V(IV)在不同电极上氧化还原动力学研究

分别以导电塑料集流板、石墨棒、铂片作工作电极,应用循环伏安法和稳态极化法研究V(IV)的阳极氧化动力学过程,计算V(IV)在不同材料电极上的反应动力学参数.结果表明,以导电塑料板作电极,硫酸氧钒有较宽的水稳定区,且析氧电位较高;在石墨电极上,V(V)/V(IV)的交换电流密度较大,表现出较好的可逆性;而在铂电极上,硫酸氧钒更易析氢.     

Poly(p‐phenylenediamine)‐coated magnetic particles: Preparation and electrochemical properties

Magnetic particles are of great interest in various biomedical applications, such as, sample preparation, in vitro biomedical diagnosis, and therapy. For biosensing applications, the used functional magnetic particles should answer numerous criteria such as; submicron size in order to avoid rapid sedimentation, high magnetic content for fast separations under applied magnetic field, and finally, good colloidal stability. Therefore, the aim of this work was to prepare submicron magnetic core and conducting polymer shell particles. The polymer shell was induced using p‐phenylenediamine as key monomer. The obtained core–shell particles were characterized in terms of particle size, size distribution, magnetization properties, Fourier transform infrared (FTIR) analysis, surface morphology, chemical composition, cyclic voltammetry, and impedance spectroscopy. The best experimental condition was found using 40 mg of povidone (PVP—stabilizing agent) and 0.16 mmol of p‐phenylenediamine. Using such initial composition, the core‐shell magnetic nanoparticles shown a narrowed size distribution around 290 nm and high magnetic content (above 50%). The obtained amino containing submicron highly magnetic particles were found to be a conducting material and superparamagnetic in nature. These promising conducting magnetic particles can be used for both transport and lab‐on‐a‐chip detection.     

聚L-甲硫氨酸修饰电极的制备及对尿酸的测定

在pH9.5的磷酸盐缓冲溶液中,利用循环伏安(CV)法制备了聚L-甲硫氨酸修饰玻碳电极(PLMet/GC/CME)。研究了尿酸(UA)在该电极上的电化学行为,建立了伏安法测定UA的新方法。在pH5.0的磷酸缓冲溶液中,扫描速率为200 mV/s,循环扫描电位在-0.3~1.0 V时,UA在PLMet/GC/CME上产生一个灵敏的氧化峰,峰电位位于0.52 V(vs.Ag/AgCl)。用CV法、线性扫描伏安(LSV)法和示差脉冲伏安(DPV)法对UA进行测定,测定的线性范围分别为2.50×10-6~1.00×10-4mol/L、5.00×10-6~1.00×10-4mol/L和8.00×10-7~1.00×10-4mol/L;检出限分别为8.0×10-7mol/L(CV、LSV法)和5.0×10-7mol/L(DPV法)。用LSV法对尿样中的UA进行测定,结果满意。     

聚l-异白氨酸修饰电极的制备及对多巴胺的测定

聚合物修饰电极;l-异白氨酸;多巴胺;循环伏安法     

聚丙烯酸/聚丙烯酰胺水溶液复合特性的研究

通过酸度、电导率、粘度、接触角的测定,研究了聚丙烯酸 (PAA) /聚丙烯酰胺 (PAM) 水溶液复合物及复合物膜的结构和性能。结果表明,酸度、温度、浓度和复合比影响PAA/PAM的复合水溶液中大分子链的构象和流体力学体积,适度的氢键作用可以形成均相的复合溶液。经过热处理和未经热处理的聚合物膜表现出了不同的亲水性能。     

Immobilization of Tyrosinase in Poly(2-thiophen-3-yl-alkyl ester) Derivatives

In this study, construction of novel biosensors for the determination of phenolic compound was performed via immobilization of tyrosinase during the electrochemical synthesis of conducting block copolymers of 2-thiophen-3-yl-alkyl ester derivatives with 3,4-ethylenedioxythiophene and synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT). The resultant biosensors were characterized in terms of their maximum reaction rates, Michaelis–Menten constants (K_m), temperature and pH stabilities. All the copolymer matrices represented higher reaction rates and higher K_m values in comparison to both polypyrrole and PEDOT matrices and a relation between the morphology of the matrice and the kinetic parameters was observed. Biosensors maintained their activity even at temperatures as high as 80°C and could be used at pHs higher than 8 with high precision. The amount of phenolics in actual samples (red wines) was investigated using electrodes, and results were compared with those found from Folin–Ciocalteau method. Hence, the present study has proven the suitability of these copolymers to be used as polymer matrices for enzyme immobilization.     

