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1.
Glassy carbon electrode modified with phosphotungstate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐PW) film was employed for iodate determination. The PLL‐GA‐PW film electrode shows excellent electrocatalytic activity towards iodate reduction with significant reduction of overpotential. Under optimized experimental conditions, a linear range from 5×10?8 to 2.27×10?2 M with a sensitivity of 61.75 μA mM?1 was obtained. Possible interfering species, in iodate determination, were evaluated and the applicability of proposed sensor for iodate estimation in table salt was also demonstrated. The PLL‐GA‐PW film electrode shows fast response, wider linear range, and good selectivity and stability.  相似文献   

2.
The present work describes reduction of iodate (IO3?), and periodate (IO4?) at silicomolybdate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐SiMo) film coated glassy carbon electrode in 0.1 M H2SO4. In our previous study, we were able to prepare the PLL‐GA‐SiMo film modified electrode by means of electrostatically trapping SiMo12O404? mediator in the cationic film of PLL‐GA, and the voltammetric investigation in pure supporting indicated that the charge transport through the film was fast. Here, the electrocatalytic activity of PLL‐GA‐SiMo film electrode towards iodate and periodate was tested and subsequently used for analytical determination of these analytes by amperometry. The two electron reduced species of SiMo12O404? anion was responsible for the electrocatalytic reduction of IO3? at PLL‐GA‐SiMo film electrode while two and six electron reduced species were showed electrocatalytic activity towards IO4? reduction. Under optimized experimental conditions of amperometry, the linear concentration range and sensitivity are 2.5×10?6 to 1.1×10?2 M and 18.47 μA mM?1 for iodate, and 5×10?6 to 1.43×10?4 M and 1014.7 μA mM?1 for periodate, respectively.  相似文献   

3.
Silicomolybdate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐SiMo) film modified glassy carbon electrode was successfully prepared by means of electrostatically trapping the silicomolybdate anion in PLL‐GA cationic coating. The PLL‐GA‐SiMo film was stable and the charge transport through the film was fast. The modified electrode shows excellent electrocatalytic activity towards bromate reduction with significant reduction of overpotential. In amperometric determination of bromate, the calibration plot was linear over the concentration range of 5×10?5 to 1.2×10?3 M with a sensitivity of 3.6 μA mM?1. Furthermore, PLL‐GA‐SiMo film electrode showed fast response and good stability.  相似文献   

4.
《Electroanalysis》2004,16(17):1401-1405
The immobilization of tris(2,2′‐bipyridyl)ruthenium(II), Ru(bpy)32+, at a glassy carbon electrode was achieved by entrapping the Ru(bpy)32+ in a vapor deposited titania sol‐gel membrane. The electrogenerated chemiluminescence (ECL) of the immobilized Ru(bpy)32+ was studied. The Ru(bpy)32+ modified electrode showed a fast ECL response to both oxalate and proline. The ECL intensity was linearly related to concentrations of oxalate and proline over the ranges from 20 to 700 μmol L?1 and 20 to 600 μmol L?1, respectively. The detection limits for oxalate and proline at 3σ were 5.0 μmol L?1 and 4.0 μmol L?1, respectively. This electrode possessed good precision and stability for oxalate and proline determinations. The electrogenerated chemiluminescence mechanism of proline system was discussed. This work provided a new way for the immobilization of Ru(bpy)32+ and the application of titania sol‐gel membrane in electrogenerated chemiluminescence.  相似文献   

5.
In this paper 1‐(2‐pyridylazo)‐2‐naphthol (PAN) and ionic liquid 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIMBF4) were mixed with graphite powder to get a modified carbon paste electrode (PAN‐IL‐CPE), which was further used for the sensitive determination of bismuth(III). By the co‐contribution of the formation of PAN‐Bi complex and the accumulation effect of IL, more bismuth(III) was electrodeposited on the surface of the PAN‐IL‐CPE. Then the reduced Bi was oxidized and detected by differential pulse anodic stripping voltammetry (DPASV) with the oxidation peak appeared at 0.17 V (vs. SCE). Under the optimal conditions the oxidation peak current was proportional to the bismuth(III) concentration in the range from 0.04 to 7.5 μmol L?1 with the detection limit as 3.9 nmol L?1. The proposed method was successfully applied to the stomach medicine sample detection with good recovery.  相似文献   

