Fabrication of conducting polymer micro/nanostructures coated with Au nanoparticles for electrochemical sensors

Polypyrrole (PPy) micro/nanostructures coated with Au nanoparticles were prepared by electropolymerization and electro-deposition. Two types of PPy structures, micro-embossed and nanowire forest, were synthesized on patterned gold electrodes using different aqueous solutions, and Au nanoparticles were coated onto the PPy micro/nanostructure surface. The size of the Au nanoparticles ranged from 10 to 100 nm, and the maximum density of the nanoparticles was 73 particles/microm2. The small size and high density of the Au nanoparticles were achieved by optimizing the deposition time and chloroauric acid (HAuCl4) concentration. Cyclic voltammograms of ferrocyanide oxidation showed that the PPy micro/nanostructures coated with Au nanoparticles exhibit good electrochemical activity. These high-performance electrodes can be used in electrochemical sensors because the Au nanoparticles enhance electron transfer and provide a binding site for biomarker molecules, such as DNA, protein, and aptamers.     

Polypyrrole/multiwall carbon nanotube nanocomposites electropolymerized on copper substrate

Polypyrrole/multiwall carbon nanotube (PPy/MWCNT) nanocomposites were successfully synthesized by electropolymerization of MWCNT-dispersed pyrrole solution on the surface of copper electrodes. The obtained nanocomposites were characterized with scanning electron microscopy (SEM), linear sweep voltammetry (LSV) and thermal gravimetric analysis (TGA). Polypyrrole structures which embraced the MWCNTs led to the formation of nanocomposite striated parallel walls. MWCNTs acted as appropriate substrates for electrodeposition of polypyrrole particulate structures and high yield synthesis of PPy was observed on them. Smooth PPy/MWCNT nanocomposite films were obtained on Cu electrodes by decreasing the potential scan rate. Thermogravimetric analysis showed that MWCNTs increased the thermal stability of polypyrrole.     

Peptide nanotube-modified electrodes for enzyme-biosensor applications

The fabrication and notably improved performance of composite electrodes based on modified self-assembled diphenylalanine peptide nanotubes is described. Peptide nanotubes were attached to gold electrodes, and we studied the resulting electrochemical behavior using cyclic voltammetry and chronoamperometry. The peptide nanotube-based electrodes demonstrated a direct and unmediated response to hydrogen peroxide and NADH at a potential of +0.4 V (vs SCE). This biosensor enables a sensitive determination of glucose by monitoring the hydrogen peroxide produced by an enzymatic reaction between the glucose oxidase attached to the peptide nanotubes and glucose. In addition, the marked electrocatalytic activity toward NADH enabled a sensitive detection of ethanol using ethanol dehydrogenase and NAD+. The peptide nanotube-based amperometric biosensor provides a potential new tool for sensitive biosensors and biomolecular diagnostics.     

Three-dimensional mesoporous gold film to enhance the sensitivity of electrochemical detection

Cell-cell and cell-extracellular matrix (ECM) adhesion are fundamental and important in the development of a cell-based chip. In this study, a novel, simple, rapid, and one-step technique was developed for the fabrication of a uniform three-dimensional mesoporous gold thin film (MPGF) onto a gold (Au) coated glass plate based on an electrochemical deposition method. Scanning electron microscopy images demonstrated that the resulting MPGF electrode had uniformly distributed pores with diameters of about 20 nm. The cyclic voltammetric behavior of [Fe(CN)(6)](4-/3-) coupled onto MPGF and Au electrodes demonstrated that the MPGF electrode had a higher electrocatalytic sensitivity and reversibility than the bare Au electrode. The Arg-Gly-Asp (RGD) sequence containing the peptide was immobilized on the MPGF and bare Au substrates. HeLa cancer cells were then cultured on the RGD peptide layer. The successful immobilization of the peptide and cells was confirmed by atomic force microscopy. The cell proliferation and viability were evaluated by cyclic voltammetry and Trypan blue dyeing assay. These results indicated that the RGD/MPGF modified electrodes showed an electrochemical sensitivity in the detection of cancer cells which is approximately three times higher, especially at low cell density, than RGD/Au electrodes. This much improved sensitivity of the MPGF modified electrode demonstrates the potential for the fabrication of a highly sensitive and low-cost cell-based chip for rapid cancer detection.     

