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1.
A new solid state fluoride ion selective electrode composed of 70% Ag2S, 10% Cu2S and 20% CaF2 has been developed. An analytically useful potential change occurred, from 1 × 10−6 to 1 × 10−1 M fluoride ion. The slope of the linear portion (1 × 10−1-1 × 10−5 M) was about 26 ± 2 mV/10-fold concentration changes in fluoride. It was found that pH change between 1 and 8 had no effect on the potential of the electrode. There was no interference of most common cations such as K+, Na+, Ca2+ and Mg2+ and anions such as Cl, NO3, SO42− and PO43−. The lifetime of the electrode was more than 2 years, when used at least 4-5 times a day, and the response time was about 60 s.The measurements were made at constant ionic strength (0.1 M NaNO3) and at room temperature. This electrode has been used for the determination of fluoride ion in Ankara city tap water and in bottled spring water using standard addition method. The validation of the electrode has been made with a commercial fluoride ion selective electrode (Orion) and high consistency was obtained.  相似文献   

2.
Qu F  Shi A  Yang M  Jiang J  Shen G  Yu R 《Analytica chimica acta》2007,605(1):28-33
Prussian blue nanowire array (PBNWA) was prepared via electrochemical deposition with polycarbonate membrane template for effective modification of glassy carbon electrode. The PBNWA electrode thus obtained was demonstrated to have high-catalytic activity for the electrochemical reduction of hydrogen peroxide in neutral media. This enabled the PBNWA electrode to show rapid response to H2O2 at a low potential of −0.1 V over a wide range of concentrations from 1 × 10−7 M to 5 × 10−2 M with a high sensitivity of 183 μA mM−1 cm−2. Such a low-working potential also substantially improved the selectivity of the PBNWA electrode against most electroactive species such as ascorbic acid and uric acid in physiological media. A detection limit of 5 × 10−8 M was obtained using the PBNWA electrode for H2O2, which compared favorably with most electroanalysis procedures for H2O2. A biosensor toward glucose was then constructed with the PBNWA electrode as the basic electrode by crosslinking glucose oxidase (GOx). The glucose biosensor allowed rapid, selective and sensitive determination of glucose at −0.1 V. The amperometric response exhibited a linear correlation to glucose concentration through an expanded range from 2 × 10−6 M to 1 × 10−2 M, and the response time and detection limit were determined to be 3 s and 1 μM, respectively.  相似文献   

3.
Somer G  Sezer S  Doğan M  Kalaycı S  Sendil O 《Talanta》2011,85(3):1461-1465
A new borate ion selective electrode using solid salts of Ag3BO3, Ag2S and Cu2S has been developed. Detailed information is provided concerning the composition, working pH and conditioning of the electrode. An analytically useful potential change occurred from 1 × 10−6 to 1 × 10−1 M borate ion. The slope of the linear portion was 31 ± 2 mV/10-fold changes in borate concentration. The measurements were made at constant ionic strength (0.1 M NaNO3) and at room temperature. The effect of Cl, Br, NO3, SO=4, H2PO4 anions and K+, Na+, Cu2+, Ag+, Ca2+ cations on borate response is evaluated and it was found that only Ag+ had a small interference effect. The lifetime of the electrode was more than two years, when used at least 4-5 times a day, and the response time was about 20-30 s. Borate content in waste water of borax factory, tap water of a town situated near to the borax factory and city tap water far from these mines were also determined. The validation was made with differential pulse polarography for the same water sample, and high consistency was obtained.  相似文献   

4.
Pankaj Kumar 《Talanta》2010,82(4):1107-1112
An all-solid-state electrode, containing a synthesized chiral A2B2 macrocyclic compound namely (4R,5R,15R,16R)-4,5,15,16-tetraphenyl-3,6,14,17-tetraazatricyclo [13.3.1.18,12] tetracosa-1(23),8,10,12(24)19,21-hexaene-2,7,13,18-tetrone as an ionophore in polyvinyl chloride (PVC)/polyurethane (PU) membrane matrix, has been developed for the selective quantification of monohydrogen phosphate ions. The best performing membrane contained PVC, PU, ionophore, and nitrophenyl octyl ether as a plasticizer in the ratio 32.2:2.6:65.1 (w/w, %). It exhibited a near-Nernstian slope of 31.0 ± 1.0 mV/decade of activity for HPO42− ions in the concentration range of 1.0 × 10−6 to 1.0 × 10−2 M at pH 7.4. The detection limit of the electrode was 8.4 × 10−7 M and the life time was six weeks. The electrode displayed excellent selectivity for monohydrogen phosphate over other anions and the selectivity sequence was determined as HPO42− > SO42− > Ac > NO3 > ClO4 > Cl > I. The selective electrode for the monohydrogen phosphate ions was evaluated with a standard reference material (SRM 1548) and the titration of the sample solution.  相似文献   