6.
This work reports the determination of 5 neonicotinoid pesticides (Clothianidin, Imidacloprid, Thiamethoxam, Nitenpyram and Dinotefuran) in water samples by cathodic differential pulse (DP) voltammetry at screen‐printed disposable sensors featuring a sputtered bismuth thick‐film working electrode, a Ag reference electrode and a carbon counter electrode. The performance of the bismuth thick‐film electrodes was compared to that of a home‐made bismuth thin‐film electrode and a bismuth‐bulk electrode. The electrodes were further characterized by electrochemical and optical techniques. The effect of the pH of the supporting electrolyte on the DP reduction currents of the 5 pesticides was studied. The limits of quantification (LOQs) in 4 water matrices (distilled water, tap water, mineral water and surface water) were in the range 0.76 to 2.10 mg L?1 but severe matrix effects were observed in the analysis of mineral and, especially, surface water samples. Using a solid‐phase extraction (SPE) procedure using Lichrolut EN cartridges and elution with methanol, the matrix effects were substantially reduced and the LOQs were in the range 9 to 17 µg L?1. The recoveries of surface water samples spiked with the 5 target neonicotinoids at two concentration levels (20 and 50 µg L?1) were in the range 89 to 109 % and the % relative standard deviations ranged from 4.3 to 7.2 %.  相似文献   

7.
A new kind of bismuth film modified electrode to sensitively detect trace metal ions based on incorporating highly conductive ionic liquids 1‐butyl‐3‐methyl‐imidazolium hexafluorophosphate (BMIMPF6) in solid matrices at glassy carbon (GC) was investigated. Poly(sodium 4‐styrenesulfonate) (PSS), silica, and Nafion were selected as the solid matrices. The electrochemical properties of the mixed films modified GC were evaluated. The electron transfer rate of Fe(CN)64?/Fe(CN)63? can be effectively improved at the PSS‐BMIMPF6 modified GC. The bismuth modified PSS‐BMIMPF6 composite film electrodes (GC/PSS‐BMIMPF6/BiFEs) displayed high mechanical stability and sensitive stripping voltammetric performances for the determination of trace metal cations. The GC/PSS‐BMIMPF6/BiFE exhibited well linear response to both Cd(II) and Pb(II) over a concentration range from 1.0 to 50 μg L?1. And the detection limits were 0.07 μg L?1 for Cd(II) and 0.09 μg L?1 for Pb(II) based on three times the standard deviation of the baseline with a preconcentration time of 120 s, respectively. Finally, the GC/PSS‐BMIMPF6/BiFEs were successfully applied to the determination of Cd(II) and Pb(II) in real sample, and the results of present method agreed well with those of atomic absorption spectroscopy.  相似文献   

8.
《Electroanalysis》2004,16(4):289-297
The polymer film of N,N‐dimethylaniline (DMA) is deposited on the electrochemically pretreated glassy carbon (GC) electrode by continuous electrooxidation of the monomer. This poly N,N‐dimethylaniline (PDMA) film‐coated electrode can be used as an amperometric sensor of ascorbic acid (AA). The polymer film (thickness (?): 0.3±0.02 μm) having positive charge in its backbone attracts the anionic species AA. Thus, the anodic peak potential (350 mV vs. Ag|AgCl|NaCl(sat)) for the oxidation of AA at the bare electrode is largely shifted to the negative value (150 mV) at this electrode. The PDMA film‐coated electrode is stable in acidic, alkaline and neutral media and can sense AA at different pH's. The diffusion coefficients of AA in solution (D) and in film (Ds) were estimated by rotating disk electrode voltammetry: D=(5.5±0.1)×10?6 cm2 s?1 and Ds=(6.3±0.2)×10?8, (6.0±0.2)×10?8 and (4.7±0.2)×10?8 cm2 s?1 for 0.5, 1.5 and 3.0 mM AA, respectively. A permeability of AA through the PDMA film was found to decrease with increasing the concentration of AA in the solution. In the chronoamperometry, the current response for the oxidation of AA at different times elapsed after potential‐step application is linearly increased with the increase in AA concentration in a wide range of its concentration from 25 μM to 1.65 mM. In the hydrodynamic amperometry, a successive addition of 10 μM AA caused the successive increase in current response with equal amplitude and the sensitivity was calculated as 0.178 μA cm?2 μM?1. So, the fouling of the electrode surface caused by the oxidized product of AA is markedly eliminated at this PDMA film‐coated electrode. A flow injection analysis based on the present electrode was performed to estimate the concentration of vitamin C in fruit juice.  相似文献   

