基于石墨/聚吡咯电极的葡萄糖生物传感器

采用电化学聚合技术,在掺杂的导电聚吡咯薄膜修饰过的铅笔芯电极上,吸附葡萄糖氧化酶制备葡萄糖生物传感器。首先在含有0.1 mol/L吡咯和0.01 mol/L HCl的溶液中,于0.7 V恒电位下吡咯单体氧化聚合,在铅笔芯电极表面形成聚吡咯薄膜;然后将葡萄糖氧化酶吸附在修饰过的电极上制备出葡萄糖氧化酶-聚吡咯-铅笔芯电极电流型生物传感器。实验考察了吡咯聚合时间、聚合温度、葡萄糖氧化酶吸附量、检测电压以及干扰物对传感器性能的影响。实验结果表明,在优化条件下,传感器的灵敏度为17.78μA/mmol/L,线性范围0.8 mmol/L,线性相关度R=0.9918,响应时间小于16 s,检测下限为18.75μmol/L,有较强的抗干扰能力。     

基于聚吡咯纳米线修饰玻碳电极的硝酸根电流型传感器研究

在玻碳电极表面,采用电聚合方法一步制备聚吡咯纳米线。由于聚吡咯的电化学氧化还原过程伴随有硝酸根的掺杂/脱掺杂,基于此构建了硝酸根电流型传感器。详细探讨了电聚合溶液的pH值、电聚合电位、电聚合时间、富集电位和富集时间对聚吡咯纳米线形貌,以及对硝酸根在修饰电极表面电化学响应的影响。在最佳条件下,构建的硝酸根传感器的线性范围为1.0×10-3～4.0×10-3 mol/L,检出限(S/N=3)达到2.2×10-4 mol/L,且具有良好的稳定性、重现性以及抗干扰能力。     

电聚吡咯固定化酪氨酸酶电极的制备及性能

在应用恒电位法电化学聚合吡咯的同时 ,将酪氨酸酶固定在导电聚吡咯膜内 ,制成一种灵敏、稳定的酪氨酸电极 .讨论了溶液 pH值和聚合电位对酶固定化的影响 ,对酶分子嵌入吡咯膜前后的SEM图和CV曲线进行了分析、比较 .该电极对甲苯酚响应的线性范围为 5 .0× 10 -8～ 1.0× 10 -6mol/L ,最适 pH值为 6 .6 ,酶反应表观上遵循Michaelis_Menten动力学 ,表观米氏常数为 2 .2× 10 -5mol/L .     

聚吡咯/聚苯胺复合型导电聚合物防腐蚀性能

采用循环伏安法,在含吡咯和苯胺的0.3 mol/L草酸水溶液中制备了聚吡咯/聚苯胺(PPy/Pani)的复合型导电聚合膜。采用红外光谱、极化曲线、自腐蚀电位-时间曲线、扫描电子显微镜和电化学阻抗谱研究了共聚膜的防腐蚀性能。结果表明,在1 mol/L H2SO4中,PPy、Pani与不锈钢基体发生氧化还原反应,促进不锈钢表面发生钝化;当苯胺与吡咯浓度比为1∶3时,制备得到的复合型导电聚合膜所保护的不锈钢自腐蚀电流最小,自腐蚀电位最高,保护时间最长。PPy、Pani及其共聚膜在3.5%NaCl溶液中电化学阻抗谱表明,所制备的PPy、Pani及其共聚物膜与不锈钢基体发生氧化还原反应,使其表面钝化;当Cl-到达不锈钢表面时,破坏钝化膜导致不锈钢腐蚀。     

天然海水中聚吡咯膜的防微生物附着及防腐蚀性能

采用恒电流法在316 L不锈钢电极表面合成聚吡咯(PPy), 通过开路电位、 生物显微镜(BM)、 Tafel极化曲线及电化学交流阻抗(EIS)研究了聚吡咯防止微生物附着及防腐蚀特性. 研究表明, 沉积聚吡咯的316 L不锈钢电极浸泡在天然海水中(0~20 d), 开路电位基本保持不变, 表明电化学合成的聚吡咯膜有良好的防止微生物附着能力, 并通过生物显微镜进行了验证, 且在浸泡的过程中其腐蚀电流密度维持在10^-7 mA/cm², 表现出良好的防腐蚀特性; 浸泡50 d后, 其防腐蚀效率仍高达97.45%. 因此, 电化学合成的聚吡咯具有优异的防止微生物附着和防腐蚀特性.     

