首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 46 毫秒
1.
《Electroanalysis》2005,17(20):1865-1869
A novel anion‐selective PVC membrane electrode based on bis‐[(3‐ferrocenyl)‐(2‐crotonic acid)] copper(II) complex [Cu(II)‐BFCA] as neutral carrier is described, which demonstrates excellent potentiometric response characteristics toward thiocyanate ion and anti‐Hofmeister selectivity sequence in following order: SCN?>I?>ClO >Sal?>Br?>NO >Cl?≈NO >SO >SO . The electrode shows a near‐Nernstian response for thiocyanate ion in a wide range of 9.0×10?7–1.0×10?1 M with a detection limit 6.8×10?7 M and a slope of ?59.1 mV/decade in pH 5.0 of phosphate buffer solution at 20 °C. The influences of lipophilic cationic and anionic additives on the response properties of the electrode were investigated. High sensitivity and wide linear dynamic range were observed for the electrode in the presence of hexadecyltrimethylammoniumborate (HTAB) as a lipophilic cationic additive. The electrode was successfully applied to the determination of thiocyanate ion in waste water and human saliva.  相似文献   

2.
《Analytical letters》2012,45(5):890-901
Abstract

A highly selective polyvinyl chloride (PVC) membrane electrode, based on N,N′‐(aminoethyl)ethylenediamide bis(2‐benzoideneimine) binuclear copper(II) complex [Cu(II)‐AEBB] as neutral carrier, was prepared for thiocyanate (SCN?) determination, which displays an anti‐Hofmeister selectivity sequence for a series of anions in the following order: SCN?>ClO4 ?>Sal? > I?>NO3 ?>Br?> Cl?>NO2 ?>SO3 2?>F?>H2PO4 ?>SO4 2?. The electrode exhibited near‐Nernst response for SCN? with a slope of –59.0 mV/decade over a wide concentration range (8.5×10?7~6.8×10?1 mol/L) with a detection limit of –5.0×10?7 mol/L in pH 5.0 phosphate buffer solution at 25°C. Alternating current (AC) impedance and equivalent circuits were used to investigate the thiocyanate response mechanism of the membrane doped with [Cu(II)‐AEBB].  相似文献   

3.
The synthesis of a new compound, amide‐linked manganese diporphyrin xanthene (Mn2Cl2ADPX), and its application for preparation of thiocyanate selective electrodes was described. The electrode was prepared with a PVC membrane combining Mn2Cl2ADPX as an electro active material, 2‐nitrophenyl octyl ether (o‐NPOE) as a plasticizer in the percentage ratio of 3 : 65 : 32 (Mn2Cl2ADPX: o‐NPOE: PVC, w : w : w). The electrode exhibited linear response within the concentration range of 2.4×10?6 to 1.0×10?1 M SCN?, with a working pH range from 3.0 to 8.0 and a fast response time of less than 60 s. Several electroactive materials and solvent mediators have been compared and the experimental conditions were optimized. The Mn2Cl2ADPX based electrode shows obviously better response characteristics than that of monoporphyrin manganese in terms of working concentration range and slope. Selectivity coefficients for SCN? relative to a number of interfering ions were investigated. The electrode exhibits anti‐Hofmeister selectivity toward SCN? with respect to common coexisting anions. The electrode was applied to the determination of SCN? in body urine with satisfactory results.  相似文献   

4.
A highly selective PVC membrane electrode was prepared for thiocyanate (SCN?) determination, based on macrotricyclic binuclear Cu(II)–Schiff base complex as an ionophore. The novel macrotricyclic compound (cryptand) was synthesized by condensation of 4,4′-diamino-dibenzo-18-crown-6 with bis(4-formyl phenyl)terephthalate under high-dilution condition and the structure was confirmed by FT-IR, 1H NMR,13C NMR and MS studies. The Cu(II) complex of the compound was prepared and was examined for use as anion-selective electrode as a carrier which displays an anti-Hofmeister selectivity sequence in following order: SCN? > ClO4 ? > NO3 ? > CN? > I? > CO3 2? > NO2 ? > Br? > Cl? > SO4 2? with a preference for thiocyanate ion over many common anions. The electrode has a linear dynamic range between 1.0 × 10?7 and 1.0 × 10?1 M, with a Nernstian slope of ?58.9 mV decade?1 and detection limit of 3.1 × 10?8 M. The working pH range of the sensor was found be in the range of 3.0–8.0. It exhibits a fast response time of 20 s and has a lifetime of about 2 months. Application of the electrode for determination of thiocyanate in waste water samples and in human urine samples have also been demonstrated.  相似文献   