9.
The application of protective overoxidized poly‐1‐naphtylamine membrane (ONAP) is demonstrated in combination with bismuth film microelectrode (ONAP‐BiFME) for anodic stripping voltammetric measurement of trace heavy metals in the presence of some selected surfactants. The ONAP membrane was electrochemically deposited on the surface of bare single carbon fiber microelectrode followed by the in situ or ex situ preparation of the bismuth film. The key operational parameters influencing the stripping performance of the ONAP‐BiFME were optimized and its electroanalytical performance was examined in the model solution containing Cd(II) and Pb(II) as test metal ions. The ONAP‐BiFME exhibited significantly enhanced stripping voltammetric response (approximately 70% for Cd(II) and 45% for Pb(II)) in comparison with unmodified BiFME in the absence of surfactants. In the presence of high concentrations, e.g., 20 mg L?1, of anionic or cationic surfactants, the stripping signal for, e.g., Cd(II) decreased for less than 6% at the ONAP‐BiFME, whereas at the unmodified BiFME the signal attenuated considerably (approximately 38%). Moreover, in the presence of 10 mg L?1 of nonionic surfactant Triton X‐100, the stripping signals at the bare BiFME were almost completely suppressed, whereas at the ONAP‐BiFME exhibited linear concentration behavior in the examined concentration range from 10 to 120 μg L?1, with the calculated limit of detection of 5.0 μg L?1 and 3.4 μg L?1 for Cd(II) and Pb(II), respectively in connection with 60 s accumulation time. The attractive behavior of ONAP‐modified BiFME expands the applicability of bismuth‐based electrodes for measurement of trace heavy metals in real environments, where the presence of more complex matrix can be expected.  相似文献   

10.
The direct electrochemistry of glucose oxidase (GOD) immobilized on the designed titanium carbide‐Au nanoparticles‐fullerene C60 composite film modified glassy carbon electrode (TiC‐AuNPs‐C60/GCE) and its biosensing for glucose were investigated. UV‐visible and Fourier‐transform infrared spectra of the resulting GOD/TiC‐AuNPs‐C60 composite film suggested that the immobilized GOD retained its original structure. The direct electron transfer behaviors of immobilized GOD at the GOD/TiC‐AuNPs‐C60/GCE were investigated by cyclic voltammetry in which a pair of well‐defined, quasi‐reversible redox peaks with the formal potential (E0′) of ‐0.484 V (vs. SCE) in phosphate buffer solution (0.05 M, pH 7.0) at the scan rate of 100 mV·s?1 were obtained. The proposed GOD modified electrode exhibited an excellent electrocatalytic activity to the reduction of glucose, and the currents of glucose reduction peak were linearly related to glucose concentration in a wider linearity range from 5.0 × 10?6 to 1.6 × 10?4 M with a correlation coefficient of 0.9965 and a detection limit of 2.0 × 10?6 M (S/N = 3). The sensitivity and the apparent Michaelis‐Menten constant (KMapp) were determined to be 149.3 μA·mM?1·cm?2 and 6.2 × 10?5 M, respectively. Thus, the protocol will have potential application in studying the electron transfer of enzyme and the design of novel electrochemical biosensors.  相似文献   

