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1.
《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   

2.
《Electroanalysis》2006,18(16):1620-1626
A polyvinylchloride membrane sensor based on N,N′‐bis(salecylidene)‐1,2‐phenylenediamine (salophen) as membrane carrier was prepared and investigated as a Al3+‐selective electrode. The sensor exhibits a Nernstian response toward Al(III) over a wide concentration range (8.0×10?7–3.0×10?2 M), with a detection limit of 6.0×10?7 M. The potentiometric response of the sensor is independent of the pH of the test solution in the pH range 3.2–4.5. The electrode possesses advantages of very fast response and high selectivity for Al3+ in comparison with alkali, alkaline earth and some heavy metal ions. The sensor was used as an indicator electrode, in the potentiometric titration of aluminum ion and in determination of Al3+ contents in drug, water and waste water samples.  相似文献   

3.
《Electroanalysis》2005,17(20):1828-1834
A recently synthesized azao‐containing Schiff's base N,N′‐adipylbis(5‐phenylazo salicylaldehyde hydrazone) was used as a suitable neutral ion carrier in construction of a highly selective La3+‐PVC membrane electrode. The electrode exhibits a Nernstian response with a slope of 19.4 mV decade?1 over a wide concentration range (1.0×10?6–1.0×10?2 M) and a limit of detection of 4.0×10?7 M (0.05 ppm). The electrode possesses a fast response time of ca. 10 s and can be used for at least 3 months without observing any deviation. The proposed electrode revealed excellent selectivity for La3+ over a wide variety of alkali, alkaline earth, transition and heavy metal ions and could be used in a pH range of 4.0–8.0. The practical utility of the electrode has been demonstrated by its use as an indicator electrode in the potentiometric titration of La3+ ions with EDTA and in determination of F? ion in some pharmaceutical preparations.  相似文献   

4.
A new, simple, rapid, sensitive, efficient and low‐cost spectrophotometric procedure for the determination of gold was developed. The method is based on the reaction of [AuCl4]? with 2‐[2‐(4‐dimethylaminophenyl)‐vinyl]‐1,3,3‐trimethyl‐3H‐indolium reagent to form a colored ion associate extractable by various organic solvents. The molar absorptivity of the ion associates is in the range (5.7–9.2) × 104 L mol?1 cm?1 depending on the extractant. Butyl acetate was chosen as the extractant. The optimum reaction conditions were established: pH 2–4, concentration of the dye reagent (0.8–1.5) × 10?4 mol L?1. The determination of gold is not hindered even by a 1000‐fold concentration of Ni and Co; a 500‐fold concentration of Pb and Zn; a 100‐fold concentration of Bi, Cu, Cd, Pt, Rh and Ru; or a 20‐fold concentration of Ag. The established method was applied to the determination of gold in model samples and enriched polymetallic ores.  相似文献   

5.
《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   

6.
《Electroanalysis》2003,15(19):1561-1565
A highly selective membrane electrode for the determination of ultratrace amounts of lead was prepared. The PVC membrane electrode based on 2‐(2‐ethanoloxymethyl)‐1‐hydroxy‐9,10‐anthraquinone (AQ), directly coated on graphite, exhibits a good Nernstian response for Pb(II) ions over a very wide concentration range (1.0×10?7–1.0×10?2 M) with a limit of detection of 8.0×10?8 M. It has a fast response time of ca. 10 s and can be used over a period 2 months with good reproducibility (SD=±0.2 mV). The electrode revealed a very good selectivity respect to common alkali, alkaline earth, transition and heavy metal ions and could be used in the pH range of 3.5–6.8. It was used as an indicator electrode in potentiometric titration of lead ions with chromate and oxalate, and in indirect determination of lead in spring water samples.  相似文献   

7.
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   

8.
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   

9.
《Electroanalysis》2004,16(21):1771-1776
In this work a dysprosium [Dy(III)]‐selective solvent polymeric membrane sensor based on N,N‐bis(pyrrolidene) benzne‐1,2‐diamine, poly(vinyl chloride)(PVC), the plasticizer benzylacetate (BA), and anionic site is described. This sensor responds to Dy(III) activity in a linear range from 1.0×10?5 to 1.0×10?1 M, with a slope of 20.6±0.2 mV per decade and a detection limit of 6.0×10?6 M at the pH range of 3.5–8.0. It has a fast response time of<20 s in the entire concentration range, and can be used for at least 2 months without any considerable divergence in the electrode potentials. The proposed sensor revealed comparatively good selectivity with respect to common alkali, alkaline earth, transition and heavy metal ions. It was used as an indicator electrode in the potentiometric titration of fluoride ions and in determination of concentration of F ions in some mouth washing solutions.  相似文献   