5.
A novel bimediator amperometric sensor is fabricated for the first time by surface modification of graphite electrode with thionine (TH) and nickel hexacyanoferrate (NiHCF). The electrochemical behavior of the TH/NiHCF bimediator modified electrode was characterized by cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The TH/NiHCF bimediator modified electrode exhibited a pair of distinct redox peaks for NiHCF and TH with formal potentials of 0.33 V and −0.27 V vs. SCE at a scan rate of 50 mV s−1 in 0.1 M NaNO3 and 0.1 M NH4NO3 respectively. The electrocatalytic activity of the bimediator modified electrode towards oxidation of gallic acid with NiHCF and reduction of hydrogen peroxide with TH was evaluated and it was observed that the modified electrode showed an electrocatalytic activity towards the oxidation of gallic acid in the concentration range of 4.99 × 10−6–1.20 × 10−3 M with a detection limit of 1.66 × 10−6 M (S/N = 3) and reduction of H2O2 in the concentration range of 1.67 × 10−6–1.11 × 10−3 M with a detection limit of 5.57 × 10−7 M (S/N = 3). The bimediator modified electrode was found to exhibit good stability and reproducibility.  相似文献   

6.
For the first time, the analytical application of integrate ionophore-transducer material based on magnetic graphene hybrids and 2,2-dithiodipyridine (DTDP) in solid-contact lanthanum (III) selective electrode is reported. The attachment of Fe3O4 nanoparticles (NPs) to graphene oxide (GO) for magnetic graphene hybrid is achieved by covalent bonding, and the universal problem, Fe3O4 NPs may easily leach out from the graphene during application, is successfully solved by the method above. The proposed electrode exhibits an excellent near-Nernstian response to lanthanum (III) ranging from 1.0 × 10−9 to 1.0 × 10−3 M with a slope of 17.81 mV/dec. Moreover, the excellent performance on fairly good selectivity, wide applicable pH range (3.0_8.0), fast response time (10 s) and long life time (2 months) reveal the superiority of the electrode. Most importantly, we have made a great improvement in the detection limit (2.75 × 10−10 M), which brings new dawn to the real-time detection of lanthanum (III) using ion selective electrode.  相似文献   

7.
A simple procedure was developed to prepare a glassy carbon electrode modified with single-wall carbon nanotubes (SWCNTs) and Os(III)-complex. The glassy carbon (GC) electrode modified with CNTs was immersed into Os(III)-complex solution (direct deposition) for a short period of time (60 s). 1,4,8,12-Tetraazacyclotetradecane osmium(III) chloride, (Os(III)LCl2)·ClO4, irreversibly and strongly adsorbed on SWCNTs immobilized on the surface of GC electrode. Cyclic voltammograms of the Os(III)-complex-incorporated-SWCNTs indicate a pair of well defined and nearly reversible redox couple with surface confined characteristic at wide pH range (1-8). The surface coverage (Γ) and charge transfer rate constant (ks) of the immobilized Os-complex on SWCNTs were 3.07 × 10−9 mol cm−2, 5.5 (±0.2) s−1, 2.94 × 10−9 mol cm−2, 7.3 (±0.3) s−1 at buffer solution with pH 2 and 7, respectively, indicate high loading ability of SWCNTs for Os(III) complex and great facilitation of the electron transfer between electroactive redox center and carbon nanotubes immobilized on the electrode surface. Modified electrodes showed higher electrocatalytic activity toward reduction of BrO3, IO3 and IO4 in acidic solutions. The catalytic rate constants for catalytic reduction bromate, periodate and iodate were 3.79 (±0.2) × 103, 7.32 (±0.2) × 103 and 1.75 (±0.2) × 103 M−1 s −1, respectively. The hydrodynamic amperometry of rotating modified electrode at constant potential (0.3 V) was used for nanomolar detection of selected analytes. Excellent electrochemical reversibility of the redox couple, good reproducibility, high stability, low detection limit, long life time, fast amperometric response time, wide linear concentration range, technical simplicity and possibility of rapid preparation are great advantage of this sensor.  相似文献   

