聚硫堇修饰微带金电极的性质及对NADH的催化氧化

报道了硫堇在微带金电极上的电化学聚合过程，用红外光谱对聚硫堇进行了表征；研究了聚硫堇的电化学性质，发现聚硫堇在＋０．５～－０．７Ｖ（ｖｓ．ＳＣＥ）电位范围内有两对氧化还原峰，峰电位分别为：Ｅ＝－０．０３Ｖ、Ｅ＝０．０５Ｖ，Ｅ＝－０．２４Ｖ、Ｅ＝－０．１７Ｖ（ｖｓ．ＳＣＥ）。它们的式量电位Ｅ~（ｏ＇）随ｐＨ而变化，在弱酸性溶液中，Ｅ~（ｏ＇）／ｐＨ为－２９ｍＶ／ｐＨ（２５℃）；而在弱碱性溶液中则为－５６ｍＶ／ｐＨ。聚硫堇修饰微带金电极对ＮＡＤＨ的氧化具有催化作用，文中对电催化过程进行了探讨。     

波长检测型表面等离子体共振传感器对硫堇电聚合成膜的原位分析

利用波长检测型表面等离子体共振(SPR)传感器对硫堇在金膜表面的电化学聚合成膜过程进行了跟踪分析.结果表明,在固定入射角下SPR共振波长随循环伏安扫描周数的增加而线性红移,表明聚硫堇膜的生长是匀速的;扫描100周后共振波长红移总量为96.6 nm.对该实验结果进行理论拟合,得出聚硫堇膜的厚度约为71 nm.聚硫堇膜在酸性缓冲液中的电化学活性很高,其电化学反应过程受扩散控制,在一个完整的循环伏安扫描过程中SPR共振波长的变化完全可逆,说明聚硫堇膜的氧化反应和还原反应是一对可逆过程.与还原态聚硫堇膜相比,氧化态聚硫堇膜对应的SPR共振波长较大,说明氧化态聚硫堇膜折射率高.     

有机小分子硫堇与DNA相互作用的研究

用光谱电化学和电化学技术研究了硫堇和硫堇与DNA相互作用的电化学和光谱电化学性质，得出了硫堇作为有机小分子能插入DNA双螺旋结构内部的结论，求得了对应的动力学参数。DNA的加入量与硫堇峰电流的降低呈一次线性关系，可望用于DNA浓度检测。     

聚硫堇/过氧化氢光致电化学敏感界面的构建及其对葡萄糖氧化酶催化活性的测定

将具有光电活性的硫堇电聚合在光透电极的表面,制备了聚硫堇膜光电极,利用该电极同时具有光敏和电子受体的性能,使其与葡萄糖氧化酶对葡萄糖催化反应产生的电子供体(过氧化氢)发生光致电化学反应,通过检测由此产生的光电流实现对蛋白质催化活性的检测.本文探讨了聚硫堇/过氧化氢光致电化学敏感界面的响应机理,讨论了偏压、电解质溶液pH和底物浓度对光致电化学反应和测定葡萄糖氧化酶催化活性的影响.通过测定商品葡萄糖氧化酶的催化活性,验证了方法的可行性.应用该敏感界面检测蛋白质的催化活性不需要过氧化物酶,比光度法经济、简便和快速.     

聚硫堇半导体性质的电化学证据

聚硫堇的电导率为9.6×10－6 S•cm－1,属有机半导体.在10 ℃至60 ℃温度范围内,测定了聚硫堇的循环伏安图、恒电位下的放电曲线和交流阻抗图,并测定了电解质溶液的电导率随温度的变化.在聚硫堇的循环伏安图上有一阳极峰和一阴极峰,它们的峰电流均随温度的升高而增加;恒电位下的放电电流也随温度升高而增加;而交流阻抗的结果表明,聚硫堇的电荷传递电阻Rct随温度升高而下降,即它的交换电流i0随温度升高而增加;而溶液电阻和膜电阻也随温度的升高而下降,这同样会引起电流随温度升高而增加.所以温度对固体半导体聚硫堇的电极反应速率的影响包含了电极反应的本身和电极的电导率等因素的影响.聚硫堇的扫描电镜图证实了它的表面是一种纤维状结构.     

