection limits of 3.2×10(-7) M and 2.3×10(-6) M and Nernstian slopes of 20.0±0.5, 19.5±0.5 mV decade(-1) of activity, respectively. The sensor no. 8 works satisfactorily in partially non-aqueous media up to 10% (v/v) content of methanol, ethanol and acetonitrile. Analytical application of the proposed sensor has been demonstrated in determination of promethium (III) ions in spiked water samples.  相似文献   

9.
Reaction of [Ru (VI)(N)(L (1))(MeOH)] (+) (L (1) = N, N'-bis(salicylidene)- o-cyclohexylenediamine dianion) with excess pyridine in CH 3CN produces [Ru (III)(L (1))(py) 2] (+) and N 2. The proposed mechanism involves initial equilibrium formation of [Ru (VI)(N)(L (1))(py)] (+), which undergoes rapid N...N coupling to produce [(py)(L (1))Ru (III) N N-Ru (III)(L (1))(py)] (2+); this is followed by pyridine substituion to give the final product. This ligand-induced N...N coupling of Ru (VI)N is utilized in the preparation of a series of new ruthenium(III) salen complexes, [Ru (III)(L)(X) 2] (+/-) (L = salen ligand; X = H 2O, 1-MeIm, py, Me 2SO, PhNH 2, ( t )BuNH 2, Cl (-) or CN (-)). The structures of [Ru (III)(L (1))(NH 2Ph) 2](PF 6) ( 6), K[Ru (III)(L (1))(CN) 2] ( 9), [Ru (III)(L (2))(NCCH 3) 2][Au (I)(CN) 2] ( 11) (L (2) = N, N'-bis(salicylidene)- o-phenylenediamine dianion) and [N ( n )Bu 4][Ru (III)(L (3))Cl 2] ( 12) (L (3) = N, N'-bis(salicylidene)ethylenediamine dianion) have been determined by X-ray crystallography.  相似文献   

10.
A highly selective poly(vinyl chloride)-based membrane sensor produced by using N,N-diethyl-N-(4-hydroxy-6-methylpyridin-2-yl)guanidine (GD) as active material is described. The electrode displays Nernstian behavior over the concentration range 7.0 x 10(-5) - 1.0 x 10(-1) M. The detection limit of the electrode is 5.0 x 10(-5) M. The best performance was obtained with the membrane containing 30% PVC, 55% benzyl acetate, 5% GD and 10% oleic acid. The response of the sensor is pH-independent in the range of 3.0 - 7.0. The sensor possesses satisfactory reproducibility, fast response time (< 20 s), and specially excellent discriminating ability for Eu(III) ion with respect to the alkali, alkaline earth, transition and heavy metal ions. The membrane sensor was used as an indicator electrode in potentiometric titration of Eu(III) ion with EDTA. It was also applied in determination of fluoride ions in mouth wash preparations.  相似文献   

11.
Yuan M  Zhao F  Zhang W  Wang ZM  Gao S 《Inorganic chemistry》2007,46(26):11235-11242
By changing ancillary tetradentate Schiff base ligands (L), two new one-dimensional azide-bridged manganese(III) coordination complexes [MnIII(L)(mu1,3-N3)]n [L = 5-Fsalen (1), 5-OCH3 (2); salen = N,N'-bis(salicylidene)-1,2-diaminoethane] as well as a mononuclear complex [MnIII(salophen)(N3)] (3) [salophen = N,N'-bis(salicylidene)-o-phenylenediamine] have been successfully obtained. All of them have been structurally and magnetically characterized. In the structures of 1-3 each MnIII ion is in a distorted octahedral geometry with an obvious Jahn-Teller effect, where the tetradentate L ligands all bind in the equatorial mode, whereas in the axial direction, the N3- ion acts as an end-to-end bridge in 1 and 2 while a terminal group in 3 with a methanol molecule at the other end. Magnetic characterization shows that the mu1,3-bridging azide ion proves to mainly transmit antiferromagnetic interaction between MnIII ions, but these three complexes exhibit various magnetic behaviors at low temperatures. Noteworthily, complex 2 behaves as a weak ferromagnet with a relatively large coercive field of 2.3 kOe, much larger than the value reported previously.  相似文献   