8.
Continuous-flow (CF) and flow-injection (FI) analysis using the fluoride ion-selective electrode (FISE) as detector have been investigated. The measurements were performed in a home-made cell under appropriate flow conditions (2.86 or 3.45 ml min−1, 0.2 ml samples, 10−6 M sodium fluoride). The calibration graph was obtained by plotting the signal height versus concentration of iron in the range of Fe(III) concentration from 10−5 to 10−1 M in acetate buffer (pH 2.8 or 3.4). In all described procedures, the range of linear response extends to the Fe(III) concentration from 1×10−3 to 1×10−1 M, with detection limit 9×10−5 M. The effect of double-line, two-line flow manifold and CF was investigated and discussed.  相似文献   

9.
A modified glassy carbon electrode was prepared by depositing a composite of polymer and mediator on a glassy carbon electrode (GCE). The mediator, flavin adenine dinucleotide (FAD) and the polymer, poly(3,4-ethylenedioxythiophene) (PEDOT) were electrochemically deposited as a composite on the GCE by applying cyclic voltammetry (CV). This modified electrode is hereafter designated as GCE/PEDOT/FAD. FAD was found to significantly enhance the growth of PEDOT. Electrochemical quartz crystal microbalance (EQCM) analysis was performed to study the mass changes in the electrode during the electrodeposition of PEDOT, with and without the addition of FAD. The optimal cycle number for preparing the modified electrode was determined to be 9, and the corresponding surface coverage of FAD (ΓFAD) was ca. 5.11 × 10−10 mol cm−2. The amperometric detection of iodate was performed in a 100 mM buffer solution (pH 1.5). The GCE/PEDOT/FAD showed a sensitivity of 0.78 μA μM−1 cm−2, a linear range of 4–140 μM, and a limit of detection of 0.16 μM for iodate. The interference effects of 250-fold Na+, Mg2+, Ca2+, Zn2+, Fe2+, Cl, NO3, I, SO42− and SO32−, with reference to the concentration of iodate were negligible. The long-term stability of GCE/PEDOT/FAD was also investigated. The GCE/PEDOT/FAD electrode retained 82% of its initial amperometric response to iodate after 7 days. The GCE/PEDOT/FAD was also applied to determine iodate in a commercial salt.  相似文献   

10.
A highly selective membrane electrode based on nickel(II)-1,4,8,11,15,18,22,25-octabutoxyphthalocyanine (NOBP) is presented. The proposed electrode shows very good selectivity for thiocyanate ions over a wide variety of common inorganic and organic anions. The sensor displays a near Nernstian slope of −58.7 ± 0.6 mV per decade. The working concentration range of the electrode is 1.0 × 10−6 to −1.0 × 10−1 M with a detection limit of 5.7 × 10−7 M (33.06 ng/mL). The response time of the sensor in whole concentration ranges is very short (<10 s). The response of the sensor is independent on the pH range of 4.3-9.8. The best performance was obtained with a membrane composition of 30% PVC, 65% dibutyl phthalate, 3% NOBP and 2% hexadecyltrimethylammonium bromide. It was successfully applied to direct determination of thiocyanate in biological samples, and as an indicator electrode for titration of thiocyanate ions with AgNO3 solution.  相似文献   

11.
This paper demonstrates the application of composite multi-walled carbon nanotube (MWNT) polyvinylchloride (MWNT-PVC) based on 1,5-diphenylcarbazide as chromium ionophore in potentiometric measurement. The sensor shows a good Nernstian slope of 19.52 ± 0.40 mV/decade in a wide linear range concentration of 6.3 × 10−8 to 1.0 × 10−2 M for Cr(NO3)3. The detection limit of this electrode was found to be 3.2 × 10−8 M of Cr(NO3)3 and is applicable in a pH range of 3.0-6.8. It has a short response time of about 10 s. This chromium electrode has a good selectivity over 16 various metal ions. The practical analytical utility of this electrode was demonstrated by measurement of Cr(III) in drinking water and mineral water samples without any serious preliminary pre-treatment and chromium in multivitamin.  相似文献   

12.
A chemically modified carbon paste electrode with 3,4-tetra pyridinoporphirazinatocobalt(II) (Co(3,4 tppa) was applied to the determination of free cyanide ion. The electrode has a linear range between 1.5 × 10−5 M and 1.0 × 10−2 M with a Nernstian slope of 60 ± 1.5 mV/decade and its detection limit is 9 × 10−6 M. The response time of electrode is 5 min. The proposed electrode was applied successfully for the determination of cyanide in commercially available spring water. Some anions, such as SCN, I, Cl, Br and oxalate that are usually serious interfering species for most of cyanide selective electrodes, did not have any interfering effect for this proposed electrode.  相似文献   