10.
To the determination of trace amount of Cd(II) present in food and water samples, a selective and extractive spectrophotometric method were developed with 2,6‐diacetylpyridine‐bis‐4‐phenyl‐3‐thiosemicarbazone as a complexing agent. The yellowish orange colored metal complex, Cd(II)‐2,6‐DAPBPTSC with 1:1 (M:L) composition was extracted in to cyclohexanol at pH 9.5 and was shows maximum absorbance at λmax 390 nm. This method obeys Beer's law in the range of 1.12‐11.25 ppm with 0.972 correlation coefficient of Cd(II)‐2,6‐DAPBPTSC complex, which is indicates linearity between the two variables. The molar absorptivity and sandell's sensitivity were found to be 6.088 × 104 L mol?1 cm?1 and 0.0018 μg cm?2, respectively. The instability constant calculated from Asmus' method (1.447 × 10?4)at room temperature. The precision and accuracy of the method were checked by relative standard deviation (n = 5), 0.929 and its detection limit, 0.0060 μg mL?1. The interfering effects of various cations and anions were also studied. The proposed method was successfully applied to the determination of Cd(II) in foods and water samples, and was evaluated its performance in terms of Student ‘t’ test and Variance ‘f’ test, which indicates the significance of present method. The inter comparison of the experimental values, using atomic absorption spectrometer (AAS), was also repoted.  相似文献   

11.
A method for the trace determination of cadmium ions in water, human urine and human blood serum samples using ultrasonic‐assisted dispersive micro‐solid‐phase extraction (UA‐D‐μSPE) was developed. Silica‐coated magnetic nanoparticles were coated with polythiophene, and the resulting sorbent was characterized using thermogravimetry, differential thermal analysis, scanning electron microscopy, Fourier transform infrared spectrometry and X‐ray diffraction. Following UA‐D‐μSPE, cadmium ions were quantified using graphite furnace atomic absorption spectrometry. A Box–Behnken design was used for optimization of important sorption and desorption parameters in UA‐D‐μSPE: in the sorption step, pH of solution, sorption amount and sonication time for sorption; in the desorption step, concentration of eluent, volume of eluent and sonication time. The optimum conditions for the method were: pH of solution, 7.5; sonication time for sorption, 3 min; sorption amount, 35 mg; type and concentration of eluent, HCl and 1.1 mol l?1; volume of eluent, 360 μl; sonication time for desorption, 110 s. Under the optimized conditions the limit of detection and relative standard deviation for the detection of cadmium ions by UA‐D‐μSPE were found to be 0.8 ng l?1 and <6%, respectively.  相似文献   

12.
《Electroanalysis》2005,17(17):1534-1539
The construction, performance, and applications of a novel ytterbium(III) sensor based on N‐(2‐pyridyl)‐N′‐(2‐methoxyphenyl)‐thiourea (PMT), as an excellent carrier, in plasticized poly(vinyl chloride) PVC matrix, is described. The influences of membrane composition and pH on the potentiometric response of the sensor were investigated. The sensor exhibits a nice Nernstian response for Yb(III) ion over a wide concentration range of 4 decades of concentration (1.0×10?6–1.0×10?2 M), and a detection limit of 5.0×10?7 M. The response time of the electrodes is between 8 and 10 s, depending on the concentration of ytterbium(III) ions. The proposed sensor can be used for about 8 weeks without any considerable divergence in potential. The sensor revealed very good selectivity for Yb(III) in the presence of several metal ions. The best performance was observed for the membrane containing; 30% PVC, 59% o‐nitrophenyloctyl ether (NPOE) as solvent mediator, 7% PMT, and 4% sodium tetraphenyl borate (NaTPB). It was successfully applied as indicator electrodes in the potentiometric titration of Yb(III) with EDTA and for the determination of fluoride ion in two mouth wash formulations. The proposed La(III) sensor was found to work well under laboratory conditions. It was also used as an indicator electrode in titration of a 1.0×10?4 M of Yb(III) with a standard EDTA solution (1.0×10?2 M). It was also used for determination of Yb(III) ion in Xenotime .  相似文献   