基于聚硫堇/过氧化氢光电化学敏感界面的胆碱传感器

将胆碱氧化酶固定在具有光电活性的聚硫堇光透电极的表面,利用壳聚糖和戊二醛键合胆碱氧化酶制备了光致电化学胆碱传感器.此传感器基于同时具有光敏和电子受体功能的聚硫堇光电界面,能与胆碱氧化酶催化胆碱反应产生的电子供体(H2O2)发生光致电化学反应的原理,实现了对胆碱的检测.探讨了传感器的光致电化学响应机理、偏压、光强及电解质...     

基于聚硫堇和层层组装碳纳米管/HRP的过氧化氢传感器研究

将电聚合和层层组装方法有效结合构筑了聚硫堇（PTH）电子介体修饰的碳纳米管（CNTs）/辣根过氧化物酶（HRP）多层膜无试剂H2O2传感器.利用电化学阻抗谱对CNTs/HRP多层膜的组装过程进行监测,用循环伏安法和计时电流法研究了该HRP电极的电化学行为.探讨了酶组装层数、工作电位、pH值和碳纳米管对电极响应的影响.该...     

以聚硫堇为电化学探针的非标记型核酸适配体传感器

采用电聚合法制备了聚硫堇氧化还原电化学探针,以金纳米粒子为固定核酸适配体的载体构建了非标记型核酸适配体传感器.用电化学阻抗谱对传感器的组装过程进行了监测,用循环伏安法和差分脉冲伏安法考察了传感器的电化学行为.结果表明,该传感器对凝血酶的检测在1.0 pg/mL～500 ng/mL范围内呈良好的线性关系,相关系数为0.998,检出限为0.38 pg/mL.该传感器制备简单、灵敏度高且抗干扰能力强.     

溶液pH对硫堇与DNA相互作用方式的影响

用电化学和光谱方法研究了溶液pH对硫堇(TH)与小牛胸腺脱氧核糖核酸(CT-DNA)相互作用方式的影响.电化学测量结果表明，在pH 7.2的磷酸盐缓冲溶液中, TH与CT-DNA之间的作用方式以嵌入结合为主，在pH 6.5的磷酸盐缓冲溶液中， TH与CT-DNA之间的作用方式既存在嵌入结合也存在静电作用.荧光光谱测量结果表明，TH与DNA结合后其荧光发生猝灭，通过Stern-Volmer方程计算得到pH 6.5时TH-DNA体系的猝灭常数高于pH 7.2时的值，表明在pH 6.5的溶液中两者相互作用更强.圆二色谱(CD)实验结果也证实了这一结论.     

聚硫堇/石墨烯复合材料修饰电极对NADH的电催化氧化研究

采用循环伏安法将硫堇在石墨烯修饰的玻碳电极表面聚合,得到了一种新的聚硫堇/石墨烯修饰电极,此电极兼备了石墨烯和聚硫堇的特性.实验表明:该修饰电极能有效降低NADH的过电位;对NADH的检测范围为2.4×10~(-6)~4.89×10~(-3) mol·L~(-1);检出限为6.826×10~(-7) mol·L~(-1);对尿酸和抗坏血酸的干扰有很好的消除作用;此电极稳定性、重现性较好,有很高的实际应用价值.     

ELECTROCHEMICAL SYNTHESIS AND PROPERTIES OF POLY(AZURE B)*

A blue poly(azure B) film has been synthesized using repeated potential cycling between -0.25 and 1. 10 V (versusSCE). The electrolytic solution consisted of 2.5 mmol dm~(-3) azure B, 0.5 mol dm~(-3) NaCl and 0.2 mol dm~(-3) NaH_2PO_4 at the pHrange of 2.0 to 11.0. The in situ visible spectrum during electrolysis of azure B shows that the intensity at 740 nm peakincreases with increasing numbers of potential cycles, which is attributable to the formation of poly(azure B). Thewavelength of its corresponding absorption peak is 98 nm longer than that of azure B. The polymerization rate is stronglyaffected by pH values. The anodic peak potential and cathodic peak potential of the poly(azure B) in a solution of pH 3.0 arenot affected by increasing the scan rate from 25 to 600 mV s~(-1). Poly(azure B) has good electrochemical reversibility and fastcharge transfer characteristic in the pH range of 2.0 and 11.0. The conductivity of poly(azure B) is 1.5×10~(-4) S cm~(-1).According to the differences between FTIR spectra of poly(azure B) and azure B, an electrochemical polymerizationmechanism of azure B is proposed in this paper.     