电聚吡咯固定化酷氨酸酶电极的制备及性能

在应用恒电位法电化学聚合吡咯的同时 ,将酪氨酸酶固定在导电聚吡咯膜内 ,制成一种灵敏、稳定的酪氨酸电极 .讨论了溶液 pH值和聚合电位对酶固定化的影响 ,对酶分子嵌入吡咯膜前后的SEM图和CV曲线进行了分析、比较 .该电极对甲苯酚响应的线性范围为 5 .0× 10 -8～ 1.0× 10 -6mol/L ,最适 pH值为 6 .6 ,酶反应表观上遵循Michaelis_Menten动力学 ,表观米氏常数为 2 .2× 10 -5mol/L .     

硝苯地平在聚吡咯膜修饰电极上的电化学行为及电位溶出分析

提出了在吡咯的聚合过程将硝苯地平掺杂富集进聚吡咯膜中 ,然后在合适的溶液中通过线性扫描将之溶出的分析方法。与空白聚吡咯修饰电极 (PPy-GCE)比较 ,在0.088mol/LH2O2-0.1mol/LH2SO4 底液中 ,以100mV/s的速率进行线性扫描时 ,硝苯地平有一灵敏的线性扫描溶出峰 ,峰电位在 -0.628V(vs.SCE)。峰电流与硝苯地平的浓度在1×10 -8～1×10 -4mol/L范围内有良好的线性关系 ,利用这一峰对硝苯地平片剂的含量进行了测试 ,分析结果令人满意     

电解质溶液对聚吡咯电聚合中过氧化行为的影响

分别以硫酸/水和高氯酸锂/乙腈为电解质溶液, 采用循环伏安法在铂基底电极上电聚合制备了聚吡咯, 研究了电解质溶液对聚吡咯电聚合过程中过氧化行为的影响. 与硫酸/水溶液相比, 在高氯酸锂/乙腈溶液中电聚合制备的聚吡咯发生过氧化的峰电位正移了0.42 V. 采用原位傅里叶变换红外(in situ FTIR)光谱技术检测, 结果表明, 电聚合制备的聚吡咯在2种电解质溶液中均发生了过氧化反应, 其β-C经氧化生成C-OH或CO. 在硫酸/水溶液中, 部分聚吡咯发生电氧化降解生成CO₂, 致使其共轭结构被破坏, 电导率迅速下降. 而在高氯酸锂/乙腈溶液中, 在更高的电位范围内, 聚吡咯并没有氧化降解成CO₂.     

用聚吡咯修饰碳糊电极测定食盐中碘

在碱性条件下 ,利用还原剂硫酸肼将加碘盐中碘酸根离子还原成碘负离子 ,在饱和氯化钠溶液介质中 ,用聚吡咯修饰碳糊电极 ,采用差分脉冲伏安法测定碘离子,峰电位Ep = 0.409V(vs.SCE),峰电流与碘负离子浓度有良好线性关系 ,线性范围6.0×10-5 ～2.2×10-3 mol/L,检出限2.0×10-5 mol/L ,并对实际样品进行了回收率测定 ,取得较好结果。该法具有快速、灵敏、高效、简单的特点。     

过氧化聚吡咯修饰金电极研究全氟化合物对脱氧核糖核酸的损伤

金电极在含有1.0 mol/L KCl的0.1 mol/L吡咯溶液中,-0.3～0.8 V循环扫描10圈制备了聚吡咯膜,在1.2 V进行过氧化处理,得到聚吡咯微孔膜,并将双链小牛胸腺DNA沉积在膜的微孔内,利用差分脉冲技术以亚甲基蓝(MB)为电化学指示剂研究了新型有机污染物全氟辛烷磺酸(PFOS)对DNA的损伤.结果表...     

