基于聚吡咯修饰膨胀石墨电极的甲胎蛋白电化学免疫传感器

构建了测定人血清中甲胎蛋白(AFP)的电化学免疫传感器。此免疫传感器的制备采用恒电位法在膨胀石墨(EG)电极表面合成聚吡咯(PPy),再以戊二醛(GA)作为交联剂,固定辣根过氧化酶标记的AFP抗体(HRP-anti-AFP)。此免疫传感器在含AFP的溶液中于35℃温育50 min后,再在传感器表面修饰普鲁士蓝(PB)作为电子介体,抗原抗体免疫结合产生的免疫复合物会导致HRP对PB催化氧化的效率降低。在优化条件下,AFP的浓度在0.01～300μg/L范围内呈线性关系,检出限为6.25 pg/mL(S/N=3)。这种基于PPy修饰EG电极的免疫传感器制备简单,灵敏度高且价格低廉,有望成为一次性电化学免疫传感器。     

纳米石墨薄片/聚吡咯复合材料的制备及导电性能

膨胀石墨经过超声处理制备了纳米石墨薄片。以其为导电填料，对甲苯磺酸为掺杂剂，FeCl₃·6H₂O为氧化剂，引发吡咯单体发生原位聚合，制备出纳米石墨薄片/聚吡咯(NanoGs/PPy)复合材料。利用红外光谱(FTIR)、扫描电镜(SEM)和透射电镜(TEM)表征了材料的组成和结构。结果表明，石墨薄片被聚吡咯完全包覆；并且以纳米级尺寸分散在聚吡咯基体中。热失重(TG)分析和电导率测试结果表明，复合材料的耐热性能和导电性能较纯聚吡咯有所提高。     

聚吡咯/硫化镉核壳纳米线的制备及整流特性

以无机多孔氧化铝膜为模板,利用气相沉积和原位电化学沉积方法成功地制备了有机-无机杂化聚吡咯/硫化镉核壳纳米线;采用扫描电子显微镜和透射电子显微镜分析了聚吡咯/硫化镉核壳纳米线的表面形貌和微结构.结果表明,内部的聚吡咯纳米线紧紧依附在外部的硫化镉纳米管中,并且硫化镉纳米管被聚吡咯全部填充.与此同时,在聚吡咯/硫化镉核壳纳米线中,外部硫化镉壳与内部聚吡咯核之间存在电荷转移;聚吡咯和硫化镉之间形成有机-无机杂化的P-N界面,从而导致单根聚吡咯/硫化镉核壳纳米线显示出不同于外部壳和内部核的整流特性.     

聚吡咯/石墨复合对电极在染料敏化太阳能电池中的应用研究

通过化学氧化法制备了聚吡咯纳米粒子, 并将其与石墨共混旋涂于ITO导电玻璃上, 作为染料敏化太阳能电池的对电极. 通过SEM观察到聚吡咯纳米粒子粒径在80～100 nm之间, 循环伏安测试表明聚吡咯电极对I₂/I^－电解质氧化还原体系具有较好的催化能力. 光伏电池的电化学交流阻抗测试结果说明掺入石墨后可有效降低聚吡咯对电极的电荷转移阻抗. 以钌染料N719为光敏剂, 聚吡咯/石墨复合电极为对电极组装成的染料敏化太阳能电池, 在AM 1.5 (100 mW•cm^－2) 的模拟太阳光照射下, 得到6.01%的光电转换效率, 达到相同条件下铂对电极性能的92%.     

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。     

聚吡咯的合成与新型双离子电池性能研究

用反相微乳聚合法制备了十二苯磺酸(DBSA)掺杂的导电聚吡咯纳米材料, DBSA既作为表面活性剂又作为掺杂剂, 能够提高聚吡咯的导电性. 用制备出的DBSA-PPy 为正极材料, 石墨为负极材料组装双离子电池, 测试结果表明, C/DBSA-PPy 电池的电化学性能已达到传统锂离子电池的水平, 这是因其具有较高的导电性和特殊掺杂结构的聚吡咯使其电化学性能得到优化.     

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...     

