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1.
《Electroanalysis》2005,17(23):2129-2136
The investigation of the dissolved iron(III)–nitrilotriacetate–hydroxide system in the water solution (I=0.1 mol L?1 in NaClO4; pH 8.0±0.1) using differential pulse cathodic voltammetry, cyclic voltammetry, and sampled direct current (DC) polarography, was carried out on a static mercury drop electrode (SMDE). The dissolved iron(III) ion concentrations varied from 2.68×10?6 to 6×10?4 mol L?1 and nitrilotriacetate concentrations were 1×10?4 and 5×10?4 mol L?1. By deconvoluting of the overlapped reduction voltammetric peaks using Fourier transformation, four relatively stable, dissolved iron(III) complex species were characterized, as follows: [Fe(NTA)2]3?, mixed ligand complexes [FeOHNTA]? and [Fe(OH)2NTA]2?, showing a one‐electron quasireversible reduction, and binuclear diiron(III) complex [NTAFeOFeNTA]2?, detected above 4×10?4 mol L?1 of the added iron(III) ions, showing a one‐electron irreversible reduction character. The calculations with the constants from the literature were done and compared with the potential shifts of the voltammetric peaks. Fitting was obtained by changing the following literature constants: log β2([Fe(NTA)2]3?) from 24 to 27.2, log β1([FeNTA]?) from 8.9 to 9.2, log β2([Fe(NTA)2]4?) from 11.89 to 15.7 and log β2([Fe(OH)2NTA]3?) from 15.63 to 19. The determination of the electrochemical parameters of the mixed ligand complex [FeOHNTA]?, such as: transfer coefficient (α), rate constant (ks) and formal potential (E°') was done using a sampled DC polarography, and found to be 0.46±0.05, 1.0±0.3×10?3 cm s?1, and ?0.154±0.010 V, respectively. Although known previously in the literature, these four species have now for the first time been recorded simultaneously, i.e. proved to exist simultaneously under the given conditions.  相似文献   

2.
The article describes the use of a fullerene (C60)‐β‐cyclodextrin conjugate, synthesized via 1,3dipolar cycloaddition, for the ultrasensitive electrochemical detection of p‐nitrophenol. This conjugate was successfully immobilized on the surface of a glassy carbon electrode and the developed device showed high activity towards p‐nitrophenol due to the synergetic effect of C60, the latter becoming highly conductive upon reduction. The determination of p‐nitrophenol was performed by using square wave voltammetry over a concentration range from 2.8×10?9 mol L?1 to 4.2×10?7 mol L?1 and the detection limit was calculated to be 1.2×10?9 mol L?1.  相似文献   

3.
A glassy carbon electrode coated the film of 4‐tert‐butyl‐1‐(ethoxycarbonylmethoxy)thiacalix[4]arene is designed for the determination of trace amounts of Hg2+. Compared with bare glassy carbon electrode, the modified electrode can improve the measuring sensitivity of Hg2+. Under the optimum experimental condition, the modified electrode in 0.1 mol L?1 H2SO4 + 0.01 mol L?1 KCl solution shows a linear voltammetric response in the range of 8.0 × 10?9 ~ 3.0 × 10?6 mol L?1 with detection limit 5.0 × 10?9 mol L?1 for Hg2+. The high sensitivity, selectivity, and stability of modified electrode also prove its practical application for a simple, rapid and economical determination of Hg2+ in water samples.  相似文献   

4.
A simple and sensitive differential pulse stripping voltammetric method was developed for the determination of antimony(III) using a selenium-doped carbon paste electrode modified with an ionic liquid, graphene, and gold nanoparticles. The conditions, including the mass of graphene, concentration of hydrochloric acid, deposition potential, and deposition time were optimized by single-factor experiments. Under the optimal conditions, a linear equation of ISb(III) (µA)?=??16.9882???11.0929 c (µmol/L) (R?=?0.9965) and a detection limit of 2.7?×?10?8?mol/L were obtained for 8.0?×?10?8 to 4.8?×?10?6?mol/L antimony(III). The response shows that the sensor enhances the sensitivity of antimony due to the high conductivity and large surface areas of the ionic liquid, graphene, and gold nanoparticles. This electrode may provide a new sensing platform for the determination of antimony.  相似文献   

