Construction of a Novel Carbon Paste Clarithromycin Sensor for Low Level Concentration Measurement,Applications to Pharmaceutical and Biological Analysis

A potentiometric carbon paste sensor was fabricated for determination of clarithromycin based on incorporation of the ion association complex of the clarithromycin‐phosphotungstate. The proposed sensor exhibited a Nernstian slope of 59.2±0.3 mV per decade for clarithromycin over a wide concentration range of 7.4×10^?7 to 1.5×10^?3 M, with a low detection limit of 5.0×10^?7 M. The proposed sensor manifested advantages of very fast response, long life time and, most importantly, excellent selectivity for clarithromycin relative to a wide variety of common foreign inorganic cation, and also biological species. The sensor was successfully applied to determine clarithromycin in clarithromycin tablet, blood serum and urine samples. The inclusion complex formation between β‐cyclodextrin and clarithromycin was studied by the proposed sensor. The influence of the temperature on the response of the sensor was investigated and the temperature coefficient of the sensor was calculated.     

Simultaneous determination of acetaminophen,dopamine and ascorbic acid using a PbS nanoparticles Schiff base-modified carbon paste electrode

A highly sensitive method was investigated for the simultaneous determination of acetaminophen (AC), dopamine (DA), and ascorbic acid (AA) using a PbS nanoparticles Schiff base-modified carbon paste electrode (PSNSB/CPE). Differential pulse voltammetry peak currents of AC, DA and AA increased linearly with their concentrations within the ranges of 3.30 × 10⁻⁸–1.58 × 10⁻⁴ M, 5.0 × 10⁻⁸–1.2 × 10⁻⁴ M and 2.50 × 10⁻⁶–1.05 × 10⁻³ M, respectively, and the detection limits for AC, DA and AA were 5.36 × 10⁻⁹, 2.45 × 10⁻⁹ and 1.86 × 10⁻⁸ M, respectively. The peak potentials recorded in a phosphate buffer solution (PBS) of pH 4.6 were 0.672, 0.390, and 0.168 V (vs Ag/AgCl) for AC, DA and AA, respectively. The modified electrode was used for the determination of AC, DA, and AA simultaneously in real and synthetic samples.     

Electrochemical droplet-based microfluidics using chip-based carbon paste electrodes for high-throughput analysis in pharmaceutical applications

This paper presents the first example of a pharmaceutical application of droplet-based microfluidics coupled with chronoamperometric detection using chip-based carbon paste electrodes (CPEs) for determination of dopamine (DA) and ascorbic acid (AA). Droplets were generated using an oil flow rate of 1.80 μL min⁻¹, whereas a flow rate of 0.80 μL min⁻¹ was applied to the aqueous phase, which resulted in a water fraction of 0.31. The optimum applied potential for chronoamperometric measurements in droplets was found to be 150 mV. Highly reproducible analysis of DA and AA was achieved with relative standard deviations of less than 5% for both intra-day and inter-day measurements. The limit of detection (LOD) and limit of quantitation (LOQ) were found to be 20 and 70 μM for DA and 41 and 137 μM for AA, respectively. Linearity of this method was in the ranges of 0.02–3.0 mM for DA and 0.04–3.0 mM for AA. This system was successfully applied to determine the amounts of DA and AA in intravenous drugs. Calibration curves of DA and AA for quantitative analysis were obtained with good linearity with R² values of 0.9984 and 0.9988, respectively. Compared with the labeled amounts, the measured concentrations of DA and AA obtained from this system were insignificantly different, with error percentages of less than ±3.0%, indicating a high accuracy of the developed method.     