5.
本文报道了一种以牛磺酸双核铜络合物为中性载体的硫氰酸根PVC膜电极。该电极对硫氰酸根有良好的电位响应并呈现出anti-Hofmeister行为,其选择性顺序SCN->I->ClO4->Sal->NO3-> NO2-> Br- > Cl- > SO3-> SO4 2-。在20℃ pH 5.0的磷酸缓冲溶液中,其线性范围为1.0´10 -1~ 1.0´10-6mol×L-1,检测线为8.0×10 -7mol•L-1,斜率为 -56.5 mV/pcSCN-。紫外、红外和交流阻抗研究表明电极的高选择性与载体的立体结构和分析物与中心金属离子的作用相关。将该电极用于废水和人体尿液中硫氰酸根的测定,获得了较满意的结果。  相似文献   

6.
《Electroanalysis》2005,17(21):1945-1951
Tin(IV) porphyrins derivatives were used as ionophores for phthalate selective electrodes preparation. The influence of ionophore structure and membrane composition (amount of incorporated ionic sites) on the electrode response, selectivity and long‐term stability were studied. Poly(vinyl chloride) polymeric membranes plasticized with o‐NPOE (o‐nitrophenyloctylether) and containing Sn(IV)‐tetraphenylporphyrin (TPP) dichloride (Sn(IV)[TPP]Cl2) or Sn(IV)‐octaethylporphyrin (OEP) dichloride (Sn(IV)[OEP]Cl2), and in some cases incorporating lipophilic cationic (tetraocthylammonium bromide ‐ TOABr) and anionic (sodium tetraphenylborate – NaTPB and potassium tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate‐KTFPB) additives, were prepared and their potentiometric characteristics compared. Both ionophores are shown to operate via a neutral mechanism, and the addition of 10 mol % of lipophilic quaternary ammonium salt derivative to the membrane is required to achieve optimal electrode performance. The potentiometric units prepared, with Sn(IV)[TPP]Cl2 (Type A) or Sn(IV)[OEP]Cl2 (Type B) without additives, presented a slope of ?52.8 mV dec?1 and ?58.8 mV dec?1 and LLLR of 9.9×10?5 mol L?1 and 9.9×10?6 mol L?1, respectively. The units prepared using the same metalloporphyrins and incorporating 10% mol TOABr presented a slope of ?55.0 mV dec?1 and ?57.8 mV dec?1 and LLLR of 5.0×10?7 mol L?1 and 3.0×10?7 mol L?1. Their analytical usefulness was assessed by potentiometric determinations of phthalate in water and industrial products providing results that presented recoveries of about 100%.  相似文献   

7.
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   

8.
《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   

9.
Electrochemical behavior of dopamine (DA) was investigated at the gold nanoparticles self‐assembled glassy carbon electrode (GNP/LC/GCE), which was fabricated by self‐assembling gold nanoparticles on the surface of L ‐cysteine (LC) modified glassy carbon electrode (GCE) via successive cyclic voltammetry (CV). A pair of well‐defined redox peaks of DA on the GNP/LC/GCE was obtained at Epa=0.197 V and Epc=0.146 V, respectively. And the peak separation between DA and AA is about 0.2 V, which is enough for simultaneous determination of DA and AA. The peak currents of DA and AA were proportional with their concentrations in the range of 6.0×10?8–8.5×10?5 mol L?1 and 1.0×10?6–2.5×10?3 mol L?1, with the detection limit of 2.0×10?8 mol L?1 and 3.0×10?7 mol L?1 (S/N=3), respectively. The modified electrode exhibits an excellent reproducibility, sensibility and stability for simultaneous determination of DA and AA in human serum with satisfactory result.  相似文献   

10.
《Electroanalysis》2006,18(21):2070-2078
A highly selective potentiometric sensor for thiocyanate ion based on the use of a newly synthesized organo‐palladium ion exchanger complex dispersed in a plasticized poly(vinyl chloride) membrane is described. The sensor displays a Nernstian response (?57.8±0.2 mV decade?1) over a wide linear concentration range of thiocyanate (1.0×10?6–1.0×10?1 mol L?1 ), low detection limit (6.3×10?7 mol L?1), fast response (20 s), stable potential readings (±0.4 mV), good reproducibility (±0.9%), long term stability (8 weeks), high precision (±0.7%) and applicability over a wide pH range (4–10). Negligible interferences are caused by F?, Cl?, I?, Br?, NO3?, NO2?, CN?, SO42?, S2O32?, PO43?, citrate, acetate and oxalate ions. Under hydrodynamic mode of operation (FIA), the calibration slope is ?51.1±0.1 mV decade?1, the linear response range is 1.0×10?5–1.0×10?1 mol L?1 SCN? and the sample throughput is 40–45 per hour. The sensor is satisfactory used for manual and flow injection potentiometric determination of SCN? in the saliva and urine of cigarette smokers and non smokers. The data agree fairly well with results obtained by the standard spectrophotometric technique. Direct potentiometry and potentiometric titration of SCN? with Ag+ are also monitored with the sensor.  相似文献   