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

6.
A new ion selective electrode for salicylate based on N,N'-(aminoethyl)ethylenediamide bis(2-salicylideneimine) binuclear copper(Ⅱ) complex [Cu(Ⅱ)2-AEBS] as an ionophore was developed. The electrode has a linear range from 1.0 × 10^-1 to 5.0 ×10^-7 mol·L^- 1 with a near-Nemstian slope of ( - 55 ±1 ) mV/decade and a detection limit of 2.0 × 10-7 mol·L^-1 in phosphorate buffer solution of pH 5.0 at 25 ℃. It shows good selectivity for Sal^- and displays anti-Hofmeister selectivity sequence: Sal^-〉SCN^-〉 ClO4^- 〉I^-〉 NO2^- 〉Br^-〉 NO3^- 〉Cl^-〉 SO3^2- 〉 SO4^2- The proposed sensor based on binuclear copper(Ⅱ)complex has a fast response time of 5-10 s and can be used for at least 2 months without any major deviation. The response mechanism is discussed in view of the alternating current (AC) impedance technique and the UV-vis spectroscopy technique. The effect of the electrode membrane compositions and the experimental conditions were studied. The electrode has been successfully used for the determination of salicylate ion in drug pharmaceutical preparations.  相似文献   

7.
许文菊  袁若  柴雅琴 《中国化学》2009,27(1):99-104
本文以2,9,16,23-四硝基酞菁铜(II) (Cu(II)TNPc) 和2,9,16,23-四氨基酞菁铜(II) (Cu(II)TAPc) 为载体制备PVC聚合膜,构建了水杨酸根选择性电极,并探讨了该电极的选择性响应性能。研究了增塑剂的性质、载体的含量及阴、阳离子添加剂对电极电位响应的影响。结果表明,基于Cu(II)TNPc为载体的PVC膜电极对水杨酸根 (Sal-) 呈现出优先选择性电位响应。具有最佳电位响应的电极的膜组成是:(w/w) 3.0% Cu(II)TNPc,67.0% o-NPOE,29.5% PVC和0.5% NaTPB。基于该组成的电极的线性响应范围为1.0×10-1-9.0×10-7 mol·L-1,检测下限为7.2×10-7 mol·L-1,斜率为-59.8±0.5 mV/decade;其响应快速,稳定性好,适宜的pH范围是3.0-7.0。并成功运用于了实际样品中水杨酸含量的测定,获得令人满意的结果。  相似文献   

8.
唐明宇袁若  柴雅琴 《中国化学》2006,24(11):1575-1580
The third generation amperometric biosensor for the determination of hydrogen peroxide (H2O2) has been described. For the fabrication of biosensor, o-aminobenzoic acid (oABA) was first electropolymerized on the surface of platinum (Pt) electrode as an electrostatic repulsion layer to reject interferences. Horseradish peroxidase (HRP) absorbed by nano-scaled particulate gold (nano-Au) was immobilized on the electrode modified with polymerized o-aminobenzoic acid (poABA) with L-cysteine as a linker to prepare a biosensor for the detection of H2O2. Amperometric detection of H2O2 was realized at a potential of +20 mV versus SCE. The resulting biosensor exhibited fast response, excellent reproducibility and sensibility, expanded linear range and low interferences. Temperature and pH dependence and stability of the sensor were investigated. The optimal sensor gave a linear response in the range of 2.99×10^-6 to 3.55×10^-3 mol·L^-1 to H2O2 with a sensibility of 0.0177 A·L^-1·mol^-1 and a detection limit (S/N = 3) of 4.3×10^-7 mol·L^-1. The biosensor demonstrated a 95% response within less than 10 s.  相似文献   

