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1.
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   

2.
Conducting polymer poly(pyrrole) (PPy) doped with Nafion was successfully used as ion-to-electron transducer in the construction of a solid-contact Pb2+-selective polymeric membrane electrode. The Nafion dopant can effectively increase the capacitance of the conducting polymer and improve the mechanical robustness of the coating. The transducer layer, PPy-Nafion, characterized by cyclic voltammetry and electrochemical impedance spectroscopy, exhibits a sufficiently high bulk (redox) capacitance and fast ion and electron transport process. The new Pb2+-selective polymeric membrane electrode, based on PPy-Nafion film as solid contact, shows stable Nernstian characteristics in Pb(NO3)2 solution within the concentration range of 1.0 × 10−7–1.0 × 10−3 M, and the detection limit is 4.3 × 10−8 M. The potential stability of the electrode and the influence of the interfacial water layer were also evaluated by chronopotentiometry and potentiometric water layer test, respectively. The results show that the solid-contact Pb2+-selective electrode, based on PPy-Nafion film as ion-to-electron transducer, can effectively overcome the potential drift and reduce the water layer between the PPy-Nafion transducer layer and the ion-selective membrane.  相似文献   

3.
The voltammetric determination of 2-mercaptobenzimidazole (MBI) was studied by using a glassy carbon electrode (GCE) coated with polymeric nickel and copper tetraaminophthalocyanine (poly-NiTAPc and poly-CuTAPc) membrane. The polymeric membrane decreases the overpotential of oxidation of MBI by 136.2 and 115.0 mV and increases the oxidation peak current by about 3.4 and 3.3 times, while the reduction peak potential shifts positively by 113.0 and 84.1 mV and the peak current increases by about 10 and 7 times in 0.1 mol·l−1 phosphate buffer solution (PBS) at pH = 2.0 for poly-NiTAPc and poly-CuTAPc, respectively, compared to the unmodified GCE. The results indicated that the developed electrode exhibited efficient electrocatalytic activity for MBI with relatively high sensitivity, stability, and long life. The oxidation and reduction peak currents of MBI were linear to its concentrations ranging from 8.0 × 10−5 to 1.0 × 10−3 mol·l−1 at poly-NiTAPc and from 2.0 × 10−5 to 1.0 × 10−3 mol·l−1 at poly-NiTAPc membranes modified electrodes, respectively, with a low limit of detection.  相似文献   

4.
A trazodone-selective electrode for application in pharmaceutical quality control and urine analysis was developed. The electrode is based on incorporation of a trazodone-tetraphenylborate ion exchanger in a poly(vinyl chloride) membrane. The electrode showed a fast, stable and Nernstian response over a wide trazodone concentration range (5 × 10−5−1 × 10−2 M) with a mean slope of 59.3 ± 0.9 mV/dec of concentration, a mean detection limit of 1.8 × 10−5 ± 2.2 × 10−6 M, a wide working pH range (5–7.5) and a fast response time (less than 20 s). The electrode also showed good accuracy, repeatability, reproducibility and selectivity with respect to some inorganic and organic compounds, including the main trazodone metabolite. The electrode provided good analytical results in the determination of trazodone in pharmaceuticals and spiked urine samples; no extraction steps were necessary. Dissolution testing of trazodone tablets, in different conditions of pH and particle size, based on a direct potentiometric determination with the new selective electrode is presented as well.  相似文献   

5.
A flow injection analysis (FIA) system was developed for the determination of phosphate efflux from wine lactic acid bacteria (Oenococus oeni and Lactobacillus hilgardii) as an indication of cell membrane damage. The system allowed the direct injection of the cell suspension, avoiding the filtration step, with minimum sample treatment and minimized reagent consumption. The developed system is characterized by a linear concentration zone between 3.23 × 10−5 and 4.84 × 10−4 mol L−1 PO4 3− and repeatability better than 2.9%. Bacterial suspensions were exposed to a chemical stress with phenolic acids and injected in the FIA system at regular intervals. The extracellular concentration of phosphate was measured spectrophotometrically. The experimental results obtained indicate that hydroxycinnamic acids (p-coumaric, ferulic and caffeic) induced faster phosphate leakage rates than hydroxybenzoic acids (vanillic and p-hydroxybenzoic) in both strains tested, which could be related to their higher lipophilic character.  相似文献   