11.
A new podand of 1,1′‐thia‐bis‐[1‐(chloroethan‐2‐acetamid‐α‐oxy)] naphtol was synthesized and used as a suitable carrier for Ag+ PVC membrane electrode. The electrode exhibited linear response with a Nernstian slope of (59.5±0.8 mV/decade) within a wide concentration range of 1.0×10?7 to 1.5×10?2 mol L?1 silver ions. The electrode had a fast response time of <10 s and detection limit of 8.6×10?8 mol L?1 with a working pH range from 3.7 to 9.0. The electrode was highly selective for Ag(I) ions over a large number of cations such as alkali, alkaline earth, and heavy metal ions. The proposed sensor has been applied as an indicator electrode for indirect determination of vitamin B1 in tablets by determination of Cl? ions in this compound with a standard solution of Ag(NO3).  相似文献   

12.
A novel selective thiocyanate PVC membrane electrode based on bis-bebzoin-semitriethylenetetraamine binuclear copper(II) [Cu(II)2–BBSTA] as neutral carrier is reported, which displays an anti-Hofmeister selectivity sequence in following order: SCN > ClO4 > I >Sal >SO32− >NO3 > H2PO4 > Cl >NO2 > SO42−. The electrode exhibits Nernstian potential linear range to thiocyanate from 1.0 × 10−1 to 9.0 × 10−7 mol/l with a detection limit 7.0 × 10−7 mol/l and a slope of −57.0 mV/decade in pH 5.0 of phosphorate buffer solution at 25 °C. The response mechanism is discussed in view of the AC impedance technique and the UV spectroscopy technique. From comparison of potentiometric response characteristics between the binuclear metallic complex copper(II) [Cu(II)2–BBSTA] and mononuclear copper(II) metallic complex [Cu(II)–BBSDA], an enhanced response towards thiocyanate from the electrode based on binuclear metallic complex copper (II) [Cu(II)2–BBSTA] was observed. The electrode based on binuclear copper(II) compound was used to determine the thiocyanate content in waste water with satisfactory results.  相似文献   

13.
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   

14.
A new solvent polymeric membrane electrode based on pyrazolone heterocyclic Schiff base complexes of Co(II) is described. It shows a preferential response towards thiocyanate over a range of 2.0 × 10–6 to 1.0 × 10–1 mol L–1 with a slope of –60.2 ± 0.6 mV/dec. The selectivity sequence observed is thiocyanate > hydroxide > nitrite > iodide > perchlorate > citrate > bromide > fluoride > chloride > nitrate > acetate > borate > sulfate > phosphate. The selectivity behavior is discussed in view of axial coordination by uv/vis spectroscopy and the transfer process of thiocyanate across the membrane interface is investigated by the ac impedance technique. The electrode was successfully applied to the determination of thiocyanate in human urine as an indicator for distinguishing between smokers and non-smokers.  相似文献   

15.
《Analytical letters》2012,45(2):369-386
Abstract

Three kinds of transition metal chelates of unsymmetrical tetradentate Schiff base, o‐hydroxybenzophenone‐1,2‐diaminobenzene‐pyrrole‐2‐carbaldehyde(H2L), were synthesized to prepare anion‐selective electrodes and their anion response characteristics were investigated. The results show that the performances of the electrodes are considerably influenced by the nature of the central metals. The proposed electrode with the Cu(II)‐chelate and cationic additive demonstrated an anti‐Hofmeister selectivity sequence with a good selectivity towards thiocyanate in the following order: Thiocyanate>iodide>salicylate>perchlorate>bromide>nitrite>chloride>acetate>fluoride>nitrate>sulfite>sulfate. The electrode had an excellent linear response to thiocyanate from 3.4×10?7 to 1.0×10?1 M in phosphate buffer solution at pH 5.0 with a slope of ?58.7 mV per decade, a detection limit of 1.6×10?7 M, and a fast response time within 5 s over the entire concentration series. Spectroscopic techniques and AC impedance were used to investigate the response mechanism to thiocyanate of the membrane doped with Cu(II)‐chelate. The preliminary application of the electrode for determination of thiocyanate in wastewater and urine samples is reported.  相似文献   