GOD/PPy/GC电极的电化学性能研究

采用电沉积法在玻碳(GC)电极表面合成纳米级聚吡咯(PPy),通过扫描电镜得到PPy的形貌。以PPy为载体,通过吸附法固定葡萄糖氧化酶(GOD),得到GOD/PPy/GC电极。利用循环伏安法对GOD/PPy/GC电极的电化学行为进行分析,结果表明,以PPy为载体可以很好地固定GOD并保持其生物活性。在0.1mol/L磷酸盐缓冲溶液中,无任何电子媒介体存在时,GOD/PPy/GC电极显示了很好的电催化性能。     

Electrochemical deposition of polypyrrole nanolayers on discontinuous ultrathin gold films

Ultrathin layers of polypyrrole (PPy) were electrochemically grown between microelectrodes on a Si/SiO(2) substrate. Conducting nanolayers of PPy are directly grown onto ultrathin discontinuous gold (Au) film between the microelectrodes, with thicknesses in the range 10-100?nm. The system therefore forms a novel (PPy/Au) nanocomposite conductor. Atomic force microscopy (AFM) imaging and conductivity measurements indicate that at all thicknesses a relatively uniform film is formed but with significant roughness that reflects the roughness of the metallic island layer. In PPy/Au films with thickness ～10?nm, the small barriers around the gold islands dominate the conduction, and as the film thickness increases to 100?nm the intrinsic conductivity of highly doped PPy dominates the charge transport.     

Characterization of copper manganite oxide-polypyrrole composite electrodes cathodically polarized in acidic medium

We have studied the electrochemical behaviour induced by polarization in sandwich-type composite electrodes with the structure GC/PPy/PPy(Ox)/PPy where GC stands for glassy carbon, PPy for polypyrrole and Ox for Cu_1.4Mn_1.6O₄ nanoparticles. The electrodes were polarized at ?0.45 V/SCE in 0.15 M KCl aqueous solution at pH 2.2 either saturated in Ar or O₂ at 25 °C. The changes occurring on these electrodes were studied using X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (EXAFS and XANES) techniques. In previous work we have shown that when the oxide particles are incorporated into the PPy matrix the Cu⁺ present in the initial oxide suffers dismutation to give Cu²⁺ and metallic Cu. In this work we show that the polarized electrodes also reveal the presence of metallic Cu and Cu²⁺. The data also show that the oxide particles embedded in the polarized electrodes contain Mn³⁺ and Mn⁴⁺, although the Mn³⁺/Mn⁴⁺ ratio is different from that found in the fresh electrodes. The Cl 2p XPS data show that in the electrode polarized in O₂ there is an enhancement of the Cl covalent contribution that appears at 200.8 eV (which is already present in the fresh electrode although with a very small intensity). This result suggests that the oxygen reduction reaction leads to an increase of the OH^? concentration inside the composite electrode that explains the charge transport in PPy at negative potentials.     

Experimental study of culture for mouse fibroblast used conductive polymer films

The purpose of this study is to develop electrodes for electrical stimulation of the nervous system using conductive polymers, polypyrrole (PPy) and/or poly(3,4-ethylenedioxythiophene), PEDOT. We evaluated biocompatibility in fibroblast and/or myoblast of mouse. Cultured cells on PPy and/or PEDOT extended their neuritis and survived over a week. These experiments have demonstrated that conductive polymers such as PPy, PEDOT, etc. have high biocompatibility, and PPy and/or PEDOT are applicable to nerve stimulation electrodes.     