Electrochemical copolymerization of pyrrole and 2,2-bithiophene and semiconducting characterization of the resulting copolymer films by electrochemical impedance spectroscopy and photoelectrochemistry

The electrochemical copolymerization of pyrrole and bithiophene was studied at a polymerization potential of 1.1 V for various monomer ratios. The cyclic voltammograms showed that the electrochemical properties of the resulting copolymer films changed gradually from those of polypyrrole to polybithiophene with an increase in concentration of bithiophene in the initial electrolyte. The evidence for copolymer formation is based on the analytical results of electrospray ionization mass spectroscopy, thermoanalysis, and Raman spectroscopy. The results showed that cooligomers and homooligomers were found in the electrolyte after copolymerization. The difference between the morphology of a copolymer of pyrrole and bithiophene and a polymer mixture of polypyrrole and polythiophene was demonstrated by scanning electron microscopy. Electrochemical impedance and photocurrent measurements were carried out in order to achieve information on the semiconducting properties of the homopolymers and copolymers obtained. A model of a very thin layer of polypyrrole formed immediately on the electrode surface covered by a thicker copolymer film was developed to explain the results.Dedicated to Zbigniew Galus on the occasion of his 70^th birthday.     

Electrocatalytic hydrogenation of 4-chlorophenol on the glassy carbon electrode modified by composite polypyrrole/palladium film

A polypyrrole/palladium composite film was prepared on a glassy carbon electrode by the electrochemical deposition method. The palladium particles were uniformly dispersed on a polypyrrole film that was previously electrodeposited on a glassy carbon electrode. By controlling the polymerization process of pyrrole, a highly porous polypyrrole film was obtained; this kind of structure provided more surface areas for depositing palladium particles. The sizes of Pd particles deposited on the porous polypyrrole film are about 15-30 nm. The X-ray photoelectron spectroscopy results showed there was strong interaction between polypyrrole film and palladium particles. This modified electrode showed excellent current efficiency (49.5%) for electrochemical hydrogenation of 4-chlorophenol and the phenol was the sole product. The potential effect on the dechlorination process was also investigated.     

Electrochemical synthesis and characterization of poly(pyrrole-co-tetrahydrofuran) conducting copolymer

The direct electrochemical copolymerization of pyrrole and tetrahydrofuran in various monomer ratios was carried out by potentiostatic methods in nitromethane solution. The copolymer has been characterized using FT-IR, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetrical analysis (TGA), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and elemental analysis. The results showed that the electrochemical oxidation of pyrrole and tetrahydrofuran comonomers generated true copolymers rather than blends of the two homopolymers. The copolymer showed a better flexibility than pure polypyrrole. The electrical conductivity of the copolymers increases with the amount of polypyrrole in the copolymer between the value of 1.69 S/cm and 0.71 S/cm.     

聚吡咯为基质的脲酶传感器生物电化学响应

用电化学方法在吡咯（Ｐｙ）聚合的同时,将脲酶掺杂进聚吡咯膜（ＰＰｙ）中形成以聚吡咯为基质的脲酶电极．将脲酶电极与ＣＯ２气敏电极结合,组成对脲有电位响应的脲酶生物传感器．测试了传感器对脲的生物电化学响应．研究了聚合条件对酶活性的影响,并测定了掺杂于聚吡咯中的脲酶的活化能等动力学参数．在５０×１０－５～１．０×１０－２ｍｏｌ／Ｌ的浓度范围内,传感器响应的电极电位与脲浓度的对数成正比．     

水介质中吡咯的电化学聚合反应

研究了扫描电位上限对循环伏安法制备聚吡咯膜性能的影响，吡咯在水溶液中于玻碳电极表面化学聚合的起始电位为0．58V，在聚吡咯（Ppy）修饰电极表面聚合的起始电位为0．55V，当聚合电位上限在0．80V以上时，Ppy的氧化还原反应可逆性变差，同时，氧化电位过高将导致Ppy膜导电性能下降；研究了聚合介质对循环伏安法制备导电聚吡咯膜的影响，实时观察了吡咯（Py）聚合过程溶液中质子含量的动态变化，发现Py聚合伴随有质掺杂←→释放过程；结合Ppy膜的元素分析、ESR分析和IR光谱分析，总结出了水介质中电化学聚合高导电性聚吡咯膜的条件。     

Electrosyntheses of high‐quality freestanding poly(fluorene‐co‐3‐methylthiophene) films with tunable fluorescence properties

