延胡索乙素在碳纳米管修饰玻碳电极上的电化学检测

本文建立了延胡索乙素在碳纳米管修饰玻碳(CNT/GC)电极上的电化学检测方法。在pH6.20的Michaelis.缓冲液中,用方波伏安法研究了延胡索乙素在CNT/GC电极上的电化学行为。延胡索乙素在+0.90v(vs.Ag/AgCl)左右产生一个灵敏的阳极氧化峰,峰电流与延胡索乙素的浓度在8.0×10-7～5.0×10-5mol/L范围内呈良好线性关系,最低检测限达3.0×10-7mol/L。该法简单、快速、灵敏,可应用于生药材和中成药中延胡索乙素的测定。     

Modified carbon paste electrode for potentiometric determination of diquat dibromide pesticide in water and urine samples

A carbon paste electrode for diquat dibromide (Dq.2Br) was prepared and fully characterized in terms of composition, usable pH range, response time and temperature. The electrode was applied to the potentiometric determination of diquat ions in water and urine samples with average recoveries of 97.5-104.0% and relative standard deviations of 0.30-4.73%. The electrode is based on the ion pair, namely, diquat-phosphotungstate dissolved in 2-nitrophenyloctyl ether (2-NPOE) as pasting liquid with 1.0% Na-TPB as an additive. The modified electrode showed a near-Nernstian slope of 30.8 mV over the concentration range of 3.8 × 10^− 6to 1.0 × 10^− 3 M with the limit of detection 9.0 × 10^− 7 over the pH range 4.5-9.5. The electrode exhibits good selectivity for Dq cations with respect to a large number of inorganic cations, organic cations, sugars and amino acids. The proposed potentiometric method offers the advantages of simplicity, accuracy, automation feasibility and applicability to turbid and colored sample solutions.     

Electrochemical determination of cadmium(II) at platinum electrode modified with kaolin by square wave voltammetry

In this work, determination of cadmium(II) using square wave voltammetry (SWV) was described. The method is based on accumulation of these metal ions on kaolin platinum electrode (K/Pt). The K/Pt performance was optimized with respect to the surface modification and operating conditions. The optimized conditions were obtained in pH of 5.0 and accumulation time of 25 min. Under the optimal conditions, the relationship between the peak current versus concentration was linear over the range of 9 × 10⁻⁸ to 8.3 × 10⁻⁶ mol L⁻¹. The detection limit (DL, 3σ) was 5.4 × 10⁻⁹ mol L⁻¹. The analytical methodology was successfully applied to monitor the Cd(II) content in natural water. Interferences were also evaluated.     

MWCNT modified carbon paste electrode for sensitive determination of nicotine

ABSTRACT

A new sensor for the determination of nicotine is proposed based on the reduction of Cu(II)–nicotine complex at MWCNT modified carbon paste electrode. In borate buffer (pH 7.0) the reduction peak of Cu(II)–nicotine complex was observed at ? 0.05 V (versus Ag/AgCl). The increment of peak current obtained by deducting the reduction peak current of the Cu(II)–nicotine complex was rectilinear with nicotine concentration in the range of 0.05–30.0 n g mL^?1, with a detection limit of 0.01 ng/mL^?1. The method was applied for the sensitive quantification of nicotine in real samples with the satisfactory results.     

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated. The hydroxyapatite plays an important role in modern analytical electrochemistry due to their usefulness for the preparation of sensors giving rise to improved responses from metals. The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between -0.3 and -0.8V. Perchlorate acid solution (1.0molL(-1)) was employed as the supporting electrolyte. The voltammetric measurements were carried out using as working electrode HAp-CPE, and a platinum electrode and an SCE electrode as auxiliary and reference electrodes, respectively. Under the optimized working conditions, calibration graph is linear for 5min of preconcentration time with the detection limit 7.68x10(-10)molL(-1). This detection limit is remarkably lower than those reported previously using other modified electrodes or amperometric detection. The results indicate that this electrode is sensitive and effective for the determination of Pb2+.     