Polypyrrole nanorod networks/carbon nanoparticles composite counter electrodes for high-efficiency dye-sensitized solar cells

Polypyrrole(PPy) nanorod networks with a high electrical conductivity of 40 S cm(-1) have been obtained in a high yield by employing an ion association of heparin-methylene blue as a new morphology-directing agent. The polypyrrole nanorod networks are mixed with different content of carbon nanoparticles to make PPy nanorod networks/carbon nanoparticles(PPy/C) counter electrodes. It is found that the PPy/C composite with 10% carbon content shows a lower charge transfer resistance and better catalytic performance for the reduction of I(3)(-), compared with the pristine PPy and carbon electrodes. The better catalytic performance is attributed to the interaction of the superior electrocatalytic activity of the unique polypyrrole nanorod networks and the carbon nanoparticles, which can accelerate triiodide reduction and electron transfer in the electrode. Under standard AM 1.5 sunlight illumination, the dye-sensitized solar cell based on the PPy/C composite with 10% carbon content as the counter electrode demonstrates a high efficiency of 7.2%, which is much higher than that of pristine PPy and carbon electrode-based DSCs and comparable to that of the thermal decomposed Pt-based DSC.     

PPy/APS-SiO2纳米导电复合材料的合成与表征

用化学氧化聚合复合方法合成聚吡咯／二氧化硅(PPy／SiO2)纳米复合材料。首先用不同百分含量的氨丙基三乙氧基硅烷(APS)处理SiO2，然后以水为反应介质，通过化学聚合方法合成PPy／APS—SiO2纳米复合材料，并利用红外光谱、热失重、X射线光电子能谱(XPS)、透射电镜和四探针等手段进行表征。结果表明，用APS处理过的SiO2合成的复合材料PPy含量增加，且通过XPS看出PPy／APS—SiO2表面富有PPy，而PPy／SiO2表面富有SiO2。其中用1％APS—SiO2合成的复合材料电导率最高，为38．46S／cm。     

硅烷偶联剂在PPy/SiO2纳米导电复合材料制备中的应用

描述了一种合成PPy／SiO2纳米复合材料的新方法。首先用不同百分含量的氨丙基三乙氧基硅烷(APS)处理SiO2,然后通过化学氧化聚合法合成PPy／APS—SiO2纳米复合材料。文中讨论了偶联剂的使用对复合材料的影响及其作用机理。结果表明,用APS处理过的SiO2合成的复合材料其PPy含量、电导率和稳定性都有很大提高,其中用1％APS—SiO2合成的复合材料电导率最高,为38．4S／cm。文中还阐述了偶联剂的预处理对PPy／SiO2纳米复合材料形貌的影响。     

New fabrication technique of conductive polymer/insulating polymer composite films and evaluation of biocompatibility in neuron cultures

Poly(vinyl alcohol), PVA, produces a flexible composite polymer film with electrical, optical and electrochemical properties very similar to those of polypyrrole (PPy). The rate of electrochemical polymerization depends on the diffusion rate of the electrolyte across the PVA film to the indium tin oxide (ITO) electrode. In particular, a solvent with a hydrophilic nature easily penetrates into the PVA film. By applying this new process, we demonstrate a unique method of forming an electrically conductive pattern in PVA film. It will be possible to develop electrodes for electrical stimulation of the nervous system using the conducting polymer, PPy. Then, by applying a similar technique, we fabricated poly(3,4-ethylenedioxythiophene), PEDOT/PVA, composite films and investigated their basic electrochemical properties. Moreover, in this study, in order to develop a novel cell-culture system which makes it possible to communicate with cultured cells, fibroblasts were cultured on PPy- and PEDOT-coated ITO conductive glass plates for 7 days. The result reveals that the PPy and PEDOT films support the secretory functions of the cells cultured on its surface. The PPy- and PEDOT-coated electrodes may be useful to culture the cells on.     

Synthesis of core-shell Au@polypyrrole nanocomposite using a dendrimer-template approach

Conducting polymeric nanostructures have been reported recently, which were produced from polypyrrole (PPy), including hollow nanocapsules, nanofibers, nanoporous membranes, nanowires, and nanofilms. In most cases, new synthetic routes were used aimed at controlling specific properties of these conducting nanostructures at the molecular level. In this communication we present a new chemical route to synthesize polypyrrole-based nanocomposites, in which polyamidoamine (PAMAM) dendrimers encapsulating Au nanoparticles are used as template. The two-step synthesis comprises the reduction of Au nanoparticles inside PAMAM molecules followed by PPy polymerization around the PAMAM-Au nanoparticles. The structure of the core-shell PAMAM-gold@polypyrrole nanospheres comprises a 40 nm PPy shell enclosing a core of 3 nm gold nanoparticles, as revealed by Transmission Electronic Microscopy (TEM). This new, environmentally-friendly approach may be suitable to produce hybrid nanomaterials for applications in catalysis, batteries, sensors, and micro/nanoelectronic devices.     

