单缺位磷钨杂多酸聚吡咯修饰电极的制备及其电化学性能

在玻碳电极（ＧＣ）上,用电化学方法将单缺位Ｄａｗｓｏｎ型磷钨杂多酸盐Ｋ１０Ｐ２Ｗ１７Ｏ６１·１５Ｈ２Ｏ的阴离子（Ｐ２Ｗ１７）掺杂到聚吡咯（ＰＰＹ）薄膜中制成的Ｐ２Ｗ１７／ＰＰＹ／ＧＣ化学修饰电极,既保持了该杂多酸的电化学活性和电催化性能,又具有良好的稳定性与灵敏度。     

Fabrication of Tiron Doped Poly-Pyrrole/Carbon Nanotubes on Low Resistance Monolayer-Modified Glassy Carbon Electrode for Selective Determination of Dopamine

In this paper, we described a novel sensor based on tiron-doped polypyrrole and carbon nanotubes (CNTs) fabricated on low resistance monolayer-modified glassy carbon electrode. First, the dodecylamine monolayer was chemically modified. Second, CNTs were controllably adsorbed onto dodecylamine. Then, tiron doped polypyrrole was electro-deposited on the CNTs film. The layer-by-layer modified electrode was sensitive to dopamine, while it made no response to even high concentration of ascorbic acid. Parameters influencing the dopamine response were optimized. High performance of the sensor was obtained, such as wide concentration range, low detection limit (3 nM), low background current, high stability, and reproducibility.     

Amperometric Glucose Biosensor on Layer by Layer Assembled Carbon Nanotube and Polypyrrole Multilayer Film

An amperometric glucose biosensor on layer by layer assembled carbon nanotube and polypyrrole multilayer film has been reported in the present investigation. Homogeneous and stable single wall carbon nanotubes (SWNTs) and polypyrrole (PPy) multilayer films were alternately assembled on platinum coated Polyvinylidene fluoride (PVDF) membrane. Since conducting polypyrrole has excellent anti‐interference ability, protection ability in favor of increasing the amount of the SWNTs on platinum coated PVDF membrane and superior transducing ability, a layer by layer approach of polypyrrole and carbon nanotubes has provided an excellent matrix for the immobilization of enzyme. The layer‐by‐layer assembled SWNTs and PPy‐modified platinum coated PVDF membrane is shown to be an excellent amperometric sensor over a wide range of concentrations of glucose. The glucose oxidase (GOx) was immobilized on layer by layer assembled film by a physical adsorption method by cross linking through Glutaraldehyde. The glucose biosensor exhibited a linear response range from 1 mM to 50 mM of glucose concentration with excellent sensitivity of 7.06 μA/mM.     

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.     

Enantioselective uptake of amino acids using an electromodulated column packed with carbon fibres modified with overoxidised polypyrrole

A column packed with carbon fibres modified with overoxidized polypyrrole was utilised for the enantioselective uptake of glutamic acid. The polypyrrole prepared with L-glutamate as a dopant was electrochemically overoxidised to create a complementary cavity for the dopant. The target amino acid enantiomers were taken up and released by applying potential to the carbon fibre stationary phase. The uptake performance of an overoxidised polypyrrole modified carbon fibre electrode was investigated by optimising various important overoxidation parameters such as an overoxidation medium and applied potential. Under optimised conditions of overoxidation and with a column wash between the consecutive measurements, the reproducible uptake of L-glutamic acid was almost six times higher than that of D-glutamic acid. Further, in a comparison, the recognition ability of overoxidized polypyrrole with a pseudo-template cavity was examined.     

Nonenzymatic sensing of glucose using a carbon ceramic electrode modified with a composite film made from copper oxide,overoxidized polypyrrole and multi-walled carbon nanotubes

Microchimica Acta - A carbon ceramic electrode was modified with a thin film composed of overoxidized polypyrrole, CuO and multi-walled carbon nanotubes. The surface morphology, electrochemical...     