Determination of cyanide in wastewaters using modified glassy carbon electrode with immobilized silver hexacyanoferrate nanoparticles on multiwall carbon nanotube

The sensitive determination of cyanide in wastewaters using modified GC electrode with silver hexacyanoferrate nanoparticles (SHFNPs) immobilized on multiwall carbon nanotube (MWCNT) was reported. The immobilization of SHFNPs on MWCNT was confirmed by transmission electron microscopy (TEM). The TEM image showed that the SHFNPs retained the spherical morphology after immobilized on MWCNT. The size of SHFNPs was examined around 27 nm. The GC/MWCNT-SHFNPs was used for the determination of cyanide in borax buffer (BB) solution (pH 8.0). Using square wave voltammetry, the current response of cyanide increases linearly while increasing its concentration from 40.0 nM to 150.0 μM and a detection limit was found to be 8.3 nM (S/N=3). The present modified electrode was also successfully used for the determination of 5.0 μM cyanide in the presence of common contaminants at levels presenting in industrial wastewaters. The practical application of the present modified electrode was demonstrated by measuring the concentration of cyanide in industrial wastewater samples. Moreover, the studied sensor exhibited high sensitivity, good reproducibility and long-term stability.     

Voltammetric determination of 4-nitrophenol using a modified carbon paste electrode based on a new synthetic crown ether/silver nanoparticles

A novel modified carbon-paste electrode (CPE) with a new synthetic ligand: 6,7,9,10,17,18,19, 20,21, 22-decahydrodibenzo[h,r][1,4,7,11,15]trioxadiazacyclonanodecine-16,23dione(DTD)/Ag nanoparticles (AgNP) was employed for 4-nitrophenol measurement in natural water. Various parameters such as pH, modifier, accumulation time and scan rate were optimized. The proposed electrode showed a good response towards 4-nitrophenol determination. Under the optimized conditions the reduction peak current, showed a good linear relationship with the nitrophenol concentration in the range comprised between 1 × 10^− 6 mol L^− 1 and 1 × 10^− 4 mol L^− 1. The developed electrode was successfully applied for the determination of 4-nitrophenol in water samples.     

Voltammetric determination of ethamsylate in bulk solution and pharmaceutical tablet by nano-material composite-film coated electrode

A sensitive electrochemical method was described for voltammetric determination of ethamsylate at a glassy carbon electrode (GCE) coated with a nano-material thin film. In this work, a nanometer material, namely, multi-wall carbon nanotubes (MWCNT) was dispersed successfully into water in the presence of dihexadecyl hydrogen phosphate (DHP) and a MWCNT–DHP composite film was conveniently obtained on the GCE surface. The electrochemical behavior of ethamsylate at this modified electrode was investigated and a pair of reversible redox peak was observed. Compared with the electrochemical response of ethamsylate at the bare GCE, the separation of peak potential (ΔE_p) of ethamsylate decreased obviously from 438 to 40 mV and the current density of redox peaks increased greatly. Based on this, differential pulse voltammetry (DPV) was employed to determine ethamsylate. Various experimental parameters such as pH value of the supporting electrolyte, the amount of modifier and so on were optimized. Under optimal conditions, a linear response of ethamsylate was obtained in the range from 1.0 × 10^− 6 to 2.0 × 10^− 5 mol/L, and the detection limit was 6.0 × 10^− 7 mol/L. The proposed method was successfully applied to detect ethamsylate in pharmaceutical samples.     

Application of different types of carbon nanotubes as PIGE surface modifier in Pd(II) electrochemical determination

Nowadays, carbon nanotubes with differences in specific surface area, dopants, or functional groups are used in a number of applications, electrolysis not excluding. Various types of carbon nanotubes could improve bare graphite electrode properties by different way and so result in obtaining the different records for the same analyte. The automobile catalysts represent mobile sources of palladium. Levels of palladium in environment are continuously increasing and they need to be monitored. Electrochemistry is a useful and inexpensive component of the field of environment monitoring. For Pd(II) electrochemical determination, six types of carbon nanotubes were used as paraffin impregnated graphite electrode (PIGE) surface modifiers. Voltammetric determination brought interesting results of LOD, LOQ, standard and relative precisions of the method. These parameters as well as prediction intervals were calculated according to the technical procedure DIN 32 645 for the six electrodes and three pH values. Modification of PIGE with nitrogen doped carbon nanotubes (LOD = 1.91 × 10^?5 mol L^?1 or 3.14 × 10^?5 mol L^?1 for pH 3 and pH 4.5, respectively) seems very promising. In laboratory, functionalized carbon nanotubes, with specific surface area 200 m² g^?1, provided LOD = 1.49 × 10^?5 mol L^?1 (pH = 3) and 1.42 × 10^?5 mol L^?1 (pH = 4.5)     