11.
《Electroanalysis》2004,16(9):736-740
A new enzyme‐based amperometric biosensor for hydrogen peroxide was developed relying on the efficient immobilization of horseradish peroxidase (HRP) to a nano‐scaled particulate gold (nano‐Au) film modified glassy carbon electrode (GC). The nano‐Au film was obtained by a chitosan film which was first formed on the surface of GC. The high affinity of chitosan for nano‐Au associated with its amino groups resulted in the formation of nano‐Au film on the surface of GC. The film formed served as an intermediator to retain high efficient and stable immobilization of the enzyme. H2O2 was detected using hydroquinone as an electron mediator to transfer electrons between the electrode and HRP. The HRP immobilized on nano‐Au film maintained excellent electrocatalytical activity to the reduction of H2O2. The experimental parameters such as the operating potential of the working electrode, mediator concentration and pH of background electrolyte were optimized for best analytical performance of amperometry. The linear range of detection for H2O2 is from 6.1×10?6 to 1.8×10?3 mol L?1 with a detection limit of 6.1 μmol L?1 based on signal/noise=3. The proposed HRP enzyme sensor has the features of high sensitivity (0.25 Almol?1cm?2), fast response time (t90%≤10 s) and a long‐term stability (>1 month). As an extension, glucose oxidase (GOD) was chemically bound to HRP‐modified electrode. A GOD/HRP bienzyme‐modified electrode formed in this way can be applied to the determination of glucose with satisfactory performance.  相似文献   

12.
The electrochemical reduction of three common insecticides such as cypermethrin (CYP), deltamethrin (DEL) and fenvalerate (FEN) was investigated at glassy carbon electrode (GCE), multiwalled carbon nanotubes modified GCE (MWCNT‐GCE), polyaniline (herein called as modifier M1) and polypyrrole (herein called as modifier M2) deposited MWCNT/GCE using cyclic voltammetry. Influences of pH, scan rate, and concentration were studied. The surface morphology of the modified film was characterized by scanning electron microscopy (SEM) and X‐ray diffraction analysis (XRD). A systematic study of the experimental parameters that affect differential pulse stripping voltammetry (DPSV) was carried out and the optimized experimental conditions were arrived at. The calibration plots were linear over the insecticide's concentration range 0.1–100 mg L?1 and 0.05–100 mg L?1 for all the three insecticides at MWCNT‐GCE and MWCNT(M1)‐GCE respectively. The MWCNT(M2)‐GCE performed well among the three electrode systems and the determination range obtained was 0.01–100 mg L?1 for CYP, DEL and FEN. The limit of detection (LOD) was 0.35 μg L?1, 0.9 μg L?1 and 0.1 μg L?1 for CYP, DEL and FEN respectively on MWCNT(M2)‐GCE modified system. Suitability of this method for the trace determination of insecticide in spiked soil sample was also determined.  相似文献   

13.
The present work describes oxidation of ascorbic acid (AA) at octacyanomolybdate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐Mo(CN) film modified glassy carbon electrode in 0.1 M H2SO4. The modified electrode has been successfully prepared by means of electrostatically trapping Mo(CN) mediator in the cationic film of glutaraldehyde‐cross‐linked poly‐L ‐lysine. The dependence of peak current of modified electrode in pure supporting indicates that the charge transfer in the film was a mixed process at low scan rates (5 to 200 mV s?1), and kinetically restrained at higher scan rates (200 to 1000 mV s?1). Cyclic voltammetry and rotating disk electrode (RDE) techniques are used to investigate the electrocatalytic oxidation of ascorbic acid and compared with its oxidation at bare and undoped PLL‐GA film coated electrodes. The rate constant of catalytic reaction k obtained from RDE analysis was found to be 9.5×105 cm3 mol?1 s?1. The analytical determination of ascorbic acid has been carried out using RDE technique over the physiological interest of ascorbic acid concentrations with a sensitivity of 75 μA mM?1. Amperometric estimation of AA in stirred solution shows a sensitivity of 15 μA mM?1 over the linear concentration range between 50 and 1200 μM. Interestingly, PLL‐GA‐Mo(CN) modified electrode facilitated the oxidation of ascorbic acid but not responded to other electroactive biomolecules such as dopamine, uric acid, NADH, glucose. This unique feature of PLL‐GA‐Mo(CN) modified electrode allowed for the development of a highly selective method for the determination of ascorbic acid in the presence of interferents.  相似文献   