Surface-imprinted nanostructured layer-by-layer film for molecular recognition of theophylline derivatives

In this article we report the introduction of the cooperativity of various specific interactions combined with photo-cross-linking of the interlayers to yield binding sites that can realize better selectivity and imprinting efficiency of a surface molecularly imprinted LbL film (SMILbL), thus providing a new approach toward fabrication of nanostructured molecularly imprinted thin films. It involves preassembly of poly(acrylic acid) (PAA) conjugated of the theophylline residue template via a disulfide bridge, denoted as PAAtheo 15, in solution, and layer-by-layer (LbL) assembly of PAAtheo 15 and a positively charged photoreactive diazo resin (DAR) to form multilayer thin film with designed architecture. After photo-cross-linking of the film and template removal, binding sites specific to 7-(beta-hydroxyethyl)theophylline (Theo-ol) molecules are introduced within the film. Binding assay demonstrates that the SMILbL has a high selectivity of SMILbL to Theo-ol over caffeine. A control experiment demonstrates that the selectivity of SMILbL derives from nanostructured recognition sites among the layers. The imprinting amount per unit mass of the film can be 1 order of magnitude larger than that of the conventional bulk molecular imprinting systems. As this concept of construction SMILbL can be easily extended to the other molecules by the following similar protocol: its applications in building many other different molecular recognition systems are greatly anticipated.     

以分子印迹电聚合膜为仿生受体检测辛可宁

结合分子印迹技术和电聚合自组装技术制备了以辛可宁为模板的印迹聚合膜．膜的厚度可通过改变扫描次数和速度加以控制,因此可在一定程度上克服传统印迹材料固有的传质较慢等缺点．实验中采用铁氰化钾作为探针分子．当模板分子被洗脱后,铁氰化钾小分子可以自由通过聚合膜所形成的识别孔穴,并在电极表面发生氧化还原反应．当识别孔穴捕获辛可宁分子后,     

掺杂聚吡咯钨磷钴和钨磷镍三元杂多酸的电合成及其电化学性质

电化学性能;掺杂聚吡咯钨磷钴和钨磷镍三元杂多酸的电合成及其电化学性质     

Enhancement of oxygen reduction at Co-porphyrin catalyst by supporting onto hybrid multi-layered film of polypyrrole and polyoxometalate-modified gold nanoparticles

Three-dimensional multi-layered films (on glassy carbon) composed of networks of polyoxometallate (PMo₁₂O₄₀ ³⁻)-modified gold nanoparticles linked together through the alternately deposited ultra-thin layers of polypyrrole have served as active supports for Co-porphyrin catalytic centers. The hybrid organic-inorganic films (supports) have been prepared by using the layer-by-layer approach. The fact that polyanionic (phosphomolybdate) adsorbates on gold nanoparticles are attracted by positively charged sites of conducting polymer (polypyrrole) structures leads to the stabilizing effect and facilitates distribution of Au nanostructures. The systems have been characterized using scanning electron microscopy, as well as with chronoamperometric and voltammetric techniques. By supporting Co-porphyrin centers onto the hybrid film of the polymer-linked phosphomolybdate-stabilized gold nanoparticles, significant electrocatalytic enhancement effects (namely voltammetric current increases) have been observed during the electroreduction of oxygen in acid medium relative to a standard response of the simple porphyrin deposit on glassy carbon measured under analogous conditions. Among important issues is the high activity of the hybrid film (support) itself toward the reductive decomposition of hydrogen peroxide to water. When it comes to performance of the Co-porphyrin-containing system, it is reasonable to expect that the O₂ reduction process is initiated at Co-porphyrin catalytic sites (two-electron reduction to H₂O₂) and continued (two-electron reduction to H₂O) at the hybrid film containing gold nanoparticles dispersed within the highly porous cauliflower-like structures of polypyrrole multi-layers. While the gold networks facilitate charge distribution within the hybrid electrocatalytic film, non-covalent π-π interactions of porphyrin rings with polypyrrole interlayers and charge transfers between negatively charged (PMo₁₂O₄₀ ³⁻ modified) gold nanoparticles and positively charged nitrogen sites of polypyrrole could also cause synergism.