On-site determination of tin in geological and water samples using novel organic reagent with iodide

A new, simple and sensitive method for spectrophotometric determination of tin (IV) with iodide and amide is described. The Sn(IV)-I(-) complex is extracted with chloroform solution of amide (N-phenylacetamide, N-alkylacetamide, alkyl=butyl, phenyl, hexyl and octyl group) in the strong sulphuric acid solution. Among five amides studied, N-octylacetamide (OAA) has been selected as it yielded best sensitivity. The apparent (at twofold preconcentration) molar absorptivity with respect to tin is (2.40)x10(5)Lmol(-1)cm(-1) at lambda(max), 410nm. The detection limit of the method is 4microgL(-1) Sn. The method is free from interferences of common ions that are normally associated with Sn. The method is highly sensitive and found to be applicable for the rapid determination of tin in water samples at micro-gram levels.     

Electrochemical characteristics of LiNiO2 films prepared for charge storable electrode application

In this paper, electrochemical investigation of LiNiO₂ films prepared by molten salt synthesis (MSS) method was performed to develop a storage electrode of solar cell energy. The preferred orientation constantly indicates (111), (012), (110) and (113). The microstructures confirmed the size of the LiNiO₂ particles in a narrow range of ~ 200 nm. Cyclic voltammogram (CV) profiles have broad cathodic peak at 3.7 V and three anodic peaks at 3.4, 3.1 and 1.9 V. For the charge and discharge range of 2.5-4.4 V, the discharge capacity was 159 mAh/g at first, and slowly decreased to 148 mAh/g during the 30th cycles.     

Bioreduction of para-chloronitrobenzene in drinking water using a continuous stirred hydrogen-based hollow fiber membrane biofilm reactor

para-Chloronitrobenzene (p-CNB) is particularly harmful and persistent in the environment and is one of the priority pollutants. A feasible degradation pathway for p-CNB is bioreduction under anaerobic conditions. Bioreduction of p-CNB using a hydrogen-based hollow fiber membrane biofilm reactor (HFMBfR) was investigated in the present study. The experiment results revealed that p-CNB was firstly reduced to para-chloraniline (p-CAN) as an intermediate and then reduced to aniline that involves nitro reduction and reductive dechlorination with H₂ as the electron donor. The HFMBfR had reduced p-CNB to a major extent with a maximum removal percentage of 99.3% at an influent p-CNB concentration of 2 mg/L and a hydraulic residence time of 4.8 h, which corresponded to a p-CNB flux of 0.058 g/m² d. The H₂ availability, p-CNB loading, and the presence of competing electron acceptors affected the p-CNB reduction. Flux analysis indicated that the reduction of p-CNB and p-CAN could consume fewer electrons than that of nitrate and sulfate. The HFMBfR had high average hydrogen utilization efficiencies at different steady states in this experiment, with a maximum efficiency at 98.2%.     

Analysis of n-alkanes in water samples by means of headspace solvent microextraction and gas chromatography

A simple and efficient headspace solvent microextraction (HSME) was developed for the simultaneous determination of the trace concentrations of some n-alkanes in water samples. Therefore, a microdrop of an organic solvent was extruded from the needle tip of a gas chromatographic syringe to the headspace above the surface of the solution in a sealed vial. Then the volatile organic compounds are extracted and concentrated in the microdrop. Next, the microdrop was retracted into the microsyringe and injected directly into the gas chromatograph. Experimental parameters which control the performance of HSME such as the type of microextraction solvent, organic drop and sample volume, sample stirring rate, sample solution and microsyringe needle temperatures, salt addition and exposure time profiles were investigated and optimized. Finally, the enrichment factor, dynamic linear range (DLR), limit of detection (LOD) and precision of the method were evaluated. Using optimum extraction conditions, good linearity with correlation coefficients in the range of 0.995相似文献   