12.
Two novel potentiometric membrane sensors responsive to the ibuprofen drug have been developed. These incorporate poly(vinyl chloride) and polyurethane matrix membranes containing 5,10,15,20-tetraphenylporphrinato (TPP) indium(II) ionophore plasticized with dibutylsebacate. The sensors show a near-Nernstian response with anionic slopes of -53 and -55 mV decade(-1), over the concentration range of 4.2 x 10(-6)-1.0 x 10(-2) and 3.3 x 10(-6)-1.0 x 10(-2) M ibuprofen within pH ranges of 4-9 and 5-9 for PVC and PU matrix membranes, respectively. A sensor based on a polyurethane membrane displays a lower detection limit and a wider linear working range, and a sensor based on a PVC membrane exhibits a better overall selectivity, especially in the presence of lipophilic organic anions. Both sensors are used for the quantification and quality-control assessment of ibuprofen in pharmaceutical preparations. The average recoveries are 99.1+/-0.3% and 99.3+/-0.3% for TPP In(III)-PVC and TPP In(III)-PU based membrane sensors, respectively. High selectivities towards ibuprofen in the presence of many anions, drug excipients and diluents are offered by both sensors, which exhibit a non-Hofmeister selectivity pattern.  相似文献   

13.
A highly selective PVC membrane electrode based on a cerium-salen complex was prepared. The sensor displays an anti-Hofmeister selectivity sequence with a preference for iodide ion over many common organic and inorganic anions. The proposed electrode exhibits a near-Nernstian behavior over a wide concentration range (5.0 x 10(-2) - 8.0 x 10(-6) M) with a slope of 57.5 mV per decade, and a detection limit of 6.0 x 10(-6) M. The electrode has a very fast response time and can be used in the pH range of 3.0 - 1 1.0. It was applied, as an indicator electrode, in potentiometric titration of Ag+ ions.  相似文献   

14.
A new tin complex namely tetracyclohexyl tin(IV) (TCHT) was synthesized and used as the ion carrier for the construction of a highly selective salicylate sensor. This sensor shows a Nernstian response to salicylate ions over a very wide concentration (1.0 × 10?7–1.0 × 10?1 M) in a pH range of 5.5–10.5. The optimum selectivity and response could be obtained for a membrane incorporating 30% PVC, 61% BA, 3% of cationic additive (HTAB) and 6% of TCHT. The response time of the electrode is very short in the whole concentration range (15 s). The electrode also shows an excellent discriminating ability for salicylate ions with respect to the most common organic and inorganic anions including chloride, sulfate, nitrate, nitrite, cyanide, sulfite, iodide, thiocyanate, phosphate, acetate, oxalate, citrate, and tartarate ions. The detection limit of the proposed sensor is 8.0 × 10?8 M. The electrode was successfully used for determining the concentration of salicylate ion in synthetic serums.  相似文献   

15.
[5,10,15,20-Tetrakis(4-N,N-dimethylaminobenzene)porphyrinato]Mn(III) acetate (MnTDPAc) was applied as an ionophore for an iodide-selective PVC membrane electrode. The influences of the membrane composition, pH of the test solution and foreign ions on the electrode performance were investigated. The sensor exhibited not only excellent selectivity to iodide ion compared to Cl- and lipophilic anions such as ClO4- and salicylate, but also a Nernstian response with a slope of -59.4 +/- 1.2 mV per decade for iodide ions over a wide concentration range from 1.0 x 10(-2) to 7.5 x 10(-6) M at 25 degrees C. The potentiometric response was independent of the pH of the solution in the pH range of 2 - 8. The electrode could be used for at least 2 months without any considerable divergence in the potential. Good selectivity for iodide ion, a very short response time, simple preparation and relatively long-term stability were the silent characteristics of this electrode. It was successfully used as an indicator electrode in the potentiometric titration of iodide ions, and also in the determination of iodide from seawater samples and drug formulations.  相似文献   

16.
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.  相似文献   

17.
A nitrate-selective electrode based on a recently synthesized bis(2-hydroxyanil)acetylacetone lead(II) complex [(haacac)Pb] has been developed. Among different compositions studied, a membrane containing 30.7% poly(vinyl chloride) (PVC), 61.3% dibutyl phthalate (DBP) as a plasticizer, 3% methyltrioctylammonium chloride (MTOAC) as a cationic additive and 5% ionophore (all w/w) exhibited the best potentiometric response toward nitrate ion in aqueous solutions. The potentiometric response of the electrode was linear with a Nernstian slope of -58.8 mV decade(-1) within the NO3- concentration range of 2 x 10(-5)-1 x 10(-1) mol dm(-3). The response time of the electrode was < or =10 s over the entire linear concentration range of the calibration plot. The electrode is suitable for use within the pH range of 5.3-11. The selectivity coefficients for the proposed electrode were improved for some interferences, when compared with those of commercially available nitrate-selective electrodes.  相似文献   