     

A novel nitrite sensor based on graphene/polypyrrole/chitosan nanocomposite modified glassy carbon electrode

A novel nitrite sensor was fabricated based on a graphene/polypyrrole/chitosan nanocomposite film modified glassy carbon electrode. The nanocomposite film was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and Raman spectroscopy. The electron transfer behaviour of the modified electrodes was investigated in [Fe(CN)(6)](3-)/(4-) redox probe using cyclic voltammetry and electrochemical impedance spectroscopy. Differential pulse voltammetry and amperometry were used to study the electrochemical properties of the proposed sensor. Under optimum conditions, the sensor exhibited good reproducibility and stability for nitrite determination. Linear response was obtained in the range of 0.5-722 μM with a detection limit of 0.1 μM (S/N = 3) for nitrite determination.     

Voltammmetric Determination of Uric Acid in the Presence of Ascorbates Using Overoxidized Polypyrrol

ＶｏｌｔａｍｍｍｅｔｒｉｃＤｅｔｅｒｍｉｎａｔｉｏｎｏｆＵｒｉｃＡｃｉｄｉｎｔｈｅＰｒｅｓｅｎｃｅｏｆＡｓｃｏｒｂａｔｅｓＵｓｉｎｇＯｖｅｒｏｘｉｄｉｚｅｄＰｏｌｙｐｙｒｒｏｌｅＦｉｌｍＣｏａｔｅｄＧｌａｓｓｙＣａｒｂｏｎＥｌｅｃｔｒｏｄｅｓＫＡＮＧ...     

Molecularly imprinted polypyrrole nanonecklaces for detection of herbicide through molecular recognition-amplifying current response

Molecularly imprinted polypyrrole (PPy) nanonecklaces were facilely synthesized through a two-step oxidative polymerization route for the amperometric detection of non-electrochemically active herbicide. It has been demonstrated that dissolved oxygen can preoxidize pyrrole to form PPy oligomer bundles, which further self-assemble into necklace-like micelles in the presence of cetyltrimethylammonium bromide. Subsequently, these microstructures were immediately gelled through quick polymerization of residual pyrrole monomers, leading to the formation of PPy nanonecklaces. Meanwhile, herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was synchronously imprinted into the formed PPy and highly dense imprinted sites were generated in PPy nanonecklaces because the necklace-like structure with microgaps/pores provides the facile and complete removal of templates. The imprinted nanonecklaces exhibit the high capacity and fast kinetics to uptake 2,4-D molecules, and produce a imprinting factor of ∼4.2. Importantly, the recognition and binding to 2,4-D significantly amplify the current response by a factor of 8 times in amperometric measurements, providing a sensitive detection of 2,4-D. The molecular imprinting strategy opens a novel avenue to the direct detection of non-electrochemically active species in a more convenient, simpler and cheaper way than the traditional competition-displacing approaches.     

掺杂靛红的聚吡咯膜的电色效应

制备了掺杂靛红的聚吡咯（ＰＰｙ）膜修饰电极，这种功能化ＰＰｙ膜电极具有很好的电色效应，其颜色变化明显，响应时间短，稳定性好，是一种新型电色材料。     

磷钼钒类杂多酸—聚吡咯薄膜修饰电极及其电催化性能研究

合成了磷钼类杂多酸，采用电化学方法首次在导电基体玻碳电极上研制了磷钼钒类杂多酸－聚吡咯薄膜修饰电极，该电极性能稳定，经久耐用，对膜修饰电极的电化学行为进行了表征，研究了膜修饰电极酸性水溶液中的氯酸根、溴酸根，、磺酸根，亚硝酸根，三阶铁离子，     

氧在铁卟啉/聚吡咯膜修饰电极上的还原

用旋转环盘电极技术研究含中位四（ 对磺基苯基） 卟啉合铁（ＦｅＴＰＰＳ） 的聚吡咯膜覆盖的玻碳电极上的氧还原过程． 结果表明该修饰膜的存在降低了氧还原的过电位,还原产物中有Ｈ２Ｏ２ ,过程用异相氧化还原催化（ＥＣ） 机理解释． 与金或铂比较,碳是较好的电极基体材料,适合于产生破坏水中有机物所需的过氧化物． 在酸性介质中氧在该膜修饰电极上的还原速度比在中性介质中大,由ＫｏｕｔｅｃｋｙＬｅｖｉｃｈ 关系式求出修饰膜中催化剂和分子氧反应的表观速度常数值．     