钴铁氧体/膨胀石墨及其聚吡咯复合物的制备和油水分离性能

用化学共沉淀法和原位乳液聚合法分别制备了钴铁氧体/膨胀石墨复合微粒(CF/EG)和钴铁氧体/膨胀石墨/聚吡咯复合物(CF/EG/PPy)。用现代分析技术表征了样品的组成、结构、形貌、电-磁性能和油水分离性能。结果表明,CF粒子已填嵌入到膨胀石墨的层间,CF/EG/PPy复合物的核(CF/EG)和壳(PPy)之间存在着一定的相互作用,样品的油水分离效果与膨胀石墨的层间空隙成正比,其次序为:EG>CF/EG>CF/EG/PPy。磁性的CF/EG微粒回收容易,重复使用性能优良,循环5次的效率不低于90%。     

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。     

金纳米粒子与聚吡咯纳米管的复合及其SERS效应研究

通过柠檬酸盐与HAuCl4水溶液在微沸状态下反应制备的金纳米粒子因其特殊的表面与界面效应在光学、生物学和催化化学领域得到了广泛应用,而聚吡咯(PPy)具有环境稳定性好、电导率高且变化范围大、容易合成等优点,聚吡咯纳米管可用作导电材料、酶封装材料、抗静电材料,也可用于制备传感器、传动器、固体电解质电容器等。     

Electrochemical modification of polypyrrole films for imparting hemocompatible properties to hemosorbent

A method of production of hemosorbent based on thermally expanded graphite is developed. The method involves the electropolymerization of pyrrole on rolled thermally expanded graphite and subsequent cyclic electrochemical doping of polypyrrole film with Cl^? anions. The method enables one to produce a hemosorbent with an open-circuit potential, which is necessary for its biocompatibility.     

Synthesis of graphite nanosheets/AgCl/polypyrrole composites via two-step inverse microemulsion method

An effective process for the synthesis of graphite nanosheets/AgCl/polypyrrole (NanoGs/AgCl/PPy) composites was developed. NanoGs were prepared by treating the expanded graphite with sonication in aqueous alcohol solution. Then nanocomposites were fabricated via in situ polymerization of pyrrole in the presence of NanoGs and AgCl particles through two-step sequentially inverse microemulsion method. The nanoscale dispersion of NanoGs and AgCl particles was evidenced by the SEM and TEM examinations. From the thermogravimetric analysis, the introduction of inorganic nano-AgCl and NanoGs exhibited a beneficial effect on the thermal stability of pure PPy. According to the four-point-probe test, the conductivity of the final NanoGs/AgCl/PPy composites was dramatically increased compared with pure PPy.     

Molecularly Imprinted Polypyrrole for DNA Determination

In this study graphite electrodes modified by a thin DNA‐imprinted polypyrrole layer, which was able to bind specific target‐DNA, are reported. For this aim, electrochemical synthesis of polypyrrole was performed on a pencil graphite electrode by cyclic voltammetry (CV) or by potential pulse sequences (PPS). The modified electrode surface was used for electrochemical determination of target‐DNA by differential pulse voltammetry. According to our best knowledge this is a first report on the application of DNA‐imprinted polymer for the determination of target‐DNA. The results showed that the molecularly imprinted polypyrrole (MIPPy) layer that formed on the carbon electrode surface was sensitive for target‐DNA, while the nonimprinted polypyrrole layer was not sensitive to the same target‐DNA. Comparison of electrodes modified using PPS and CV techniques is presented.     

Development of a Chloride Ion‐Selective Solid State Sensor Based on Doped Polypyrrole‐Graphite‐Epoxy Composite

This paper reports the development and characterization of a solid state potentiometric sensor for chloride ions, based on doped polypyrrole‐graphite‐epoxy composite. The optimum mixture proportion found for polypyrrole:graphite was 60 : 40 meanwhile a 50 : 50 proportion was used for the polypyrrol+graphite:epoxy mixture. The stabilization time was approximately 16 min, while the response times varied within 2 and 23 s. The sensor displayed a sensitivity of 58 mV/decade [Cl^?], and 3×10^?6 M detection limit. The selectivity coefficients showed a greater selectivity to that reported for commercial‐type sensors. The statistical analysis for chlorides' determination in commercial saline serums did not show significant differences respect to data reported by the manufacturers.     

石墨及石墨/双马来酰亚胺减摩树脂复合材料的XRD研究

利用X射线衍射对鳞片石墨、可膨胀石墨、膨胀石墨和纳米石墨薄片以及石墨 /双马来酰亚胺、纳米石墨薄片 /双马来酰亚胺减摩复合材料进行了研究,探讨它们之间在结构上的关系以及以复合材料中双马来酰亚胺预聚体对石墨层间距的影响.实验结果表明:可膨胀石墨中插层剂的插入除了增大石墨层间距外,还减小相邻插层剂未插入的石墨层间距;膨胀石墨的结构除了保留强度很弱的石墨特征峰外,还有大量强度极其微弱、层间距大小不一的峰;超声波对膨胀石墨的结构有整合、均匀化作用;双马来酰亚胺预聚体不能插入鳞片石墨层间,而能插入纳米石墨薄片的层间.     