Nonlinear transport in hybrid Polypyrrole-gold nanostructures

We have studied charge transport in nanometer scale films of polypyrrole (PPy) that were grown electrochemically onto discontinuous ultrathin films of gold. The gold films consisted of 100 nm size islands, separated from each other by nanometer-size gaps. The thickness of PPy can be varied from 30 to 200 nm. The I-V characteristics of these hybrid PPy-Au nanostructures show strong non-linearity at low temperatures, and in particular for the more insulating samples. The hopping transport is further verified from the log I versus V(1/4) plots. Furthermore, the I-V data follow an empirical relation dlogI/dV(1/4) - T(-1/2).     

Hybrid composite material based on polythiophene derivative nanofibers modified with gold nanoparticles for optoelectronics applications

Conjugated polymers have been extensively applied as active materials in nanostructured platforms for optical and electrical devices. The incorporation of metal nanoparticles (NPs) into the polymer-based platform arises as a strategy to develop novel hybrid functional nanocomposites with enhanced electrical and optical properties. However, efficient and simple processing routes to produce such nanocomposites are still on demand. In this work, we present an effective route to obtain functional nanocomposites based on electrospun nanofibers coated with gold nanoparticles, displaying interesting optical and electrical properties. Polymethyl methacrylate (PMMA) electrospun nanofibers doped with poly(3-hexyl thiophene-2,5-diyl) (P3HT) were obtained by the electrospinning technique, and displayed a strong red emission centered at 650 nm assigned to P3HT. Such nanofibers were deposited on to fluorine-doped tin oxide electrodes and with modified with gold nanoparticles (AuNPs) in order to produce hybrid composite materials. The performance of electrodes modified with PMMA/P3HT-AuNPs composite material was evaluated by impedance spectroscopy and revealed an enhancement of electron transfer kinetics, which indicates it as a potential platform for optical and electrochemical (bio)sensors.     

Detection of attomole quantities [correction of quantitites] of DNA targets on gold microelectrodes by electrocatalytic nucleobase oxidation

The electrochemical detection of nucleic acid targets at low concentrations has a number of applications in diagnostics and pharmaceutical research. Self-assembled monolayers of alkanethiol-derivatized oligonucleotides on gold electrodes provide a useful platform for such detectors, and the electrocatalytic oxidation of nucleobases included in the DNA targets is a particularly sensitive method of electrochemical detection. A strategy has been developed for combining these two aspects by substituting either 7,8-dihydro-8-oxoguanine (8G) or 5-aminouridine (5U) into DNA targets. Upon hybridization of targets containing these modified nucleobases, electrocatalytic signals at probe-modified gold electrodes are observed in the presence of Os(bpy)(3)(2+), which oxidizes both 8G and 5U upon oxidation to the Os(III) state. Self-assembled monolayers were prepared on both macro (1.6 mm) and micro (25 microm) gold electrodes using published procedures involving C6-terminated alkanethiol oligonucleotides and mercaptohexanol as the diluent. The extent of electrode modification by the modified probe was assessed using radiolabeling and a standard chronocoulometry method; both approaches gave loading levels within expected ranges ((1-6) x 10(12) molecules/cm(2)). Hybridization of the modified targets where the non-native nucleobase was incorporated by solid-phase synthesis produced electrocatalytic signals from strands that were independently detected using radiolabeling and chronocoulometry. This result was used as a basis to develop an on-electrode amplification scheme where Taq polymerase was used to extend the immobilized DNA probes from solution-phase polymeric templates using modified nucleotriphosphates. This reaction produced an electrode that was modified with extended DNA containing the appropriate modified nucleotide. Radiolabeled nucleotide triphosphates were used to confirm the desired on-electrode DNA synthesis. When these electrodes were cycled in the presence of Os(bpy)(3)(2+), electrocatalytic signals were observed when as little as 40 amol (400 fM) of the desired target was present in the hybridization solution.     