6.
Three platinum(II) complexes were synthesized and studied to characterize their ability as an anion carrier in a PVC membrane electrode. The polymeric membrane electrodes (PME) and also coated glassy carbon electrodes (CGCE) prepared with one of these complexes showed excellent response characteristics to perchlorate ions. The electrodes exhibited Nernstian responses to ClO4 ions over a wide concentration range from 1.5 × 10−6 to 2.7 × 10−1M for PME and 5.0 × 10−7 to 1.9 × 10−1M for CGCE with low detection limits (9.0 × 10−7M for PME and 4.0 × 10−7M for CGCE). The electrodes possess fast response time, satisfactory reproducibility, appropriate lifetime and, most importantly, good selectivity toward ClO4 relative to a variety of other common anions. The potentiometric response of the electrodes is independent of the pH of the test solution in the pH range 2.0–9.0. The proposed sensors were used in potentiometric determination of perchlorate ions in mineral water and urine samples. Correspondence: Ahmad Soleymanpour, Department of Chemistry, Damghan Basic Science University, Damghan, Iran.  相似文献   

7.
Determination of the effective components in traditional Chinese medicine is one of the key steps for its identification. In this paper a novel and sensitive chemiluminescence (CL) method for the determination of rhein coupled with flow-injection analysis (FIA) is developed. It is based on the strong sensitizing effect on the weak CL reaction between luminol and ferricyanide in alkaline solution. Under optimal experimental conditions, the relative CL intensity is proportional to the concentration of rhein in the range of 7.0 × 10−12–7.0 × 10−10 mol L−1 and 1.0 × 10−9–4.0 × 10−5 mol L−1, the detection limit is 1.478 × 10−13 mol L−1, and the relative standard deviation (RSD) for 9 parallel measurements of 1.408 × 10−7 mol L−1 rhein is 3.4%. The method was successfully applied to the determination of rhein in pharmaceutical preparations. The possible mechanism of CL is also briefly discussed.  相似文献   

8.
Glassy carbon electrode modified with electrodeposited cobalt oxide nanostructure shows an excellent electrocatalytic activity toward insulin oxidation at a wide pH range. Cyclic voltammetry, hydrodynamic amperometry, and flow injection analysis (FIA) were used for insulin determination at a picomolar and higher-concentration range. Amperometric determination of insulin at this modified electrode yielded a calibration curve with the following characteristics; linear range, 100 pM–15 nM; sensitivity of 83.9 nA nM−1 and detection limit 10 pM. FIA yielded the calibration curve with sensitivity and detection limit of 2.0 nA nM−1 and 25 pM, respectively. Furthermore, the RSD of repetitive FIA for 200 pM insulin (n = 13) is 2%. In addition, the interference effect of electroactive existing species (lactic acid, cholesterol, ascorbic acid, uric acid, and glucose) was eliminated by covering the surface of the modified electrode with nafion film. Fast response time, signal stability, high sensitivity, low cost, and ease of preparation are the advantages of the proposed insulin sensor.  相似文献   

9.
A poly(caffeic acid) thin film was deposited on the surface of a glassy carbon electrode by potentiostatic technique in an aqueous solution containing caffeic acid. The poly(caffeic acid)-modified electrode was used for the determination of ascorbic acid (AA), dopamine (DA), and their mixture by cyclic voltammetry. This modified electrode exhibited a potent and persistent electron-mediating behavior followed by well-separated oxidation peaks toward AA and DA at a scan rate of 10 mV s−1 with a potential difference of 135 mV, which was large enough to determine AA and DA individually and simultaneously. The catalytic peak current obtained was linearly dependent on the AA and DA concentrations in the range of 2.0 × 10−5−1.2 × 10−3 and 1.0 × 10−6−4.0 × 10−5 mol L−1 in 0.15 mol L−1 phosphate buffer (pH 6.64). The detection limits for AA and DA were 9.0 × 10−6 and 4.0 × 10−7 mol L−1, respectively. The modified electrode shows good sensitivity, selectivity, and stability and has been applied to the determination of DA and AA in real samples with satisfactory results.  相似文献   