电化学合成吡咯与己内酰胺导电共聚物

采用恒电位方法实现了吡咯与己内酰胺在导电玻璃电极上的直接电化学共聚,聚合反应在含有0.1mol/L吡咯和1.5 mol/L己内酰胺的硝基甲烷电解质溶液中进行,外加电位控制在1.2 V以上.聚合产物中聚吡咯与聚己内酰胺链段的组成可通过调节合成电位加以控制.共聚物的形貌、结构与性质采用扫描电子显微镜、热重分析、红外光谱等手...     

Electrochemical immuno-bioanalysis for carcinoma antigen 125 based on thionine and gold nanoparticles-modified carbon paste interface

A novel electrochemical immunosensor for the determination of carcinoma antigen 125 (CA125) was developed by means of immobilizing CA125 antibody (anti-CA125) on gold nanoparticles (Au) and thionine (Thi)-modified carbon paste interface. To avoid the leak of hydrophilic gold nanoparticles and thionine from carbon paste interface, the Au-Thi-modified carbon paste electrodes (CPEs) were first treated in the mixture solution containing 10% HNO₃ and 2.5% K₂Cr₂O₇ for 1.5 min at +1.5 V to make the carbon surface with -COOH groups, which can react with -NH₂ groups on the thionine molecule, in the meantime, gold nanoparticles were absorbed on the thionine surface. Subsequently, CA125 antibodies were assembled onto the surface of gold nanoparticles. The fabrication process of the immunosensor was characterized by fourier transform infrared spectroscopy (FTIR) and UV-vis absorption spectroscopy. The performance and factors influencing the performance of the immunosensor were studied in detail. A direct electrochemical immunoassay format was employed to detect CA125 antigen based on the current change before and after the antigen-antibody reaction. The current change was proportional to CA125 concentration ranging from 10 to 30 U/ml with a detection limit of 1.8 U/ml (at 3δ). The immunosensors were used to analyze CA125 in human serum specimens. Analytical results of clinical samples show that the developed immunoassay has a promising alternative approach for detecting CA125 in the clinical diagnosis.     

ELECTROCHEMICAL POLYMERIZATION OF ANILINE IN PHOSPHORIC ACID AND THE PROPERTIES OF POLYANILINE

The behavior of the electrochemical polymerization of aniline in a weak acid, phosphoric acid, is very similar to that in strong acids, i.e. its polymerization rate increases quickly with the electrolysis time. The FTIR spectra of polyaniline samples synthesized in phosphoric acid indicate that the counter ion H2PO4^- is present in both the oxidized form and the reduced form of polyaniline. The counter ion plays an important role in adjusting the pH value at the electrode surface of polyaniline during the oxidation and reduction processes. As a result, a pair of redox peaks still appear in cyclic voltammograms of polyaniline in a solution of sodium sulfate of pH 5.5 and in a solution of NaH2PO4 of pH 7.0,respectively, at low potential scan rate; and the color of polyaniline film also changes with applied potential at pH 7.0. Thus,the pH region for the electrochemical activity and the electrochromism of polyaniline is extended to pH 5.5 for a solution of sodium sulfate and to pH 7.0 for a solution of NaH2PO4. The conductivity of polyaniline is 3.3 S cm^-1, depending on the concentration of phosphoric acid used in the stage of polymerization of aniline. The result of elemental analysis of polyaniline is presented here.     

天然氨基酸水溶液中聚吡咯的电化学合成及其表征

报道了各种天然α-氨基酸水溶液中电化学聚合吡咯获得氨基酸掺杂的聚吡咯.实验表明吡咯在酸性氨基酸电解质中的氧化聚合电位较低,速度较快;而在碱性氨基酸水溶液中几乎无法进行电化学聚合.在电化学聚合过程中,氨基酸既作为支持电解质,又作为对离子被掺杂到聚合物中.该聚吡咯的电导率被测定为0.3～1.0 S/cm,在酸性氨基酸溶液中得到的聚合物电导率明显高于酸性较弱的氨基酸溶液中得到的聚合物,同时聚合物还具有良好的电化学活性和电化学稳定性,在-0.5 V到+0.5 V区间有一对氧化还原峰,该氧化还原峰的形状和特性在100次循环后基本保持不变.通过扫描电镜和透射电镜照片可以看出,不同种氨基酸的掺杂对聚吡咯的形貌具有影响,由于氨基酸的软模板效应,在数种氨基酸水溶液中能制得具有纳米纤维结构的聚吡咯.     