14.
Voltammetric studies of rabbit liver metallothioneins (MTs, containing both Zn and Cd ions) and Zn7‐MT were carried out at Nafion‐coated mercury film electrodes (NCMFEs). The accumulation of MT molecules into the NCMFEs enhances the voltammetric signals and the electrostatic interaction between the Nafion membrane and MT facilitates facile electron transfer reactions. Two well‐defined redox waves, with reduction potential (Epc) values at ?0.740 and ?1.173 V, respectively, were observed. The peak at Epc =?0.740 V is attributable to the reduction of the Cd‐MT complex, whereas that at Epc=?1.173 V was assigned to the reduction of the Zn‐MT complex. Zn7‐MT exhibits only one redox wave with Epc=?1.198 V. The NCMFE was found to be more advantageous than thin mercury film electrode (MFE), because the pristine metal ions in MTs (e.g., Cd2+ and/or Zn2+) are not significantly replaced by Hg2+. The NCMFE is also complementary to Nafion‐coated bismuth film electrode in that it has a greater hydrogen overpotential, which allows the reduction of the Zn‐MT complex to be clearly observed. Moreover, intermetallic compound formation between Cd and Zn appears to be less serious at NCMFEs. Consequently, the amounts of Cd and Zn deposited into the electrode upon the reduction reactions can be quantified more accurately.  相似文献   

15.
The present work describes preparation of hemoglobin‐incorporated multiwalled carbon nanotubes‐poly‐L ‐lysine (MWCNT‐PLL)/Hb) composite modified electrode film modified glassy carbon electrode (GCE) and its electrocatalytic behavior towards reduction of bromate ( ) in 0.1 M acetate buffer (pH 5.6). The modified electrode has been successfully fabricated by immobilizing hemoglobin on MWCNT dispersed in poly‐L ‐lysine. The surface morphologies of MWCNT, PLL and Hb were characterized using atomic force microscopy (AFM). The voltammetric features suggested that the charge transport through the film was fast and the electrochemical behavior resembles that of surface‐confined redox species. Cyclic voltammetry was used to investigate the electrocatalytic behavior of the modified electrode towards bromate and was compared with that of the CNT‐modified as well as bare electrode. The analytical determination of bromate has been carried out in stirred solution at an optimized potential with a sensitivity of 7.56 μA mM?1 and the calibration curve was linear between 1.5×0?5 to 6.0×0?3 M.  相似文献   

16.
A surface‐renewable tris(1, 10‐phenanthroline‐5, 6‐dione) iron (D) hexafluorophosphate (FePD) modified carbon ceramic electrode was constructed by dispersing FePD and graphite powder in methyltrimethoxysilane (MTMOS) based gels. The FePD‐modified electrode presented pH‐dependent voltammetric behavior, and its peak currents were diffusion‐controlled in 0.1 mol/L Na2SO4 + H2SO4 solution (pH = 0.4). In the presence of iodate, dear electrocatalytic reduction waves were observed and thus the chemically modified electrode was used as an amperometric sensor for iodate in common salt. The linear range, sensitivity, detection limit and response time of the iodate sensor were 5 × 10?6–1 × 10?2 mol/L, 7.448 μA·L/ mmol, 1.2 × 10?6 mol/L and 5 s, respectively. A distinct advantage of this sensor is its good reproducibility of surface‐renewal by simple mechanical polishing.  相似文献   