10.
 The construction of a plasticised PVC matrix-type promazinium cation-selective membrane electrode and its use in the potentiometric determination of promazine hydrochloride in pharmaceutical preparations are described. It is based on the use of the ion-associate species, formed by promazinium cation and tetraphenylborate (TPB) counter ion. The basic electrode performance characteristics are evaluated according to IUPAC recommendations. It exhibited a linear response for 1 × 10−2−1 × 10−5 M of promazine hydrochloride solutions with a cationic Nernstian slope over the pH range 2–6. Common organic and inorganic cations showed negligible interference. Direct potentiometric determination of 1 × 10−2−1 × 10−5 M aqueous promazine hydrochloride using this membrane electrode system showed an average recovery of 99.5% with a mean standard deviation of 1.5%. This electrode was successfully used for monitoring the titration of promazine hydrochloride with sodium tetraphenyl borate and for determining promazine hydrochloride in ampoules. Received June 15, 2001 Revision November 6, 2001  相似文献   

11.
The electrocatalytic oxidation of quinine sulfate (QS) was investigated at a glassy carbon electrode, modified by a gel containing multiwall carbon nanotubes (MWCNTs) and room-temperature ionic liquid of 1-Butyl-3-methylimidazolium hexafluorophate (BMIMPF6) in 0.10 M of phosphate buffer solution (PBS, pH 6.8). It was found that an irreversible anodic oxidation peak of QS with E pa as 0.99 V appeared at MWCNTs-RTIL/glassy carbon electrode (GCE). The electrode reaction process was a diffusion-controlled one and the electrochemical oxidation involved two electrons transferring and two protons participation. Furthermore, the charge-transfer coefficient (α), diffusion coefficient (D), and electrode reaction rate constant (k f) of QS were found to be 0.87, 7.89 × 10−3 cm2⋅s−1 and 3.43 × 10−2 s−1, respectively. Under optimized conditions, linear calibration curves were obtained over the QS concentration range 3.0 × 10−6 to 1.0 × 10−4 M by square wave voltammetry, and the detection limit was found to be 0.44 μM based on the signal-to-noise ratio of 3. In addition, the novel MWCNTs-RTIL/GCE was characterized by the electrochemical impedance spectroscopy and the proposed method has been successfully applied in the electrochemical quantitative determination of quinine content in commercial injection samples and the determination results could meet the requirement.  相似文献   

12.
Sensitive fluorescent probes for the determination of hydrogen peroxide and glucose were developed by immobilizing enzyme horseradish peroxidase (HRP) on Fe3O4/SiO2 magnetic core–shell nanoparticles in the presence of glutaraldehyde. Besides its excellent catalytic activity, the immobilized enzyme could be easily and completely recovered by a magnetic separation, and the recovered HRP-immobilized Fe3O4/SiO2 nanoparticles were able to be used repeatedly as catalysts without deactivation. The HRP-immobilized nanoparticles were able to activate hydrogen peroxide (H2O2), which oxidized non-fluorescent 3-(4-hydroxyphenyl)propionic acid to a fluorescent product with an emission maximum at 409 nm. Under optimized conditions, a linear calibration curve was obtained over the H2O2 concentrations ranging from 5.0 × 10−9 to 1.0 × 10−5 mol L−1, with a detection limit of 2.1 × 10−9 mol L−1. By simultaneously using glucose oxidase and HRP-immobilized Fe3O4/SiO2 nanoparticles, a sensitive and selective analytical method for the glucose detection was established. The fluorescence intensity of the product responded well linearly to glucose concentration in the range from 5.0 × 10−8 to 5.0 × 10−5 mol L−1 with a detection limit of 1.8 × 10−8 mol L−1. The proposed method was successfully applied for the determination of glucose in human serum sample.  相似文献   

13.
The potential application of ordered mesoporous carbon (OMC)-modified glassy carbon electrode (OMC/GCE) in electrochemistry as a novel electrode material was investigated. X-ray diffraction, transmission electron micrographs, and cyclic voltammetry were used to characterize the structure and electrochemical behaviors of this material. Compared to GC electrode, the peak currents of potassium ferricyanide (K3[Fe(CN)6]) increase and the peak potential separation (ΔE p) decreases at the OMC/GC electrode. These phenomena suggest that OMC-modified GC electrode possesses larger electrode area and faster electron transfer rate, as compared with bare GC electrode. Furthermore, riboflavin was detected using OMC/GC electrode in aqueous solutions. The results showed that, under an optimum condition (pH 7.0), the OMC/GC electrode exhibited excellent response performance to riboflavin in the concentration range of 4.0 × 10−7 to 1.0 × 10−6 M with a high sensitivity of 769 μA mM−1. The detection limit was down to around 2 × 10−8 M. With good stability and reproducibility, the present OMC/GC electrode was applied in the determination of vitamin B2 content in vitamin tablets, and satisfactory results were obtained.  相似文献   