13.
A new preconcentration method is presented for lead on TAN‐loaded polyurethane foam (PUF) and its measurement by differential pulse anodic stripping voltammetry (DPASV). The optimum sorption conditions of 1.29 × 10?5 M solution of Pb(II) ions on TAN‐loaded PUF were investigated. The maximum sorption was observed at pH 7 with 20 minutes equilibrated time on 7.25 mg mL?1 of TAN‐loaded foam. The kinetic study indicates that the overall sorption process was controlled by the intra‐particle diffusion process. The validity of Freundlich, Langmuir and Dubinin ‐ Radushkevich adsorption isotherms were tested. The Freundlich constants 1/n and KF are evaluated to be 0.45 ±0.04 and (1.03 +0.61) × 10?3 mol g?1, respectively. The monolayer sorption capacity and adsorption constant related to the Langmuir isotherm are (1.38 ± 0.08) × 10?5 mol g?1 and (1.46 ± 0.27) × 105 L mol?1, respectively. The mean free energy of Pb(II) ions sorption on‐TAN loaded PUF is 11.04 ± 0.28 kJ mol?1 indicating chemisorption phenomena. The effect of temperature on the sorption yields thermodynamics parameters of ΔH, ΔS and ΔG at 298 K that are 15.0 ± 1.4 kJ mol?1, 74 ±5 J mol?1 K?1 and ‐7.37 ± 0.28 kJ mol?1, respectively. The positive values of enthalpy (ΔH) and entropy (ΔS) indicate the endothermic sorption and stability of the sorbed complexes are entropy driven. However, the negative value of Gibb's free energy (ΔG) indicates the spontaneous nature of sorption. On the basis of these data, the sorption mechanism has been postulated. The effect of different foreign ions on the sorption and desorption studies were also carried out. The method was successfully applied for the determination of lead from different water samples at ng levels.  相似文献   

14.
Acibenzolar‐S‐methyl (ASM) is a novel fungicide applied for crop protection. A renewable silver amalgam film electrode was used for the determination of ASM in pH 3.4 Britton? Robinson buffer using square wave adsorptive stripping voltammetry (SW AdSV). The parameters of the method were optimized. The electroanalytical procedure made possible to determine ASM in the concentration range of 5×10?8–3×10?7 mol L?1 (LOD=4.86×10?9, LOQ=1.62×10?8 mol L?1). The effect of common interfering pesticides and heavy metal ions was checked. The validated method was applied in ASM determination in spiked water samples.  相似文献   

15.
A chloride ion‐selective electrode (ISE) membrane was developed by using a copolymeric ion‐exchanger resin (trimethyl ethenyl quaternary ammonium chloride polystyrene‐divinylbenzene copolymer resin, TMEQAC PSDVB), the ionophore ({μ‐[4,5‐Dimethyl‐3,6‐bis(dodecyloxy)‐1,2‐phenylene]}bis(mercury chloride), ETH9033), the plasticizer (bis(2‐ethylhexyl) sebacate, DOS), and the membrane substrate (polyvinylchloride, PVC). At 25 °C, the electrode exhibited an ideal Nernstian response of 59.2 mV/decade with the linear calibration concentration range from 1.0 × 10?4‐1.0 × 10?2 M (r2 = 0.9930). The limit of detection was 2.45 ppm (6.9 × 10?2 mM) and the measurement response time was less than 10 seconds. The working temperature range of electrode was 10‐45 °C. The working pH range for chloride ion measurement was 2.0‐11.0. Among the various anions examined in this work, only I?, SCN?, and MnO4? ions show significant interference to the electrode measurement. The chloride ISE can be used at least 72 days. The determination of chloride ion content in three kinds of environmental water sample with the electrode method was accurate (92‐95%) and precise (RSD < 4.4%) and did not show significance difference from the high‐performance liquid chromatography method.  相似文献   

16.
Electrochemical behavior of remarkably low levels of Ribonucleic acid yeast (yRNA) is studied through differential pulse voltammetry (DPV), and kinetic parameters of the electrochemical reaction have also been calculated through square‐wave voltammetry (SWV), based on immobilization of yRNA on the surface of a CPB‐cellulose modified electrode. YRNA/ CPB‐cellulose/ITO conductive glass electrode is demonstrated by Infrared reflect (IR) and electrochemical impedance spectroscopy (EIS). The oxidation peak potential of yRNA shifts negatively with increasing pH. The peak currents decrease gradually in successive scans and no corresponding reduction peaks occur, indicating that oxidation process of yRNA is completely irreversible. Variables influencing DPV response of yRNA, such as pH, pulse amplitude and electrolyte concentration, are explored and optimized. Peak currents are proportional to the concentration of yRNA in the range of 0.1 μg mL?1–1.0 μg mL?1, and the linear regression coefficient equals 0.9923. The detection limit for yRNA is 1.0×10?10 g mL?1. Interferences of L ‐cysteine, L ‐alanine, Hemoglobin, Uridine 5′‐monophosphate, Guanosine 5′‐monophosphate, Adenosine 5′‐triphosphate and some metal ions (Co3+, Cr3+, Ni2+, Hg2+, Zn2+, etc) are negligible. The methods adopted here are more sensitive and selective than currently applied techniques and overcome the drawback of absorption spectroscopy arising from a strong interference due to other UV‐absorbing substances.  相似文献   