9.
《Electroanalysis》2005,17(21):1945-1951
Tin(IV) porphyrins derivatives were used as ionophores for phthalate selective electrodes preparation. The influence of ionophore structure and membrane composition (amount of incorporated ionic sites) on the electrode response, selectivity and long‐term stability were studied. Poly(vinyl chloride) polymeric membranes plasticized with o‐NPOE (o‐nitrophenyloctylether) and containing Sn(IV)‐tetraphenylporphyrin (TPP) dichloride (Sn(IV)[TPP]Cl2) or Sn(IV)‐octaethylporphyrin (OEP) dichloride (Sn(IV)[OEP]Cl2), and in some cases incorporating lipophilic cationic (tetraocthylammonium bromide ‐ TOABr) and anionic (sodium tetraphenylborate – NaTPB and potassium tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate‐KTFPB) additives, were prepared and their potentiometric characteristics compared. Both ionophores are shown to operate via a neutral mechanism, and the addition of 10 mol % of lipophilic quaternary ammonium salt derivative to the membrane is required to achieve optimal electrode performance. The potentiometric units prepared, with Sn(IV)[TPP]Cl2 (Type A) or Sn(IV)[OEP]Cl2 (Type B) without additives, presented a slope of ?52.8 mV dec?1 and ?58.8 mV dec?1 and LLLR of 9.9×10?5 mol L?1 and 9.9×10?6 mol L?1, respectively. The units prepared using the same metalloporphyrins and incorporating 10% mol TOABr presented a slope of ?55.0 mV dec?1 and ?57.8 mV dec?1 and LLLR of 5.0×10?7 mol L?1 and 3.0×10?7 mol L?1. Their analytical usefulness was assessed by potentiometric determinations of phthalate in water and industrial products providing results that presented recoveries of about 100%.  相似文献   

10.
A new electrochemical method was proposed for the determination of adenosine‐5′‐triphosphate (ATP) based on the electrooxidation at a molecular wire (MW) modified carbon paste electrode (CPE), which was fabricated with diphenylacetylene (DPA) as the binder. A single well‐defined irreversible oxidation peak of ATP appeared on MW‐CPE with adsorption‐controlled process and enhanced electrochemical response in a pH 3.0 Britton‐Robinson buffer solution, which was due to the presence of high conductive DPA in the electrode. The electrochemical parameters of ATP were calculated with the electron transfer coefficient (α) as 0.54, the electron transfer number (n) as 1.9, the apparent heterogeneous electron transfer rate constant (ks) as 2.67 × 10?5 s?1 and the surface coverage (ΓT) as 4.15 × 10?10 mol cm?2. Under the selected conditions the oxidation peak current was proportional to ATP concentration in the range from 1.0 × 10?7 mol L?1 to 2.0 × 10?3 mol L?1 with the detection limit as 1.28 × 10?8 mol L?1 (3σ) by sensitive differential pulse voltammetry. The proposed method showed good selectivity without the interferences of coexisting substances and was successful applied to the ATP injection samples detection.  相似文献   

11.
A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with single‐walled carbon nanotubes (SWCNTs) and polyoxometalate. With immersing SWCNTs modified GC electrode in silicon polyoxomolybdate (α‐SiMo12O404?) solution (direct deposition) for a short period of time (2–10 s) oxoanion adsorbed strongly and irreversibly on SWCNTs. Cyclic voltammograms of the α‐SiMo12O404? incorporated‐SWCNTs indicates three well‐defined and reversible redox couples with surface confined characteristic at wide pH range (1–7). The surface coverage (Γ) of α‐SiMo12O404? immobilized on SWCNTs was 2.14 (±0.11)×10?9 mol cm?2 indicating high loading ability of SWCNTs for polyoxometalate. The charge transfer rate constant (ks) of three redox couples of adsorbed α‐SiMo12O404? were 9.20 (±0.20), 8.02 (±0.20), and 3.70 (±0.10) s?1, respectively, indicate great facilitation of the electron transfer between α‐SiMo12O404? and CNTs. In this research the attractive mechanical and electrical characteristics of CNTs and unique properties and reactivity of polyoxometalates were combined. The modified electrode in buffer solution containing Sb(III) shows a new redox system at 0.38 V in pH 1. The voltammetric peak current increased with increasing Sb(III) concentration. The differential pulse voltammetry (DPV) technique was used for detection micromolar concentration of antimony. Furthermore, the interference effects various electroactive compounds on voltammetric response of Sb(III) were negligible. Finally the ability of the modified electrode for antimony detection in real samples was evaluated.  相似文献   