13.
A graphene, chitosan and Fe3O4 nanoparticles (nano-Fe3O4) modified glassy carbon electrode (graphene-chitosan/nano-Fe3O4/GCE) was fabricated. The modified electrode was characterized by scanning electron microscope and electrochemical impedance spectroscopy. The electrochemical oxidation behavior of guanosine was investigated in pH 7.0 phosphate buffer solution by cyclic voltammetry and differential pulse voltammetry. The experimental results indicated that the modified electrode exhibited an electrocatalytic and adsorptive activities towards the oxidation of guanosine. The transfer electron number (n), transfer proton number (m) and electrochemically effective surface area (A) were calculated. Under the optimized conditions, the oxidation peak current was proportional to guanosine concentration in the range of 2.0 × 10−6 to 3.5 × 10−4 mol L−1 with the correlation coefficient of 0.9939 and the detection limit of 7.5 × 10−7 mol L−1 (S/N = 3). Moreover, the modified electrode showed good ability to discriminate the electrochemical oxidation response of guanosine, guanine and adenosine. The proposed method was further applied to determine guanosine in spiked urine samples and traditional Chinese medicines with satisfactory results.  相似文献   

14.
Singh AK  Saxena P 《Talanta》2005,66(4):993-998
A new highly Tl(I)-selective PVC membrane electrode based on tetrathia macrocycle 6,7: 14,15-dibenzo-5,8,13,16-tetraoxo-1,4,9,12-tetrathiacyclohexadecane [Bz2O4(16)aneS4] (I) as membrane carrier, o-nitrophenyloctyl ether (o-NPOE) as solvent mediator and potassium tetrakis(p-chlorophenyl)borate (KTpClPB) as lipophilic additive has been developed. The best performance was given by the membrane of macrocycle (I) with composition 3:120:1.5:50 (I:o-NPOE:KTpClPB:PVC). This electrode exhibits a Nernstian response to Tl(I) ions in the concentration range 1.0 × 10−1-2.23 × 10−6 M with a slope of 58.2 mV/decade of concentration and a detection limit of 1.58 × 10−6 M. The response time of the sensor is 12 s and can be used over a period of 4 months with good reproducibility. The proposed electrode revealed good selectivity over a wide variety of other cations including alkali, alkaline earth, heavy and transition metals. The electrode works well over a pH range of 3.2-11.5 and in partially non-aqueous medium with up to 30% organic content. The sensor was also used as an indicator electrode in potentiometric titration of Tl(I) ions with KI solution.  相似文献   

15.
A simple procedure has been used for preparation of modified glassy carbon electrode with carbon nanotubes and copper complex. Copper complex [Cu(bpy)2]Br2 was immobilized onto glassy carbon (GC) electrode modified with silicomolybdate, α-SiMo12O404− and single walled carbon nanotubes (SWCNTs). Copper complex and silicomolybdate irreversibly and strongly adsorbed onto GC electrode modified with CNTs. Electrostatic interactions between polyoxometalates (POMs) anions and Cu-complex, cations mentioned as an effective method for fabrication of three-dimensional structures. The modified electrode shows three reversible redox couples for polyoxometalate and one redox couple for Cu-complex at wide range of pH values. The electrochemical behavior, stability and electron transfer kinetics of the adsorbed redox couples were investigated using cyclic voltammetry. Due to electrostatic interaction, copper complex immobilized onto GC/CNTs/α-SiMo12O404− electrode shows more stable voltammetric response compared to GC/CNTs/Cu-complex modified electrode. In comparison to GC/CNTs/Cu-complex the GC/CNTs/α-SiMo12O404− modified electrodes shows excellent electrocatalytic activity toward reduction H2O2 and BrO3 at more reduced overpotential. The catalytic rate constants for catalytic reduction hydrogen peroxide and bromate were 4.5(±0.2) × 103 M−1 s−1 and 3.0(±0.10) × 103 M−1 s−1, respectively. The hydrodynamic amperommetry technique at 0.08 V was used for detection of nanomolar concentration of hydrogen peroxide and bromate. Detection limit, sensitivity and linear concentration range proposed sensor for bromate and hydrogen peroxide detection were 1.1 nM and 6.7 nA nM−1, 10 nM-20 μM, 1 nM, 5.5 nA nM−1 and 10 nM-18 μM, respectively.  相似文献   

16.
Electrochemical behavior of cerium hexacyanoferrate (CeHCF) incorporated on multi-walled carbon nanotubes (MWNTs) modified GC electrode is investigated by scanning electron microscopy (SEM) and electrochemical techniques. The CeHCF/MWNT/GC electrode showed potent electrocatalytic activity toward the electrochemical oxidation of tryptophan in phosphate buffer solution (pH 7.0) with a diminution of the overpotential of 240 mV. The anodic peak currents increased linearly with the concentration of tryptophan in the range of 2.0 × 10−7 to 1.0 × 10−4 M with a detection limit of 2.0 × 10−8 M (at a S/N = 3). And the determination of tryptophan in pharmaceutical samples was satisfactory.  相似文献   