18.
New amphiphilic and spin-labile Mn(III) complexes based on dianionic N(4)O(2)-hexadentate sal(2)trien or sal(2)bapen ligands, which contain OC(6)H(13), OC(12)H(25), or OC(18)H(37) alkoxy substituents at different positions of the salicylidene unit were prepared (H(2)sal(2)trien = N,N'-bis(salicylidene)-1,4,7,10-tetraazadecane, H(2)sal(2)bapen = N,N'-bis(salicylidene)-1,5,8,12-tetraazadodecane). According to electrochemical measurements, these complexes undergo two (quasi)reversible redox processes. Temperature-dependent magnetic measurements revealed a high-spin configuration for all sal(2)trien complexes (S = 2) and gradual spin crossover for sal(2)bapen complexes from high to low spin (S = 1). The chain length strongly influences the spin crossover, as C(18)-functionalization stabilizes the low spin state at much higher temperatures than shorter alkyl chains. Moreover, long alkyl chains allow for spontaneous self-assembly of the molecules, which was investigated in single crystals and in Langmuir-films at the air-water interface. Long alkyl chains (C(12) or C(18)) as well as a mutual syn-orientation of these molecular recognition sites were required for the Langmuir monolayers to be stable.  相似文献   

19.
The two chromium chelates of Schiff bases, N-(acetoacetanilide)-1,2-diaminoethane (L1) and N,N′-bis(acetoacetanilide)-triethylenetetraammine (L2), have been synthesized and explored as neutral ionophores for preparing poly(vinylchloride) (PVC) based membrane sensors selective to Cr(III). The addition of lipophilic anion excluder (NaTPB) and various plasticizers viz. o-Nitrophenyloctyl ether (o-NPOE), dioctylpthalate (DOP), dibutylphthalate (DBP), tris(2-ethylhexyl)phosphate (TEHP), and benzyl acetate (BA) have found to improve the performance of the sensors. The best performance was obtained for the membrane sensor having a composition of L1:PVC:DBP:NaTPB in the ratio 5:150:250:3 (w/w). The sensor exhibits Nernstian response in the concentration range 8.9 × 10−8 to 1.0 × 10−1 M Cr3+ with limit of detection 5.6 × 10−8 M. The proposed sensor manifest advantages of relatively fast response (10 s) and good selectivity over some alkali, alkaline earth, transition and heavy metal ions. The selectivity behavior of the proposed electrode revealed a considerable improvement as compared to the best previously PVC-membrane electrode for chromium(III) ion. The potentiometric response of the proposed sensor was independent of pH of the test solution in the range of 2.0-7.0. The sensor has found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol, ethanol and acetonitrile and could be used for a period of 3 months. The proposed electrode was used as an indicator electrode in potentiometric titration of chromium ion with EDTA and in direct determination in different water and food samples.  相似文献   

20.
Huang Y  Liu T  Lin J  Lü J  Lin Z  Cao R 《Inorganic chemistry》2011,50(6):2191-2198
One-dimensional (1D) homochiral nickel coordination polymers [Ni(3)(bpdc)(RR-L)(2)·(DMF)](n) (2R, RR-L = (R,R)-(-)-1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene), bpdc = 4,4'-biphenyldicarboxylic acid) and [Ni(3)(bpdc)(SS-L)(2)·(DMF)](n) (2S, SS-L = (S,S)-(-)-1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene) based on enantiopure pyridyl-functionalized salen(Ni) metalloligand units NiL ((1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene))Ni(II)) have been synthesized and characterized by microanalysis, IR spectroscopy, solid-state UV-vis spectroscopy, thermogravimetric analysis (TGA), circular dichroism (CD) spectroscopy, cyclic voltammetric measurement, and powder and single crystal X-ray diffraction. Each NiL as unbridging pendant metalloligand uses one terminal pyridyl group to coordinate achiral unit (nickel and bpdc(2-)) building a helical chain, while the other pyridyl group remains uncoordinated. Both 2R and 2S contain left- and right-handed helical chains made of the achiral building blocks, while the NiL as remote external chiral source is perpendicular to the backbone of the helices. The nickel coordination polymers 2R and 2S containing unsaturated active nickel center in metalloligand NiL can be used as self-supported heterogeneous catalysts. They show catalytic activity comparable with their homogeneous counterpart in alkene epoxidation and exhibit great potential as recyclable catalysts.  相似文献   

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