14.
Jadwiga Opydo 《Mikrochimica acta》2001,137(3-4):157-162
 Necessary conditions were established for simultaneous nickel and cobalt determination in environmental samples, such as oak wood and soil, based on cathodic adsorptive stripping voltammetry. Ni(II) and Co(II), complexed with dimethylglyoxime, were determined using a hanging mercury drop electrode. Optimum conditions were found to be: accumulation time 90 s, accumulation potential −0.80 V vs. SCE, supporting electrolyte 0.2 mol dm−3 ammonia-ammonium chloride buffer (pH = 9.4) + 0.05 mol dm−3 NaNO2 and dimethylglyoxime 2 × 10−4 mol dm−3. A linear current-concentration relationship was observed up to 7.51×10 −7 mol dm−3 for Ni(II) and 7.0 × 10−7 mol dm−3 for Co(II). Excess amounts of zinc(II) interfering with cobalt peaks were masked by complexation with EDTA. Wood and soils were mineralized by applying a microwave digestion system, using the mixtures H2O2 + HNO3 or HNO3 + HF, respectively. The developed procedure was tested by analysing international reference materials (BCR 62 Olive Leaves and GBW 08302 Tibet Soil). The developed procedure was used to determine pollution of oak stand with nickel and cobalt in different regions of Poland. Received August 10, 2000. Revision May 22, 2001.  相似文献   

15.
 A PVC membrane electrode selective for cetyldimethylethylammonium (CDEA) ion was prepared. The active element is a plasticized poly vinyl chloride membrane containing a dissolved ion associate complex of CDEA with phosphotungstic acid (PTA). The electrode showed a near-Nernstian response within the CDEA+ concentration range 2.34 × 10−6 to 1.96 × 10−4 M at 25 ± 1^C, good selectivity, and is usable within the pH range 3.5–9.0. The isothermal temperature coefficient of the electrode amounted to −0.00012 V/°C. The electrode has been used for the direct determination of cetyldimethylethylammonium bromide either by the standard addition method or by potentiometric titration against PTA. Received January 1, 1998. Revision June 13, 2000.  相似文献   

16.
Copper (II) complex of 2,4-dimethyl-1,5,9,12-tetraazacyclopentadeca-1,4-diene, [Me2(15)dieneN4] was synthesized and used in the fabrication of Cu2+ – selective ISE membrane in PVC matrix. The membrane having Cu(II) macrocyclic complex as electroactive material along with sodium tetraphenyl borate (NaTPB) as anion discriminator. Dibutyl phthalate (DBP) as plasticizer in poly(vinyl chloride) (PVC) matrix was prepared for the determination of Cu2+. The best performance was observed by the membrane having Cu(II) complex–PVC–NaTPB–DBP with composition 1:5:1:3. The sensor worked well over a concentration range 1.12 × 10−6 M–1.0 × 10−1 M between pH 2.1–6.2 and a fast response time 10±2 s and a lifetime of 6 months. Their performance in partially non-aqueous medium was found satisfactory. Electrodes exhibited excellent selectivity for Cu2+ ion over other mono-, di-, trivalent cations. It can also be used as indicator electrode in the potentiometric titration of Cu2+ against EDTA as well as in the determination of Cu2+ in real samples.  相似文献   

17.
 A differential pulse voltammetric method for the determination of nitrate has been described, which is applicable to the analysis of natural water samples with nitrate levels greater than 2.8 × 10−6 M. A reduction peak for the nitrate ions at a freshly copper plated glassy carbon electrode was observed at about −0.50 V vs Ag ∣AgCl∣KClsatd electrode in a solution of 2.0 × 10−2 M Cu2+, 0.5 M H2SO4 and 1.0 × 10−3 M KCl and exploited for analytical purposes. The working linear range was established by regression analysis and found to extend from 2.8 ×10−6 M to 8.0 × 10−5 M. The proposed method was applied for the determination of nitrate in natural waters. The detection limit of the method was 2.8 × 10−6 M and the sensitivity was 0.9683 A·L/mol. The possible interferences by some ions such as phosphate, nitrite and some halides were determined and found to lead to shifts of the peak position and increasing the peak heights. Received March 15, 1999. Revision July 9, 1999.  相似文献   