Effect of Surface Structure on Behavior of RuO2 Electrodes in Sulfuric Acid Aqueous Solution

The electrochemical properties of RuO₂ electrodes are studied by means of cyclic voltammetry, potential step, and impedance measurements in aqueous 0.5 mol/dm³ H₂SO₄ as a supporting electrolyte solution and applying the hanging electrolyte meniscus technique. Two types of the electrodes are used: bulk as-grown single-crystal having (101) exposed interface and 500 nm film produced by reactive RF magnetron sputtering at 450°C. The surface structure of the RuO₂ electrodes prepared by different techniques is defined from X-ray LAUE backscattering. Experimental data show that, for both RuO₂ electrodes, the charging components include a slow diffusion-controlled contribution, due to proton injection–ejection. The diffusion characteristics and the diffusion coefficients for the same electrodes are estimated and reported.     

Electrosynthesis of Poly(para)phenylene in an Ionic Liquid: Cyclic Voltammetry and in Situ STM/Tunnelling Spectroscopy Studies

The electropolymerization of benzene in the air and water‐stable ionic liquid 1‐hexyl‐3‐methylimidazolium tris(pentafluoroethyl)trifluorophosphate (HMIm)FAP is investigated. The study comprises cyclic voltammetry, IR and in situ STM/tunnelling spectroscopy measurements. The IR results indicate that poly(para)phenylene is the end product of the electropolymerization of benzene in the employed ionic liquid. The resulting conjugation lengths of the product fall between 19 and 21. A polymer reference electrode is used successfully for the electrochemical polymerization of benzene. The first in situ STM results show that the electropolymerization of benzene in the ionic liquid can be probed on the nanoscale and the band gap of the prepared polymer can be determined. The electrodeposited polymer film obtained at a constant potential of 1.0 V vs PPP (polyparaphenylene) exhibits a band gap of 2.9±0.2 eV.     

银掺杂聚L-天冬氨酸修饰电极的制备及对肾上腺素的测定

利用循环伏安法,研究了银和L-天冬氨酸在玻碳电极表面电化学聚合的条件,制备了银掺杂聚L-天冬氨酸修饰电极。研究了肾上腺素在修饰电极上的电化学行为,建立了循环伏安法测定肾上腺素的新方法。在pH=3.5的磷酸盐缓冲溶液中,扫描速率为50mV/s时,肾上腺素在修饰电极上产生一对明显的氧化还原峰,峰电位分别为Epa=0.447V,Epc=0.387V。用循环伏安法测定时,氧化峰电流与肾上腺素浓度分别在8.00×10-8～1.00×10-5mol/L和1.00×10-5～1.00×10-4mol/L范围内呈良好的线性关系,检出限为8.0×10-9mol/L。     

Detection of Intermediate during Electrochemical Polymerization of Azure A and X‐ray Photoelectron Spectroscopy of Poly(azure A)

The electrochemical polymerization of azure A has been investigated by the rotating ring‐disk electrode (RRDE) and the X‐ray photoelectron spectroscopy (XPS). The electrolysis of azure A was studied in the pH region of 1.0 and 12.0. The results from the RRDE experiments show that the electrochemical polymerization of azure A was performed by two steps, i.e., oxidation of azure A and followed by polymerization. The intermediates generated at the disk were detected at the ring electrode in the ring potential region of ?0.2–0.20 V (vs. Ag/AgCl reference electrode). The collection efficiencies of the intermediates increase with decreasing the ring potential as well as increasing the rotation rate of the RRDE. Thus, the intermediate is to carry a positive charge species and not too stable. The results from the XPS experiments show that the anions can be doped into poly(azure A) film and be dedoped from it during oxidation and reduction processes.     