An investigation into the electrochemical recovery of rare earth ions in a CsCl-based molten salt

A CsCl-based melt, was used as a supporting electrolyte for a fuel cycle in pyrochemical separation, as it has a high solubility for lanthanide oxide. Cyclic voltammetry and square wave voltammetry were carried out to investigate the cathodic reduction of those rare earth ions. The results prove that the cathodic process of La(III) ions dissolved in a CsCl-based melt, with a one-step reduction La(3+)+3e(-)=La, and is similar to those of other reports which have utilised LiCl-KCl or CaCl(2)-KCl molten salt systems. However, for the Ce(III) ions that dissolved in a CsCl-based melt, there is a significant difference when compared with published literature as there are two reduction steps instead of the reported single step Ce(3+)+e(-)=Ce(2+) and Ce(2+)+2e(-)=Ce. In order to explain the novel result, a detailed investigation was focused on the cathodic process of Ce(III) in a CsCl-based melt. The identification of the M-O (M=La, Ce) compounds that are stable in the electrolyte, as well as the determination of their solubility products, were carried out by potentiometric titration using an oxide ion sensor. Furthermore, the E-pO(2-) (potential-oxide ion) diagram for the M-O stable compound was constructed by combining both theoretical and experimental data.     

Electrochemical manufacturing of nanocarbons from carbon dioxide in molten alkali metal carbonate salts: roles of alkali metal cations

One simple and fast way to manufacture a useful product from CO₂ is to capture the gas by, and then carry out electrolysis in molten alkali metal carbonates. Carbon electro-deposition in molten Li₂CO₃-Na₂CO₃-K₂CO₃ (molar ratio: 43.5:31.5:25.0) has been widely reported in literature. However, studies in each of the individual alkali metal carbonates either have received less attention or are simply lacking in literature. Electrochemical studies of these molten carbonates are important to understand their underlying processes and reactions during the electrolysis. In this work, cyclic voltammograms (CVs) were recorded in each of the above-mentioned molten alkali carbonate salts using a 0.25 mm diameter Pt wire working electrode. In molten Na₂CO₃ and K₂CO₃, the main cathodic reaction was likely the formation of alkali metal, while that in Li₂CO₃ was carbon deposition. The results also suggest that other competing reactions such as CO and alkali metal carbide formation are possible as well in different molten salts. On the CVs, the anodic current peaks observed are mostly associated with the oxidation of cathodic products. Flake/ring/sheet-like structures and quasi-spherical particles were observed in the produced carbon. The morphology of the carbon contained both amorphous and graphitic structures, which varied with different electrolysis variables.     

Electrical properties of diamond films prepared from carbon disulfide and ethanol in hydrogen

Sulfur doping of diamond samples produced by the hot-filament chemical vapor deposition (CVD) process using carbon disulfide highly diluted in ethanol and hydrogen has been investigated. The polycrystalline morphology observed by Scanning Electron Microscopy (SEM) and the characteristic diamond Raman peak were practically not affected by addition of CS₂ in the range of 0.8-2.0% by volume. The electrical resistivity dependence due to CS₂ addition showed a “down-and-up” curve with minimum resistivity of about 3.6 × 10⁻⁴ Ωcm. Hall mobility as high as 325.9 cm²V⁻¹s⁻¹ have been achieved. PIXE and XRF measurements showed that sulfur (100-400 ppm) was incorporated during the deposition independent of the CS₂ added. Unintentional contaminations with Si, W, Cu and Cr have been detected. All the samples, measured by hot-point method and Hall effect, showed p-type characteristics.     