17.
The simple PVC‐based membrane containing N,N′,N″,N′′′‐tetrakis(2‐pyridylmethyl)‐1,4,8,11‐tetraazacyclotetradecane (tpmc) as an ionophore and dibutyl phthalate as a plasticizer, directly coated on a glassy carbon electrode was examined as a new sensor for Cu2+ ions. The potential response was linear within the concentration range of 1.0×10?1–1.0×10?6 M with a Nernstian slope of 28.8 mV/decade and detection limit of 7.0×10?7 M. The electrode was used in aqueous solutions over a wide pH range (1.3–6). The sensor exhibited excellent selectivity for Cu2+ ion over a number of cations and was successfully used in its determination in real samples.  相似文献   

18.
MOGHIMI Ali 《中国化学》2008,26(10):1831-1836
A novel, simple, sensitive and effective method has been developed for preconcentration of thallium on N,N’-bis(3-methylsalicylidene)-ortho-phenylenediamine (MSOPD) adsorbent in a pH range 5.0—10.0, prior to its spectrophotometric determination, based on the oxidation of bromopyrogallol red at λ=520 nm. This method makes it possible to quantitize thallium in a range of 3.6×10-9 to 2.0×10-5 mol/L, with a detection limit (S/N=3) of 1.42×10-9 mol/L. This procedure has been successfully applied to determine the ultra trace levels of thallium in the environmental samples, free from the interference of some diverse ions. The precision, expressed as relative standard deviation of three measurements, is better than 2.9%.  相似文献   

19.
Anion sensor properties of N‐alkyl‐substituted 1,4′‐diazaflavonium bromides in methanol–water were evaluated by UV–vis spectrometry. Pronounced changes were observed in the absorption spectra of all compounds for only OH?, CO32?, and CN? among F?, Cl?, Br?, I?, OH?, CO32?, NO3?, PO43?, CN?, SO42?, HSO4?, HCO3?, SCN?, NO2?, and P2O72? ions. Two new absorption bands at 385 and 685 nm accompanying the distinct color change for OH?, CO32?, and CN? ions were observed in case of all compounds. The color changes were from pink to blue for CO32? and OH? ions and from pink to purple for CN? ion. Thanks to the distinct color change, the compounds can be used as selective colorimetric anion sensors. Linear changes of absorbance of N‐heptyl‐substituted compound at 385 nm as a function of the ion concentration were used to determine CN? ion in water samples. Detection and quantification limits of the proposed method were 0.94 and 2.82 mg/L, respectively.  相似文献   

20.
Fullerence C60‐cryptand 22 was prepared and successfully applied as the electric carrier in the PVC electrode membrane of a bifunctional ion‐selective electrode for cations, e.g., Ag+ ions as well as anions, e.g., I? ions. The bifunctional ion‐selective electrode based on C60‐cryptand 22 can be applied as a Silver (Ag+) ion selective electrode with an internal electrode solution of 10?3 M AgNO3 in water (pH = 6.3), or as an Iodide (I?) ion selective electrode with an acidic internal electrode solution of 10?4 M KI(aq) (pH = 2) in which the cryptand 22 is protonated, and the C60‐cryptand 22 is changed to C60‐Cryptand22–H+ and becomes an anionic electro‐carrier to absorb the I? ion. The Ag+ ion selective electrode based on C60‐cryptand 22 gave a linear response with a near‐Nernstian slope (59.5 mV decade?1) within the concentration range 10?1‐10?3 M Ag+(aq). The Ag+ ion electrode exhibited comparatively good selectivity for silver ions, over other transition‐metal ions, alkali and alkaline earth metal ions. The Ag+ ion selective electrode with good stability and reproducibility was successfully used for the titration of Ag+(aq) with Cl? ions. The Iodide (I?) Ion selective electrode based on protonated C60–cryptand22‐H+ also showed a linear response with a nearly Nernstian slope (58.5 mV decade?1) within 10?1 ‐ 10?3 M I? (aq) and exhibited good selectivity for I? ions and had small selectivity coefficients (10?2–10?3) for most of other anions, e.g., F? , OH?, CH3COO?, SO42?, CO32?, CrO42?, Cr2O72? and PO43? ions.  相似文献   

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