Enantioselective uptake of amino acid with overoxidized polypyrrole colloid templated with L-lactate

An overoxidized polypyrrole colloid, which can recognise enantiomers of amino acids has been prepared by a newly developed molecular imprinting technique. A polypyrrole colloid, which had been polymerised from a mixture of pyrrole (monomer), polyvinylpyrrolidone (steric stabiliser), peroxodisulfate (oxidant) and L-lactate (dopant), was overoxidized to create a dopant-complementary cavity. The enantioselectivity of the overoxidized colloid was evaluated by comparing the uptake of L-alanine and L-cysteine with that of the respective D-enantiomers. The L/D uptake ratios for these amino acids were about 2, while phenylalanine showed suppressed uptake for both the enantiomers. The absence of phenylalanine uptake can be explained in terms of the molecular size, which is too large to be accommodated by the cavity created by L-lactate. In contrast, a colloid templated with L-phenyllactate took up L-phenylalanine with a higher enantioselectivity of about 7. A colloid templated with L-lactate was applied to surface chirality analysis through enantioselective adsorption on cysteine-modified gold surfaces. Quartz microbalance experiments and scanning electron microscope observation of the gold surface revealed that the colloidal particle has higher affinity to a surface modified with L-cysteine than to one modified with D-cysteine.     

Development of a thickness shear mode acoustic sensor based on an electrosynthesized molecularly imprinted polymer using an underivatized amino acid as the template

The preparation and characterization of electrosynthesized poly(o-phenylenediamine) (iPoPD) as a molecular imprinting material were studied by an in situ quartz crystal impedance method. The changes of delta f0, delta R1, delta L1 and delta C0 suggest that the polymer film was compact and rigid. The thickness shear mode (TSM) acoustic sensor modified with this material exhibits molecular recognition ability to the template molecule of DL-phenylalanine. In the range 2-20 mM, a linear relationship between the frequency shift delta f0 and logC was found from the calibration graph. Scatchard analysis of the relevant calibration graph offers information on the equilibrium of the binding interaction and the recognition sites. Using this electropolymerization technology, the preparation of the sensor was very simple and the reproducibility of preparation was very good. In particular, it offers possibilities for sensor miniaturization.     

Recognition of gram-negative and gram-positive bacteria with a functionalized conducting polymer film

In this work, we successfully developed bacterial templates on the surface of an overoxidized polypyrrole film using both gram-negative and gram-positive bacteria in which bacterial surface chemical structures are precisely transferred at a molecular level. The sensor film identified target bacteria within minutes through a unique combination with dielectrophoresis. The bacterial cavities had high selectivity for distinguishing specific target bacteria in bacterial mixtures containing gram-negative (Escherichia coli and Pseudomonas aeruginosa) and gram-positive (Bacillus subtilis and Staphylococcus aureus) bacteria. This rapid and specific recognition system will enable not only bacterial sensing but also analysis of various biological species.     

Permselectivity of neurotransmitters at overoxidized polypyrrole-film-coated glassy carbon electrodes

The permselectivity of neurotransmitters such as dopamine, epinephrine, and norepinephrine at overoxidized polypyrrole (OPPY)-film-coated glassy carbon electrodes has been investigated. The chemically-modified electrodes exhibit attractive permselectivity and antifouling properties of rejecting anionic species, e.g. ascorbate, etc. Compared with the response of neurotransmitters at modified electrodes overoxidized in phosphate buffer solution (pH 7.4), higher sensitivity and reversibility response can be obtained at modified electrodes overoxidized in sodium hydroxide solution. The effect of film thickness on the permselective response was tested. Rotating disk electrode experiments were used to determine the apparent diffusion coefficients of several electroactive solutes in the OPPY films. The influence of the hydrophobicity of the organic ions on the permeability within the polymer films was discussed. Dopamine and epinephrine were determined at the 1 x 10(-6)-1 x 10(-4) M level by means of voltammetry after an exposure period of 2 min in 0.1 M phosphate buffer (pH 7.4) with detection limits of 8 x 10(-7) M and 6 x 10(-7) M respectively.