Lung counting: Comparison of a four detector array that has either metal or carbon fiber end caps, and the effect on array performance characteristics

This study described the performance of an array of HPGe detectors, made by ORTEC. In the existing system, a metal end cap was used in the detector construction. In general, the natural metal contains some radioactive materials, create high background noises and signals during in vivo counting. ORTEC proposed a novel carbon fiber to be used in end cap, without any radio active content. This paper described the methodology of developing a model of the given HPGe array-detectors, comparing the detection efficiency and cross talk among the detectors using two end cap materials: either metal or carbon fiber and to provide a recommendation about the end cap material. The detector's counting efficiency were studied using point and plane sources. The cross talk among the array detectors were studied using a homogeneous attenuating medium made of tissue equivalent material. The cross talk was significant when single or multiple point sources (simulated to heterogeneous hot spots) were embedded inside the attenuating medium. With carbon fiber, the cross talk increased about 100% for photon energy at about 100 keV. For a uniform distribution of radioactive material, the cross talk increased about 5-10% when the end cap was made of carbon instead of steel. Metal end cap was recommended for the array of HPGe detectors.     

Diffusion of Pb in carbon ion-implanted silicon: Discovery of a new crystalline phase after electron beam annealing

A novel phase has been discovered by dual low-energy ion implantation and high vacuum electron beam annealing. (100) p-type Si was implanted with (a) 20 keV ¹²C⁺ ions to the fluence of 6 × 10¹⁶ cm⁻² and (b) 7 keV Pb⁺ ions to the fluence of 4 × 10¹⁵ cm⁻². The ¹²C ion implantation results in an understoichiometric shallow SiC_x layer that intersects with the surface. The implanted Pb ions decorate a shallow subsurface region. High vacuum electron beam annealing at 1000 °C for 15 s using a temperature gradient of 5 °C s⁻¹ leads to the formation of large SiC nanocrystals on the surface with RBS measurements showing Pb has diffused into the deeper region affected by the ¹²C implantation. In this region, a new crystalline phase has been discovered by XRD measurements.     

Simultaneous preconcentration and removal of iron, chromium, nickel with N,N'-etylenebis-(ethane sulfonamide) ligand on activated carbon in aqueous solution and determination by ICP-OES

In this study, Fe, Cr and Ni have been preconcentrated and removed by using N,N'-ethylenebis (ethane sulfonamide), (ESEN) ligand on activated carbon (AC) in aqueous solution. For this purpose, complexes between these metals and ligands have been investigated and used in preconcentration and removal studies. Factors which have affected adsorption of metals on activated carbon have been optimized. Adsorbed metals have been preconcentrated 10-fold and determined by ICP-OES. Interferences of Ca, Mg and K to this process have been investigated. The proposed method has been applied to the tap water and Ankara Creek water in order to Fe, Cr, and Ni remediation and preconcentration. Determination of metals by ICP-OES has been checked with standard reference material (NIST 1643e). The proposed method provides the recoveries of 87%, 108% and 106% for Fe, Cr and Ni, respectively, in preconcentration. It also provides the removal of Fe, Cr and Ni by 93%, 100% and 100% removal from waters, respectively.     

Transformation of carbon tetrachloride by biogenic iron species in the presence of Geobacter sulfurreducens and electron shuttles

The transformation of carbon tetrachloride (CT) by biogenic iron species produced from the bioreduction of various Fe(III) oxides in the presence of Geobacter sulfurreducens and electron shuttles were investigated. Cysteine and anthraquinone-2,6-disulfonate (AQDS) at concentrations of 0.5mM and 10microM, respectively, were added as the electron shuttles. Addition of electron shuttles enhanced the extent of reduction and rate of ferric oxide reduction. The bioreduction extents of ferric oxides by G. sulfurreducens in the presence of electron shuttles were 22.8-48.3% for ferrihydrite, 6.5-17.2% for hematite, and 3.0-11.3% for goethite. After normalization to the surface areas, a higher rate of CT reduction was observed per unit of adsorbed Fe(II) on crystalline oxides. The produced biogenic Fe(II) from crystalline iron oxides was 2.8-7.6 times lower than that obtained from ferrihydrite, while the surface area-normalized rate constant for iron-mediated CT transformation in the presence of goethite and hematite were, by factors of 2-21, higher than that obtained using ferrihydrite. These results clearly depict that G. sulfurreducens drove the reduction of CT primarily through the formation of biogenic iron species in the presence of electron shuttle under iron-reducing conditions and that it is a surface area dependent process.