The Influencing Mechanism of Acidity on the Oxidation Peak Currents of Uric Acid and Ascorbic Acid at the PACPE by Cyclic Voltammetry

In this paper, a pre‐anodized carbon paste electrode (PACPE) is fabricated by a simple electrochemical pretreatment method, which can be used for the simultaneous determination of uric acid (UA) and ascorbic acid (AA). The influencing mechanism of the acidity on the size of oxidation peak current (i_p,a) of UA and AA is discussed in detail. According to the results, in different pH conditions, the intensity of hydrogen bonding between UA, AA and the surface of PACPE, the degree of reduction reaction at the auxiliary electrode, and the structural configurations of UA and AA with different species in reaction system have evident influence on the size of oxidation peak current. In pH 7.00 phosphate buffer solution, the calibration curves for UA and AA are obtained in the range of 5.0 x 10^‐7–5.0 x 10^‐5 mol/L and 3.0 x 10^‐5–5.0 x 10^‐3 mol/L, respectively. The detection limits for UA and AA are found to be 2.0 x 10^‐8 mol/L and 1.2 x 10^‐6 mol/L, respectively. This proposed method has been successfully applied to determine UA and AA in human urine simultaneously with satisfactory results.     

芬苯达唑在石墨烯与[Bupy]PF_6复合修饰碳糊电极上的电化学性质及电分析方法研究

本文研究了芬苯达唑(Fenbendazole,FBZ)在石墨烯(RGO)与离子液体(N-丁基吡啶六氟磷酸盐)复合修饰碳糊电极上的电催化氧化及电化学动力学性质。同时用CC法(计时库仑法)、计时电流法(CA)测定FBZ在RGO-[Bupy]PF6/CPE上的电极反应动力学参数,并用方波伏安法(SWV)测定FBZ氧化峰电流(Ip)与其浓度c在4.0×10-8~1.0×10-5mol·L-1范围内呈良好线性关系,线性回归方程为Ip(μA)=1.471+5220.78c(10-3mol·L-1),R=0.9995,检测限(S/N=3)为1.4×10-9mol·L-1,在此基础上用SWV法对FBZ片剂中FBZ含量进行了电化学定量测定,RSD在0.2%~0.9%之间,回收率在99.0%~101.4%之间。     

Simultaneous and Sensitive Detection of Cd(II) and Pb(II) Using a Novel Bismuth Film/Ordered Mesoporous Carbon‐molecular Wire Modified Graphite Carbon Paste Electrode

An electrochemical sensor for the simultaneous and sensitive detection of Cd(II) and Pb(II) is proposed on the basis of square‐wave anodic stripping voltammetry (SWASV) experiments using a novel bismuth film/ordered mesoporous carbon‐molecular wire modified graphite carbon paste electrode (Bi/OMC‐MW/GCPE). Ordered mesoporous carbon (OMC) and molecular wire (MW) (diphenylacetylene) were used as the modifier and binder, respectively. The Bi/OMC‐MW/GCPE was prepared with the addition of graphite powder, OMC and DPA at the ratio of 2 : 1 : 1. The electrochemical properties and morphology of the electrode were characterized by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), SWASV and scanning electron microscopy (SEM). The parameters affecting the stripping current response were investigated and optimized. The experimental results show that the prepared electrode exhibited excellent electrochemical performance, good electrical conductivity and a high stripping voltammetric response. Under optimized conditions, a linear range was achieved over a concentration range from 1.0 to 70.0 μg/L for both Cd(II) and Pb(II) metal ions, with detection limits of 0.07 μg/L for Cd(II) and 0.08 μg/L for Pb(II) (S/N=3) with the deposition time 150 s. Moreover, the sensor exhibited improved sensitivity and reproducibility compared to traditional CPEs. The fabricated electrode was then successfully used to satisfactorily detect Cd(II) and Pb(II) in real soil samples.     