17.
《Electroanalysis》2004,16(23):1992-1998
A carbon nanotubes‐based amperometric cholesterol biosensor has been fabricated through layer‐by‐layer (LBL) deposition of a cationic polyelectrolyte (PDDA, poly(diallyldimethylammonium chloride)) and cholesterol oxidase (ChOx) on multi‐walled carbon nanotubes (MWNTs)‐modified gold electrode, followed by electrochemical generation of a nonconducting poly(o‐phenylenediamine) (PPD) film as the protective coating. Electrochemical impedance measurements have shown that PDDA/ChOx multilayer film could be formed uniformly on MWNTs‐modified gold electrode. Due to the strong electrocatalytic properties of MWNTs toward H2O2 and the low permeability of PPD film for electroacitve species, such as ascorbic acid, uric acid and acetaminophen, the biosensor has shown high sensitivity and good anti‐interferent ability in the detection of cholesterol. The effect of the pH value of the detection solution on the response of the biosensor was also investigated. A linear range up to 6.0 mM has been observed for the biosensor with a detection limit of 0.2 mM. The apparent Michaelis‐Menten constant and the maximum response current density were calculated to be 7.17 mM and 7.32 μA cm?2, respectively.  相似文献   

18.
《Electroanalysis》2005,17(24):2217-2223
Glassy carbon electrode modified by microcrystals of fullerene‐C60 mediates the voltammetric determination of uric acid (UA) in the presence of ascorbic acid (AA). Interference of AA was overcome owing to the ability of pretreated fullerene‐C60‐modified glassy carbon electrode. Based on its strong catalytic function towards the oxidation of UA and AA, the overlapping voltammetric response of uric acid and ascorbic acid is resolved into two well‐defined voltammetric peaks with lowered oxidation potential and enhanced oxidation currents under conditions of both linear sweep voltammetry (LSV) and Osteryoung square‐wave voltammetry (OSWV). At pH 7.2, a linear calibration graph is obtained for UA in linear sweep voltammetry over the range from 0.5 μM to 700 μM with a correlation coefficient of 0.9904 and a sensitivity of 0.0215 μA μM?1 . The detection limit (3σ) is 0.2 μM for standard solution. AA in less than four fold excess does not interfere. The sensitivity and detection limit in OSWV were found as 0.0255 μA μM?1 and 0.12 μM, for standard solution respectively. The presence of physiologically common interferents (i.e. adenine, hypoxanthine and xanthine) negligibly affects the response of UA. The fullerene‐C60‐modified electrode exhibited a stable, selective and sensitive response to uric acid in the presence of interferents.  相似文献   

19.
易清风  黄武  于文强  李磊  刘小平 《中国化学》2008,26(8):1367-1372
利用电热法,一步制备出新型的钛基Ni-Sn/Ti电极(Ni8Sn/Ti, Ni7Sn3/Ti 和 Ni/Ti)。扫描电镜(SEM)图像表明,催化剂以片状的纳米颗粒形式沉积于钛基体上。利用电化学伏安技术、电位阶跃法和电化学交流阻抗谱(EIS),研究了这些电极在1mol.L�1NaOH溶液中对甲醇氧化反应的电催化活性。研究表明,与Ni7Sn3/Ti,Ni/Ti以及多晶镍电极相比,Ni8Sn/Ti电极对甲醇氧化反应表现出更高的阳极氧化电流和更低的起始电位。EIS分析表明,在本文所考察的阳极电位和甲醇浓度下,Ni8Sn/Ti电极对甲醇氧化反应显示出极低的电荷传递电阻。结果表明,这种新型的钛基Ni8Sn/Ti电极对甲醇氧化反应具有极高的电催化活性。  相似文献   

20.
Single‐wall carbon nanotubes (SWCNTs) were used as an immobilization matrix to incorporate [Ir(ppy)2(phen‐dione)](PF6) complex onto a glassy carbon electrode for the study of electrocatalytic reduction of periodate ion. Detailed preliminary electrochemical data for the Ir(III)‐complex in acetonitrile solution and for the modified GCE/SWCNTs/[Ir(ppy)2(phen‐dione)](PF6)/CGE are presented. The modified electrode was applied to selective amperometric detection of periodate through its electrocatalytic reduction to iodide at 0.200 V and pH 2.0. The use of amperometry resulted in two calibration plots over the concentration ranges of 1‐20 μM and 20‐450 μM, with a detection limit of 0.6 μM and sensitivity of 198 nA μM?1.  相似文献   

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