12.
A facile, rapid and ultra‐sensitive method for the determination of vitamin B12 (cyanocobalamin) at the sub‐nanomolar concentration range by using low‐cost, disposable graphite screen‐printed electrodes is described. The method is based on the cathodic preconcentration of square planar vitamin B12s, as occurred due to the electro reduction of Co(III) center in vitamin B12a to Co(I), at ?1.3 V versus Ag/AgCl/3 M KCl for 40 s. Then, an anodic square wave scan was applied and the height of the peak appeared at ca. ?0.73 V versus Ag/AgCl/3 M KCl, due to the oxidation of Co(I) to Co(II) in the adsorbed molecule, was related to the concentration of the vitamin B12 in the sample. EDTA was found to serve as a key‐component of the electrolyte by eliminating the background signal caused by metal cations impurities contained in the electrolyte (0.1 M phosphate buffer in 0.1 M KCl, pH 3). It also blocks trace metals contained in real samples, thus eliminating their interference effect. The method was optimized to various working parameters and under the selected conditions the calibration curve was linear over the range 1×10?10–8×10?9 mol L?1 vitamin B12 (R2=0.994), while the limit of detection for a signal‐to‐noise ratio of 3 (7×10?11 mol L?1 vitamin B12) is the lowest value of any reported in the literature for the electrochemical determination of vitamin B12. The sensors were successfully applied to the determination of vitamin B12 in pharmaceutical products.  相似文献   

13.
The voltammetric behavior of 3‐nitrofluoranthene and 3‐aminofluoranthene was investigated in mixed methanol‐water solutions by differential pulse voltammetry (DPV) at boron doped diamond thin‐film electrode (BDDE). Optimum conditions have been found for determination of 3‐nitrofluoranthene in the concentration range of 2×10?8–1×10?6 mol L?1, and for determination 3‐aminofluorathnene in the concentration range of 2×10?7–1×10?5 mol L?1, respectively. Limits of determination were 3×10?8 mol L?1 (3‐nitrofluoranthene) and 2×10?7 mol L?1 (3‐aminofluoranthene).  相似文献   

14.
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   

15.
When the concentration of dodecyl benzene sulfonic acid sodium salt (SDBS) is 0.7 mmol·L?1, the electrochemical and electrochemiluminescence (ECL) intensity of Ru(bpy)32+‐chlorpheniramine maleate (CPM) system at the Au electrode were studied. The results showed that compared with the absence of SDBS, enhancement of the ECL intensity was 14‐fold at Au electrode. Base on this, an ECL method was established for efficient and simple determination of CPM at Au electrode. Under the optimum experimental condition, the enhanced ECL intensities had good linear relationship with the concentration of CPM in the range of 1.0×10?4–1.0×10?7 mol·L?1, and a linear regression equation was obtained as follows: I (counts)=48.805×106c+394.03 (r=0.9975), the detection limit for CPM was 1.4×10?8 mol·L?1. The RSD for 5 times determinations of 1.0×10?5 mol·L?1 CPM was 3.2%. The results of recovery test were between 96.3%–102.5%, and the RSD of recovery test (n=5) was 2.7%. In addition, eleven kinds of tertiary amines‐Ru(bpy)32+ systems were investigated in the absence and presence of SDBS. The results showed that the enhancement of SDBS on ECL intensity of tertiary amines‐Ru(bpy)32+ systems was universal.  相似文献   