The copolymerization of 3‐methylthiophene (MeT) and fluorene (FE) was successfully achieved in boron trifluoride diethyl etherate by the direct anodic oxidation of the monomer mixtures on a platinum electrode. The optimal feed ratio together with the best suitable potential for their copolymerization was determined. The as‐formed copolymer films, which were copolymerized with a feed ratio of FE/MeT = 2:1 at a constant potential of 1.3 V (vs a saturated calomel electrode), had the advantages of both poly(3‐methylthiophene) and polyfluorene, such as good electrochemical behavior, high conductivity, excellent thermal stability, and high film quality. The structure of the copolymer was investigated with ultraviolet–visible, infrared spectroscopy, and thermal analysis. Fluorescence spectroscopy studies revealed that the dedoped copolymer film in the solid state was a good blue‐light emitter with a strong emission at 435 nm and a shoulder at 459 nm. The emitting properties of the copolymer could be tuned by parameters during the electrochemical polymerization, such as the applied potential and monomer feed ratio. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4904–4915, 2006     

聚吡咯(PPY)/聚己内酰胺(Nylon 6)——导电复合材料的研究

本文用电化学氧化聚合的方法制备出了既具有优良的导电性能又具有良好机械性能的聚吡咯(PPY)/聚己内酰胺(Nylon 6)的复合材料,该复合材料的导电率可达119s/cm,并对聚吡咯/聚己内酰胺导电复合材料进行了扫描电子显微镜、电导率及机械性能的测试及表征。     

Polypyrrole: Synthesis and electronic device application

A Ta solid electrolytic capacitor using conducting polypyrrole as a counter electrode has been developed by means of the direct film formation of electrochemical and chemical polymerization methods. Two-step electrochemical polymerization at a rapid and gentle rate yields a polypyrrole film on the dielectric surface of the capacitor. On the other hand, the homogeneous mixture dissolving pyrrole and oxidant under −70 °C allows chemical polymerization at elevated temperature, which also produces polypyrrole film on the dielectric surface. The capacitors produced by these methods demonstrate the improved characteristics, i.e., a high capacitance, low inner resistance and small leakage current, that correspond to the high-speed electronic devices.     

氧化铜-过氧化聚吡咯-还原氧化石墨烯复合膜修饰电极非酶检测葡萄糖

先以氧化石墨烯(Graphen oxide,GO)为阴离子掺杂剂,采用电化学聚合法制备了聚吡咯-氧化石墨烯复合膜(PPy-GO)。分别在0.10 mol/L Na Cl和0.10 mol/L NaOH溶液中对其进行还原和过氧化处理,制得过氧化聚吡咯-还原氧化石墨烯复合膜(OPPy-ERGO)。再以此OPPy-ERGO复合膜为载体,采用电化学沉积法制备了氧化铜-过氧化聚吡咯-还原氧化石墨烯复合膜修饰电极(CuO-OPPy-ERGO/CCE)。通过扫描电镜和电化学方法对此电极进行表征,研究了葡萄糖在此修饰电极上的电化学行为。结果表明,此电极对葡萄糖的电氧化过程表现出高的催化活性和良好的抗干扰能力。在0.20 mol/L NaOH溶液中,安培法检测葡萄糖的线性范围为5.0×10~(-7)~1.0×10~(-3)mol/L,检出限(3Sb)为2.0×10~(-7)mol/L,灵敏度为121.8μA/(mmol·L~(-1))。该电极用于血清中葡萄糖含量的测定,加标回收率为96.0%~110.1%。     

Characterization of Conducting Copolymer of Pyrrole via Pyrolysis Mass Spectrometry

In this work, structural and thermal characterization of BF₄ ^? doped copolymer of pyrrole (PPy) with 2‐methylbutyl‐2‐(3‐thienyl)acetate prepared by electrochemical polymerization were performed via a pyrolysis mass spectrometry technique. The pyrolysis mass spectrometry data of the copolymer PPy/PMBTA, and the homopolymers; polypyrrole, PPy, and poly(2‐methylbutyl‐2‐(3‐thienyl)acetate), PMBTA were analyzed and compared. It has been determined that when the electrochemical polymerization of pyrrole was achieved on a PMBTA coated anode through the thiophene moieties of PMBTA, thermal stability of PMBTA chains increased slightly and the decomposition of both units followed quite similar pathways indicating an increase in the thermal stability of PMBTA chains unlike what was observed for PTSA doped PPy/PMBTA copolymer.