Molecular Dynamics Simulations of the Orientation and Reorientational Dynamics of Water and Polypyrrole Rings as a Function of the Oxidation State of the Polymer

Summary: Polypyrrole is one of the most widely‐studied conducting polymers due to its steady electrochemical response and good chemical stability in different solvents, including organic and inorganic ones. In this work, we provide for the first time valuable information in atomic detail concerning the steady and dynamic properties of pyrrole rings as a function of the oxidation state of the polymer. The study was carried out by Classical molecular dynamics simulation, where the system was modelled by 256 polypyrrole chains of 10 pyrrole rings each. Water was explicitly introduced in our simulations. Besides the uncharged or reduced state, two steady oxidation states of the polymer have been simulated by introducing a net charge (+1) on 85 and 256 of the polypyrrole chains. To balance the charges emerging in these oxidised states, 85 and 256 chloride ions (Cl⁻¹) respectively, were introduced into the system. From an analysis of the simulated trajectories, the orientation and relaxation times of water and pyrrole rings were evaluated for the different oxidation states of the polymer across the polypyrrole/water interface. The calculated densities for different oxidation states describe the swelling or shrinking process during electrochemical oxidation or reduction respectively. The rotational relaxation times calculated for the polypyrrole rings decrease with increasing oxidation of the polymer, which is in a good agreement with experimental electrochemical data. Almost no variation in pyrrole ring orientation was measured for the different oxidation states of the polymer, even compared with polypyrrole bulk. As regards the water structure in the vicinity of the polypyrrole/water interface, both the orientation and orientation relaxation time were strongly affected by the presence of charges in the polymer. Thus, the water dipole was strongly orientated in the vicinity of the water/polypyrrole interface and its orientational relaxation time increased by one order of magnitude compared with bulk water, even when only one‐third of the total polymer chains were oxidised. The results attained in this work were validated with experimental results, when they were available.

Polypyrrole ring orientation and water orientation at the polypyrrole/water interface. (a) 256 rPPy and (b)171 rPPy + 85 oPPy.     

Preparation and characterization of anode materials using expanded graphite/pitch composite for high-power Li-ion secondary batteries

Expanded graphite was prepared by the intercalation of natural graphite using ammonium peroxodisulfate as an oxidizing agent and a high purity of sulfuric acid as an intercalate. The amounts of oxidizing agent and intercalate were changed to determine the preparation conditions of expanded graphite as the anode material for high-power Li-ion batteries. The expanded graphite was tested as the anode material and further composited with the different amounts of petroleum pitch to improve the electrochemical properties. Although the expanded graphite anode showed the improved electrochemical properties such as initial reversible capacities of around 400 mAh/g and a charge capacity at 5 C-rate of 83 mAh/g as compared with those for the natural graphite anode of 378 and 19.4 mAh/g, respectively, it still had some weak points for a high-power anode material such as low initial efficiency and potential plateaus with the stage characteristic. The anode composites with high performance could be obtained by compositing the expanded graphite and the petroleum pitch at the ratio of 1:2, showing an improved initial efficiency of 78 % and decreased potential plateaus with 389 mAh/g of the initial reversible capacity.     

A Renewable Potentiometric Immunosensor Based on Fe3O4 Nanoparticles Immobilized Anti‐IgG

A renewable potentiometric immunosensor for detection of immunoglobulin G (IgG) has been developed by magnetic force attraction of Fe₃O₄ nanoparticles immobilized goat‐anti‐human IgG antibody. For preparing sensitive film of the sensor, cysteine was bonded on the nano‐Fe₃O₄ particles surface. The cysteine functionalized magnetic nanoparticles was attracted on a solid paraffin carbon paste electrode surface to covalently immobilize of anti‐immunoglobulin G (anti‐IgG) by employing a conventional glutaraldehyde‐crosslinking method. The immunosensor showed a specific response to human immunoglobulin G in the range of 0.1–1.2 ng/mL with a detection limit of 0.023 ng/mL. The immunosensor based on the magnetic nanoparticles was made easily by this method. It can be used expediently, renewed easily and low‐cost relatively. The renewable potentiometric immunosensor with better stability and higher sensitivity can be employed extensively in clinical diagnosis, monitoring of disease and environmental studies and etc.