聚丁基噻吩的合成及性能

用化学聚合方法合成了聚丁基噻吩导电材料,并研究了不同的聚合条件对聚合物性能的影响。聚丁基噻吩导电材料具有较好的稳定性和加工性,其掺杂态的导电率可达到10s/cm。     

新型电活性聚(2,2'-二氨基苯氧基二硫化物)的电化学合成

在Pt电极上,LiClO4和不同酸的乙腈/四氢呋喃溶液中,通过动电位连续扫描法合成了新型电活性聚（2,2'-二氨基苯氧基二硫化物）（PDAPD）,研究了电解质LiClO4及不同酸（HCl、CF3COOH、CCl3COOH、CH3COOH）的浓度对合成产物的影响,实验结果表明：浓度为0.1mol/L的LiClO4及浓度在0.05-0.5mol/L之间的HCl是获得高电活性的聚合物导电膜的最佳实验条件。     

聚酸性铬蓝K修饰电极测定对乙酰氨基酚

研究对乙酰氨基酚(ACOP)在聚酸性铬蓝K(PACBK)修饰石墨电极上的电化学行为,并利用该电极建立测定对乙酰氨基酚的电化学方法。采用循环伏安法制备了聚酸性铬蓝修饰石墨电极,利用脉冲伏安法对对乙酰氨基酚的含量进行测定。对乙酰氨基酚的浓度在0.8~100μmol/L范围与脉冲峰电流呈现良好的线性关系(r~2=0.998 2),检出限为0.1μmol/L(S/N=3),实际样品的平均加标回收率为96.5%~101.7%,测定结果的相对标准偏差为1.2%(n=6)。该方法可用于药物对乙酰氨基酚片的质量控制。     

Poly(Methyl Red) Modified Glassy Carbon Electrodes: Electrosynthesis,Characterization, and Sensor Behavior

Poly(methyl red), PMR, was electropolymerized on glassy carbon electrodes by potential cycling in 50 mM phosphate buffer solution at pH 7.0 and 8.0 and Britton Robinson buffer solution in the pH range 7.0‐11.0. The electrochemical behavior of PMR modified electrodes was investigated by cyclic voltammetry in Britton Robinson buffer solution at different pHs from 5.0 to 10.0 and found that the best PMR film formation was obtained at pH 9.0. Uric acid was quantitatively determined at PMR modified electrodes by cyclic voltammetry and differential pulse voltammetry in Britton Robinson buffer at pH 5.0. Both methods presented a linear dependence between the anodic peak current and the concentration of uric acid in the range of 0.4 to 60 μM and 0.08 to 100 μM with the limits of detection of 0.038 and 0.009 μM for cyclic voltammetry and differential pulse voltammetry, respectively. Poly(methyl red) as redox mediator allowed the determination of uric acid without any interferences from the substances in serum samples.     

Core‐Shell Structured Monodisperse Poly(3,4‐Ethylenedioxythiophene)/Poly(Styrenesulfonic Acid) Coated Polystyrene Microspheres and Their Electrorheological Response

We report the successful synthesis of transparent thin film of conducting poly(3,4‐ethylenedioxythiophene)/poly(styrenesulfonic acid) (PEDOT/PSS) coated monodisperse polystyrene (PS) microspheres via a simple physical adsorption route in an aqueous media and their electrorheological (ER) application under an applied electric field. Due to the insulating PS core, the PEDOT/PSS wrapped PS (PEDOT/PSS/PS) particles possess a low volume conductivity appropriately applied as ER active materials. Tested by a rotational rheometer under an applied electric field, the PEDOT/PSS/PS based ER fluid dispersed in a silicone oil shows a typical Bingham‐fluid behavior with increased yield stresses according to the increase of electric field strength.

     

盐酸吡哆辛在聚烟酸修饰电极上的电化学行为及测定

采用电聚合方法制备了聚烟酸修饰玻碳电极(PNA/GCE),并利用循环伏安法(CV)和差分脉冲伏安法(DPV)考察了盐酸吡哆辛(VB6)在该修饰电极上的电化学行为。结果表明,VB6在PNA/GCE上的氧化峰电流显著提高,电极反应为扩散控制的一电子两质子反应。利用差分脉冲伏安法对VB6进行测定,线性范围为0.08~400μmol/L,VB6的检出限为0.02μmol/L,测定结果的相对标准偏差为3.1%(n=8),加标回收率为95.8%~103.7%。该方法可用于VB6片中VB6含量的测定。