Electrochemical Polymerization of Methylene Green

The electrochemical polymerization of methylene green has been carried out using cyclic voltammetry. The electrolytic solution consisted of 4° 10^?3 mol/L methylene green, 0.1 mol/L NaNO₃ and 1 × 10^?2 mol/L sodium tetraborate with pH 11.0. The temperature for polymerization is controlled at 60°C. The scan potential is set between ?0.2 and 1.2 V (vs. Ag/AgCl with saturated KCl solution). There are an anodic peak and a cathodic peak on the cyclic voltammogram of poly (methylene green) at pH≤3.8. Both peak potentials shift towards negative potentials with increasing pH value, and their peak currents decrease with increasing pH value. Poly (methylene green) has a good electrochemical activity and stability in aqueous solutions with pH≤3.8. The UV‐Visible spectrum and FTIR spectrum of poly (methylene green) are different from those of methylene green.     

ELECTROCHEMICAL COPOLYMERIZATION OF ANILINE AND AZURE B*

The electrochemical copolymerization of aniline and N,N,N'-trimethylthionin (azure B) in aqueous solutions hasbeen carried out using the potential sweep method, The optimum conditions for the coelectrodeposition are that the pH valueand the temperature of the electrolytic solution are controlled at 5.57 and 30℃, respectively, and the scan potential range isset between - 0.25 and 1.10 V (versus SCE). The copolymerization rate of aniline and azure B is about 3 times larger thanthat of aniline in the absence of azure B. The copolymerization of aniline and azure B was verified from the results of visiblespectra during electrolysis, FTIR spectra and the atomic force microscopy (AFM) images of the polymers. The in situ visiblespectrum for the electrolysis of the solution containing aniline and azure B is different from that of the respective aniline andazure B. The FTIR spectrum of the copolymer is not a superposition of that of polyaniline and poly(azure B). The AFMimage of the copolymer is different from those of polyaniline and poly(azure B) and is not a mixture of individual polymers.The conductivity of thc copolymer synthesized at pH 5.57 is four orders of magnitude higher than that of polyanilinesynthesized under the same conditions, bat in the absence of azure B. The clectrochemical properties of the copolymer aremainly attributed to polyaniline, but the copolymer has a better electrochemical reversibility and a much faster charge transferthan those of polyaniline.     

SYNTHESIS OF POLYCATECHOL WITH ELECTROCHEMICAL ACTIVITY AND ITS PROPERTIES

The electrochemical polymerization of catechol on platinum has been carried out using repeated potential cyclingbetween-0.2 and 1.1 V (versus SCE). The electrolytic solution consisted of 0.2 mol dm~(-3) catechol, 0.5 mol dm~(-3) NaCl and0.1 mol dm~(-3) Na_2HPO_4 with pH 8.72. Catechol can not be polymerized at pH≥10.12. Polycatechol has an electrochemicalactivity at pH≤4. The anodic and cathodic peak potentials of polycatechol shift towards more negative values as the pH ofthe solution increases from 1 to 4. The electrochemical activity of polycatechol hardly changes in this pH region, but itdecreases slowly with time. This is caused by oxygen in air, which leads to an irreversible oxidation of polycatechol. Thisproperty is favorable for protecting metals from corrosion. Raman and FTIR spectra of polycatechol and catechol are quitedifferent. AFM images of polycatechol films provide evidence that the image of the oxidized state of polycatechol ismarkedly different from that of the reduced one. This difference is caused by doping and dedoping of polycatechol.     

Electroactive polyimide with oligoaniline in the main chain via oxidative coupling polymerization

By oxidative coupling polymerization of the imidic macromonomer of oligoaniline and p-phenylenediamine we have prepared an electroactive polyimide, exhibiting exciting molecular structure, electrochemical properties and excellent thermal stability. The polymerization characteristics and structure of the electroactive polyimide were systematically studied by Fourier-transform infrared (FTIR) spectra and X-ray powder diffraction (XRD). Electrochemical activity of the polyimide was tested in 1.0 M H₂SO₄ aqueous solution and it shows two redox peaks, which is the same as that of polyaniline. Moreover, the thermal properties of the polyimide were evaluated by thermogravimetric analysis (TGA). Its electrical conductivity is about 8.87 × 10⁻⁶ S cm⁻¹ at room temperature upon preliminarily protonic-doped experiment.