Development of an Osmium Redox Polymer Mediated Bioanode and Examination of its Performance in Gluconobacter oxydans Based Microbial Fuel Cell

Gluconobacter oxydans (G. oxydans ) cells together with an osmium redox polymer (ORP) [Osmium (2,2’‐bipyridine)2(poly‐vinylimidazole)10Cl]Cl were combined with a glassy carbon paste electrode (GCPE) to form a bioanode for a microbial fuel cell (MFC) based on G. oxydans . Although there are G.oxydans / ORP combined bioanode in the literature, as far as it is known, this system is the first one where G.oxydans /ORP bioanode is combined with a cathode and a MFC is formed. After the optimization of experimental parameters, analytical characteristics of ORP/G. oxydans /GCPE bioanode were investigated. ORP/G. oxydans /GCPE showed two linear ranges for ethanol substrate as 1.0–30 mM (R²=0.902) and 30–500 mM (R²=0.997) and analytical range as 1.0–1000 mM. Limit of detection (3.0 s/m) and limit of quantification (10 s/m) values were calculated as 1.29 mM and 4.30 mM respectively where the RSD value was 1.16 % for n=5. Combining the developed bioanode in the presence of 5.0 mM K₃Fe(CN)₆ mediator with a Pt wire cathode a double compartment MFC was obtained via a salt bridge. G. oxydans /GCPE bioanode based MFC had maximum power density of 0.133 μW cm⁻² (at 33.5 mV), maximum current density as 8.73 μA cm⁻² and OCP value of 156 mV. On the other hand, ORP/G. oxydans /GCPE based MFC showed maximum power density as 0.26 μW cm⁻² (at 46.8 mV), maximum current density as 15.079 μA cm^‐2 and OCP value of 176 mV.     

Development of a Sensor Based on Modified Carbon Paste with Com Iron(III) Protoporphyrin Immobilized on SiNbZn Silica Matrix for L‐tryptophan Determination

In this work, SiO₂/Nb₂O₅/ZnO prepared by the sol‐gel processing method was used as substrate base for immobilization of the protoporphyrin‐IX ion. Iron(III) ion was inserted into the porphyrin ring (SiNbZn‐PPFe). A simple square wave voltammetry method based on a composite sensor carbon paste electrode of this material,designed as EPC‐SiNbZn‐PPFe, was developed and validated successfully for the determination of L‐tryptophan (Trp). The optimum conditions were obtained by using sensor modified with 18.00 mg SiNbZn‐PPFe material, 12.00 mg graphite powder and 6.0 μL mineral oil and phosphate buffer 0.3 mol L⁻¹ pH 7.0. The sensitivity of the sensor was found to be 0.523 AL mol ⁻¹, linear range from 10 to 70 μmol L⁻¹ and limit of detection of 3.28 μmol L⁻¹. Therefore, the developed method was successfully applied for the Trp determination in real samples of pharmaceutical formulation and can be used for routine quality control pharmaceutical formulations containing Trp.     

The use of the capillary rheometer for the rheological evaluation of extrudable cement-based materials

In this paper, the rheological properties of an extrudable cement-based paste are investigated by means of an original ram extrusion apparatus (capillary rheometer). The experimental results indicate that a careful measurement of the die pressure is necessary to obtain a realistic viscosity vs shear rate curve, as required in extrusion technology. In particular, it is shown that the optimal test configuration is when the pressure measurement is made directly inside the rheometer die. By applying this rheological methodology in steady-state conditions, it has been observed that the extrudable cement-based material here evaluated obeys to a simple power–law equation, in the range of shear rates investigated, which are suitable for an industrial extrusion process. This paper was presented at the third Annual European Rheology Conference (AERC) held in Hersonissos, Crete, Greece, April 24–27, 2006.     

Capillary Imbibition and Pore Characterisation in Cement Pastes

The kinetics of capillary imbibition in ordinary Portland cement pastes has been studied experimentally and theoretically. Nuclear magnetic resonance stray field imaging (STRAFI) has been used to record water concentration profiles for various ingress times. The profiles follow a t law and thus a master curve can be formed using the Boltzmann transformation. The distribution of pore sizes within the sample as measured by NMR cryoporometry shows a prominent peak at 100Å. A computer model of the pore structure was developed consisting of a lattice of interconnecting pores with a size distribution consistent with the cryoporometry results. The Hagen–Poiseuille law was used to describe the kinetics of the water in this pore structure. The best agreement between the computer simulations and the experimental master curve was obtained by using a narrower range of pore sizes than indicated by the cryoporometry results.