16.
An ionic liquid (IL) 1‐(3‐chloro‐2‐hydroxy‐propyl)‐3‐methylimidazolium trifluoroacetate was used as the modifier for the preparation of the modified carbon paste electrode (CPE). The IL‐CPE showed excellent electrocatalytic activity towards the oxidation of guanosine‐5′‐triphosphate (5′‐GTP) in a pH 5.0 Britton‐Robinson buffer solution. Due to the presence of high conductive IL on the electrode surface, the electrooxidation of 5′‐GTP was greatly promoted with a single well‐defined irreversible oxidation peak appeared. The electrode reaction was an adsorption‐controlled process and the electrochemical parameters of 5′‐GTP on IL‐CPE were calculated with the electron transfer coefficient (α) as 0.44, the electron transfer number (n) as 1.99, the apparent heterogeneous electron transfer rate constant (ks) as 2.21 × 10?9 s?1 and the surface coverage (ΓT) as 1.53 × 10?10 mol cm?2. Under the selected conditions a linear calibration curve between the oxidation peak currents and 5′‐GTP concentration was obtained in the range from 2.0 to 1000.0 μmol L?1 with the detection limit as 0.049 μmol L?1 (3σ) by differential pulse voltammetry. The proposed method showed good selectivity to the 5‘‐GTP detection without the interferences of coexisting substances and the practical application was checked by measurements of the artificial samples.  相似文献   

17.
A biomimetic sensor containing the oxo‐bridged dinuclear manganese‐phenanthroline complex incorporated into a cation‐exchange polymeric film deposited onto glassy carbon electrode for detection of sulfite was studied. Cyclic voltammetry at the modified electrode in universal buffer showed a two electron oxidation/reduction of the couple MnIV(μ‐O)2MnIV/MnIII(μ‐O)2MnIII. The sensor exhibited electrocatalytic property toward sulfite oxidation with a decrease of the overpotential of 450 mV compared with the glassy carbon electrode. A plot of the anodic current versus the sulfite concentration for potential fixed (+0.15 V vs. SCE) at the sensor was linear in the 4.99×10?7 to 2.49×10?6 mol L?1 concentration range and the concentration limit was 1.33×10?7 mol L?1. The mediated mechanism was derived by Michaelis? Menten kinetics. The calculated kinetics values were Michaelis? Menten rate constant= =1.33 µmol L?1, catalytic rate constant=6.06×10?3 s?1 and heterogeneous electro‐chemical rate constant=3.61×10?5 cm s?1.  相似文献   

18.
《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   

19.
《Electroanalysis》2006,18(15):1457-1462
This work describes an electroanalytical method for determining gold(I) thiomalate, aurothiomalate, widely used for treatment of reumatoid arthiritis, using a screen‐printed carbon electrode (SPCE). Aurothiomalate (AuTM) was determined indirectly at the same electrode by accumulating it first at ?1.5 V vs. printed carbon. At this potential in the adsorbed state, the AuTM is reduced to Au(0), which is then oxidized at two steps at ?0.22 V and +0.54 V on SPCE. Using optimized conditions of 60 s deposition time, ?1.5 V (vs. printed carbon) accumulation potential, 100 mV s?1 scan rate, linear calibration graphs can be obtained by monitoring the peak at +0.54 V for AuTM in HCl 0.1 mol L?1 from 1.43×10?6 to 1.55×10?4 mol L?1. A limit of detection obtained was 6.50×10?7 mol L?1, and the relative standard deviation from five measurements of 3.0×10?5 mol L?1 AuTM is 4.5%. The method was successfully applied for AuTM determination in human urine sample.  相似文献   

20.
In this study for the first time a novel erbium(III) voltammetric ion‐selective nanocomposite carbon‐paste electrode was introduced based on the concept of ion transfer at the interface between two immiscible electrolyte solutions. N′‐(2‐hydroxy‐1,2‐diphenylethylidene) benzohydrazide (HDB) was used as a selective ionophore in the composition of the carbon paste. The ionophore facilitates transfer of Er(III) from the aqueous solution to the room temperature ionic liquid (RTIL) phase after reduction of the redox probe to maintain charge neutrality. The plot of the peak potential versus the logarithm of the concentration exhibits a Nernstian response (19.9±0.2 mV decade?1) toward Er(III) in the range of 7.5×10?7–1.0×10?1 mol L?1 with detection limit of 5.0×10?7 mol L?1. The proposed sensor shows a fast response time of about 5 s.  相似文献   

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