18.
In the presence of carbonate and uranine, the chemiluminescent intensity from the reaction of luminol with hydrogen peroxide was dramatically enhanced in a basic medium. Based on this fact and coupled with the technique of flow-injection analysis, a highly sensitive method was developed for the determination of carbonate with a wide linear range. The method provided the determination of carbonate with a wide linear range of 1.0 × 10−10–5.0 × 10−6 mol L−1 and a low detection limit (S/N = 3) of carbonate of 1.2 × 10−11 mol L−1. The average relative standard deviation for 1.0 × 10−9–9.0 × 10−7 mol L−1 of carbonate was 3.7% (n = 11). Combined with the wet oxidation of potassium persulfate, the method was applied to the simultaneous determination of total inorganic carbon (TIC) and total organic carbon (TOC) in water. The linear ranges for TIC and TOC were 1.2 × 10−6–6.0 × 10−2 mg L−1 and 0.08–30 mg L−1 carbon, respectively. Recoveries of 97.4–106.4% for TIC and 96.0–98.5% for TOC were obtained by adding 5 or 50 mg L−1 of carbon to the water samples. The relative standard deviations (RSDs) were 2.6–4.8% for TIC and 4.6–6.6% for TOC (n = 5). The mechanism of the chemiluminescent reaction was also explored and a reasonable explanation about chemical energy transfer from luminol to uranine was proposed. Figure Chemiluminescence profiles in batch system. 1, Injection of 100 μL of K2CO3 into 1.0 mL luminol-1.0 mL H2O2 solution; 2-3 and 4-5, Injection in sequence of 100 μL of K2CO3 and 100 μL of uranine into 1.0 ml luminol-1.0 mL H2O2 solution; Cluminol = 1.0 × 10−7 mol/L, CH2O2 = 1.0 × 10−5 mol/L, Curanine = 1.0 × 10−5 mol/L, CK2CO3 = 1.0 × 10−7 mol/L except for 4-5 where CK2CO3 = 1.0 × 10−4 mol/L  相似文献   

19.
In this work, a highly-sensitive polymeric membrane ion selective electrode for determination of tetracycline was constructed by using molecularly imprinted polymer (MIP) particles as quasi-ionophore. The water-compatible MIP particles targeting tetracycline were synthesized with tetracycline as a template molecule, methacrylic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linker, 2,2′-azobisisobutyronitrile as an initiator and lanthanum ion as a mediator. Benefited from the distinctive performance of the quasi-ionophore and the optimized composition of the membrane and the inner filling solution, the lower detection limit of the electrode was decreased to about 1 × 10−8 mol/l. It exhibited a good electrode slope 59.8 mV/decade near the theoretical Nernstian one, with a wide linear working range from 2.0 × 10−8 to 1.0 × 10−3 mol/l. Due to the specific recognition of tetracycline by the MIP particles, the selectivity coefficients for routine interferences were less than 10−4. The fabricated electrode should be used in pH 2–4, response time of which was less than 200 s when the concentration of tetracycline was higher than 1.0 × 10−6 mol/l and no more than 30 min at the concentration of 1.0 × 10−8 mol/l. Finally, the proposed highly-sensitive ion selective electrode has been successfully applied to the determination of tetracycline in aqueous samples.  相似文献   

20.
A disposable screen-printed electrode was designed and evaluated for direct detection of chromium(VI) in batch and flow analysis. The carbon screen-printed electrode was modified with a graphite–epoxy composite. The optimal graphite–epoxy matrix contains 37.5% graphite powder, 12.5% diphenylcarbohydrazide, a selective compound for chromium(VI), and 50% epoxy resin. The principal analytical parameters of the potentiometric response in batch and flow analysis were optimized and calculated. The screen-printed sensor exhibits a response time of 20 ± 1 s. In flow analysis, the analytical frequency of sampling is 70 injections per hour using 0.1 M NaNO3 solution at pH 3 as the carrier, a flow rate of 2.5 mL·min−1, and an injection sample volume of 0.50 mL. The sensor shows potentiometric responses that are very selective for chromium(VI) ions and optimal detection limits in both static mode (2.1 × 10−7 M) and online analysis (9.4 × 10−7 M). The disposable potentiometric sensor was employed to determine toxicity levels of chromium(VI) in mineral, tap, and river waters by flow-injection potentiometry and batch potentiometry. Chromium(VI) determination was also carried out with successful results in leachates from municipal solid waste landfills.  相似文献   

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