16.
《Electroanalysis》2003,15(22):1751-1755
A sensitive, selective and economic stripping voltammetry is described for the determination of trace amounts of zirconium at a morin‐modified carbon paste electrode (morin‐MCPE). Zirconium(IV) can be preconcentrated on the surface of the morin‐MCPE due to forming the Zr(IV)–morin complex. The complex produces two second‐order derivative anodic peaks at 0.69 V (vs. SCE) and 0.75 V when linear‐scanning from 0.0 to 1.0 V. The optimum analytical conditions are: 2.2 mol L?1 HCl, 0.0 V accummulation potential, 90 s accummulation time, 250 mV s?1 scan rate. A linear relationships between the peak currents at 0.75 V and the Zr(IV) concentration are in the range of 2.0×10?8 to 3.0×10?6 mol L?1. The detection limit is 1.0×10?8 mol L?1 (S/N=3) for 120 s accumulation. The RSD for determination of 4.0×10?7 mol L?1 Zr(IV) is 4.8% (n=8). The proposed method has been applied to determine zirconium in ore samples, unnecessarily extracted.  相似文献   

17.
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   

18.
The two podand chelates based on diethylsulfide, 1,5‐bis(2′‐hydroxy‐4′‐nitrophenoxy)‐3‐thiapentane (L1) and 1,5‐bis(8′‐oxybenzopyridine)‐3‐thia pentane (L2), have been synthesized and explored as neutral ionophores for preparing poly(vinyl chloride) based membrane electrodes selective to Pb2+. The addition of anionic additives and various plasticizers has been found to substantially improve the performance of the electrode. The best performance was obtained with the electrode No. 1 having a membrane of ionophore (L1) with the composition PVC:o‐NPOE:ionophore (L1):NaTFPB (%w/w) of 33 : 62 : 3 : 2. The electrode exhibits Nernstian response with a slope of 31.57±0.3 mV decade?1 of activity in the concentration range from 2.0×10?9 to 1.0×10?1 M Pb2+, performs satisfactorily over a wide pH range (1.6–7.0), with a fast response time (5 s).  相似文献   

19.
New Mn(III)‐L and Mn(IV)‐L complexes were prepared from the highly lipophilic salophen ligand (L): phenol 2,2′‐[(4,5‐dimethyl‐1,2‐phenylene)bis[(E)‐nitrilomethylidyne]]bis[4,6‐bis(1,1‐dimethylethyl). The prepared complexes were fully characterized and used for the construction of thiocyanate membrane electrodes. Optimized membrane electrodes contained 33.0 mg PVC, 66.0 mg o‐nitrophenyloctylether, 50 or 5 (mole %) tetrakis(trifluoromethyl)phenyl borate and 1 mg Mn(III)‐L (sensor 2) or Mn‐(IV)‐L (sensor 12), respectively. Such electrodes exhibited linear responses toward thiocynate in a concentration range of 10?1–10?5 M and detection limits of 8.3×10?6, 8.9×10?6 M for sensor 2 and 12, respectively. Optimized membrane electrodes exhbited high selectivty toward thiocayante compared to more lipophilic anions. The observed thiocyanate selectivity of the optimized membranes was confirmed by formation constant calculations for Mn(III)‐L and Mn(IV)‐L with SCN?, β=1014.1 and 1012.5, which was measured potentiometrically using the sandwich membrane method. Furthermore, computational study using DFT calculations was performed to at DFT/B3LYP level of theory to confirm the observed selectivity data. The response times were 3 and 0.5 min for low and high concentrations. The lifetimes of the optimized electrodes were ~4–6 weeks. The analytical utility of the optimized membrane electrodes was demonstrated by the analysis of thiocyanate level in different saliva samples.  相似文献   

20.
A new ion selective electrode for salicylate based on N,N'-(aminoethyl)ethylenediamide bis(2-salicylideneimine) binuclear copper(Ⅱ) complex [Cu(Ⅱ)2-AEBS] as an ionophore was developed. The electrode has a linear range from 1.0 × 10^-1 to 5.0 ×10^-7 mol·L^- 1 with a near-Nemstian slope of ( - 55 ±1 ) mV/decade and a detection limit of 2.0 × 10-7 mol·L^-1 in phosphorate buffer solution of pH 5.0 at 25 ℃. It shows good selectivity for Sal^- and displays anti-Hofmeister selectivity sequence: Sal^-〉SCN^-〉 ClO4^- 〉I^-〉 NO2^- 〉Br^-〉 NO3^- 〉Cl^-〉 SO3^2- 〉 SO4^2- The proposed sensor based on binuclear copper(Ⅱ)complex has a fast response time of 5-10 s and can be used for at least 2 months without any major deviation. The response mechanism is discussed in view of the alternating current (AC) impedance technique and the UV-vis spectroscopy technique. The effect of the electrode membrane compositions and the experimental conditions were studied. The electrode has been successfully used for the determination of salicylate ion in drug pharmaceutical preparations.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号