17.
In this contribution, a novel method is described for the determination of platinum metals. The procedure developed employs a carbon paste electrode modified in situ with cationic surfactants of the quaternary ammonium salt type. The pre-concentration step is based on a specific accumulation mechanism involving ion-pair formation; the detection being performed by cathodic scanning in the differential pulse voltammetric mode. Regarding the individual forms of platinum metals, the method has been found convenient for the determination of three heavy platinum metals in the form of Pt(IV), Ir(III) and Os(IV), whereas for the remaining elements (Ru, Rh, and Pd) was almost inapplicable. Platinum metals of the former group can be pre-concentrated in chloride-containing supporting media via PtCl62−, IrCl63− and OsCl62− complex anions, the central atom of each species being fairly reducible during the voltammetric scan. Stripping signals for both platinum and iridium were proportional to the concentration in a range of 1-10 × 10−6 M Pt(IV) and Ir(III); the response for osmium being linear within 0.1-6 × 10−7 M Os(IV) with a detection limit of about 5 × 10−9 mol l−1. During optimisation, special attention was paid to the accumulation mechanism, choice of key experimental conditions, and to interference effects from foreign ions with potentially ion-pairing capabilities (AuCl4, TlCl4, CrO42−, MnO4, SCN, and I). The method elaborated has been tested on both model solutions and real samples of industrial waste water, showing in both cases satisfactory analytical performance.  相似文献   

18.
?ükriye Ulubay 《Talanta》2010,80(3):1461-5138
Cu nanoparticles have been electrochemically incorporated polypyrrole film that was used for modification of the glassy carbon electrode surface. The performance of the electrode has been characterized by cyclic voltammetry and atomic force microscopy. The electrode has shown high electrocatalytic activity towards the oxidation of dopamine (DA) and uric acid (UA) simultaneously in a phosphate buffer solution (pH 7.00). The electrocatalytic oxidation currents of UA and DA were found linearly related to concentration over the range 1 × 10−9 to 1 × 10−5 M for UA and 1 × 10−9 to 1 × 10−7 M for DA using DPVs method. The detection limits were determined as 8 × 10−10 M (s/n = 3) for UA and 8.5 × 10−10 M (s/n = 3) for DA at a signal-to-noise ratio of 3.  相似文献   

19.
The preparation and electrochemical characterization of a carbon paste electrode modified with the N,N-ethylene-bis(salicylideneiminato)oxovanadium(IV) complex [VO(Salen)] as well as its behavior in relation to the oxidation of pyridoxine (Vitamin B6) are described. The electrochemical behavior of the modified electrode and the electrooxidation of pyridoxine were investigated using cyclic voltammetry. The best voltammetric response was obtained for an electrode composition of 15% (m/m) [VO(Salen)] in the paste, KCl solution of pH 5.5-8.0 and scan rate of 25 mV s−1. A sensitive linear voltammetric response for pyridoxine was obtained in the concentration range of 4.5×10−4 to 3.3×10−3 mol l−1 with a slope of 42.5 μA mmol−1 l, and a detection limit (3σ/slope) of 3.7×10−5 mol l−1 using linear sweep voltammetry. Among several compounds tested only Vitamin B1 seems to interfere in the analyte signal. The concentrations of pyridoxine in pharmaceutical formulations using the proposed electrode and an official spectrophotometric method based in the reaction with N,N-diethyl-p-phenylenediamine are in agreement at the 95% confidence level and within an acceptable range of error.  相似文献   

20.
A fullerene-C60-modified glassy carbon electrode (GCE) is used for the simultaneous determination of adenosine and guanosine by differential pulse voltammetry. Compared to a bare glassy carbon electrode, the modified electrode exhibits an apparent shift of the oxidation potentials in the cathodic direction and a marked enhancement in the voltammetric peak current response for both the biomolecules. Linear calibration curves are obtained over the concentration range 0.5 μM-1.0 mM in 0.1 M phosphate buffer solution at pH 7.2 with a detection limit of 3.02 × 10−7 M and 1.45 × 10−7 M for individual determination of adenosine and guanosine, respectively. The interference studies showed that the fullerene-C60-modified glassy carbon electrode exhibited excellent selectivity in the presence of hypoxanthine, xanthine, uric acid and ascorbic acid. The proposed procedure was successfully applied to detect adenosine and guanosine in human blood plasma and urine, without any preliminary pre-treatment.  相似文献   

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