Development and characterization of fluorine tin oxide electrodes modified with high area porous thin films containing gold nanoparticles

Different electrode materials are prepared using fluoride doped tin oxide (FTO) electrodes modified with high area porous thin films of metal oxides containing gold nanoparticles. Three different metal oxides (TiO₂, MgO and SnO₂) have been assayed to this end. The effect of the metal oxide nature and gold loading on the structure and performance of the modified electrodes was examined by Scanning Electron Microscopy, Transmission Electron Microscopy, X-Ray Diffraction (XRD), Diffuse Reflectance Spectroscopy and electrochemical techniques. XRD measurements reveal that MgO electrodes present the smallest gold nanoparticles after the sintering step however, the electrochemical response of these electrodes shows important problems of mass transport derived from the high porosity of these materials (Brunauer Emmett Teller area of 125 m²/g). The excellent sintering properties of titania nanoparticles result in robust films attached to the FTO electrodes which allow more reliable and reproducible results from an electroanalytical point of view.     

Electrochemical surface plasmon resonance measurement based on gold nanohole array fabricated by nanoimprinting technique

In this paper, we describe our development of an electrochemical surface plasmon resonance (EC-SPR) measurement device based on a bottom-filled gold nanohole array. The polymer based gold nanohole array was fabricated with a UV nanoimprint technique and electron beam gold deposition. Direct reflection mode measurement was used to monitor the SPR dip in the reflection spectra. A cyclic voltammogram was also operated by using the standard three electrodes containing working electrode having a gold nanohole array and counter and reference electrodes. The gold nanohole array was modified with an osmium-poly(vinylpyridine)-wired horseradish peroxidase (Os-gel-HRP) film, and its redox state induced by the change in potential was monitored simultaneously. The redox state of the local film was obtained simply by scanning the sample substrate stage. The substrate modified with Os-gel-HRP film was incorporated in a microfluidic chip, and then the hydrogen peroxide was determined in terms of the redox change in the Os complex mediator from the slope of the SPR dip shift. The linear relation of hydrogen peroxide from 10 to 250 μM was successfully monitored, and a high conversion efficiency was realized.     

Synthesis and characterization of gold–polypyrrole film composite

Polypyrrole (PPy) coatings have potential applications in batteries, fuel cells, sensors, anti-corrosion coatings, and drug delivery systems. In this article, PPy film coating on the electrode of quartz crystal microbalance (QCM) was exposed to acidic aqueous HAuCl₄ solution. The reduction for gold ions took place and gold particles were produced at the film surface. The gold content at the PPy film was monitored by using QCM. The concentration of gold uptake increases as the original concentration of HAuCl₄ solution increases. The morphology of the film before and after the deposition of the gold particles was studied by the scanning electron microscopy coupled with energy dispersive X-ray spectrometry. The gold particles are of undefined shape and have diameters around 200–600 nm. However, the image of the composite powder shows that gold particles of sizes 100–120 nm are distributed over the surface of the polymer particles with some aggregation. Infrared spectroscopy and X-ray diffraction were used to characterize the composite.     

Radiolytic synthesis of conducting polypyrrole/carbon nanotube composites

Conducting polypyrrole (PPy)/multi-wall carbon nanotube (MWNT) composites have been synthesized by the in situ gamma radiation-induced chemical polymerization method at room temperature. The resulting cable-like morphology of the composite (PPy–MWNT) structures was characterized by elemental analysis, Fourier transform infrared, field-emission scanning electron microscope, thermal gravimetric analysis, X-ray photoelectron spectroscopy, and transmission electron microscope. The standard four-point probe method was utilized for measuring the conductivity of the samples. We observed no significant chemical reaction between the polymer and carbon nanotube, which only showed that polypyrrole chains are tightly coated on to MWNT. The physical properties of the composites (PPy–MWNT) were measured and showed that the MWNT were modified by conducting polypyrrole with various properties enhanced.