Recent Progress in the Development of Conducting Polymer‐Based Nanocomposites for Electrochemical Biosensors Applications: A Mini‐Review

Among various immobilizing materials, conductive polymer‐based nanocomposites have been widely applied to fabricate the biosensors, because of their outstanding properties such as excellent electrocatalytic activity, high conductivity, and strong adsorptive ability compared to conventional conductive polymers. Electrochemical biosensors have played a significant role in delivering the diagnostic information and therapy monitoring in a rapid, simple, and low cost portable device. This paper reviews the recent developments in conductive polymer‐based nanocomposites and their applications in electrochemical biosensors. The article starts with a general and concise comparison between the properties of conducting polymers and conducting polymer nanocomposites. Next, the current applications of conductive polymer‐based nanocomposites of some important conducting polymers such as PANI, PPy, and PEDOT in enzymatic and nonenzymatic electrochemical biosensors are overviewed. This review article covers an 8‐year period beginning in 2010.     

Enhanced electrical properties of PEDOT:PSS via synergistic effect

As a representing conducting polymer, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) has been widely employed in organic electronics. However, the electrical conductivity for pristine PEDOT:PSS is only between 0.1 and 0.5 S/cm. In order to enhance the conductivity, the silver nanowires (Ag NWs) were synthesized to dope PEDOT:PSS. It was found the electrical conductivity of PEDOT:PSS was improved to about 200 S/cm with Ag NWs. When double-wall carbon nanotube (DWCNT) was employed together with Ag NWs, the electrical conductivity was further improved to over 2800 S/cm. We proposed the synergistic working model between Ag NWs and CNTs for such enhancement. In this work, UV-vis-NIR spectra and SEM images were also employed to investigate the mechanism of electrical conductivity enhancement.     

Protein-sheathed SWNT as a versatile scaffold for nanoparticle assembly and superstructured nanowires

One dimensional (1D) nanostructures have many possible applications in electronic, optical, and sensing devices associated with their nanosized lateral dimensions. In this regard, a general and bottom-up strategy to synthesize 1D nanoparticle arrays and conductive nanowires with a facile structural/compositional control is highly desired. We herein report a protein-sheathed single walled carbon nanotube (SWNT) that satisfies the criteria for an ideal template to assemble micron-long gold nanoparticle (AuNP) linear arrays with high structural rigidity. The resulting AuNP array has minimized inter-particle gaps, which is especially useful to template the overgrowth of Ag, Pd, and Pd/Ag metals into continuous nanowires (Au@M, M=Ag, Pd, Ag/ Pd). Our method successfully overcomes the incompatibility between carbon and metal materials, and the resulting superstructured metal nanowires have a tunable diameter below 100 nm and a shape closely replicating a SWNT. The Ag nanowires are composed of coalesced Au@Ag coreshell nanoparticles, while the Pd and Pd/Ag nanowires are made of very fine Pd nanocrystallites around the AuNP cores. These unique structural features are pivotal to various applications including surface enhanced Raman scattering (SERS), electrocatalysis, and gas sensors.     

Collision of a long DNA molecule with an isolated nanowire

We provide an experimental test of the universal behavior arising in simulations of the electrophoretic collision of a long DNA molecule with an isolated, thin post. Our experiments take advantage of a robust protocol to embed matrices of circa 100 nm radius ZnO nanowires in a microfluidic channel. The density and height of the nanowires are easily controlled by the seeding and growth conditions. Single-molecule videomicroscopy of λ-DNA electrophoresis in a sparse nanowire array shows that the average holdup time decays exponentially with the impact parameter, in agreement with simulations. Only at the largest electric field studied here does the hooking probability approach that for an infinitesimally thin post.     

Coordinated organogel templated fabrication of silver/polypyrrole composite nanowires

A new method to fabricate metal/conducting polymer composite nanowires is presented by taking silver/polypyrrole composite nanowires as an example.A silver(Ⅰ)-coordinated organogel as template was prepared firstly,and redox-polymerization of pyrrole took place on the gel fiber,giving product of silver/polypyrrole nanowires.The silver/polypyrrole nanowires were characterized by multiple techniques.This strategy could be carried out in one-step procedure at room temperature,and it proves the utility of coordinated organogels in template synthesis of polymer nanostructures.     

Manipulating Nanowire Assembly for Flexible Transparent Electrodes

Manipulating nanowire assembly could help the design of hierarchical structures with unique functionalities. Herein, we first report a facile solution‐based process under ambient conditions for co‐assembling two kinds of nanowires which have suitable composition and functionalities, such as Ag and Te nanowires, for the fabrication of flexible transparent electrodes. Then Te nanowires can be etched away easily, leaving Ag nanowire networks with controllable pitch. By manipulating the assembly of Ag and Te nanowires, we can precisely tailor and balance the optical transmittance and the conductivity of the resulting flexible transparent electrodes. The network of Ag nanowires which have tunable pitch forms a flexible transparent conducting electrode with an averaged transmission of up to 97.3 % and sheet resistances as low as 2.7 Ω/sq under optimized conditions. The work provides a new way for tailoring the properties of nanowire‐based devices.     

Electrochemistry of conductive polymers 39. Contacts between conducting polymers and noble metal nanoparticles studied by current-sensing atomic force microscopy

Electrical properties of contacts formed between conducting polymers and noble metal nanoparticles have been examined using current-sensing atomic force microscopy (CS-AFM). Contacts formed between electrochemically prepared pi-conjugated polymer films such as polypyrrole (PPy), poly(3-methylthiophene) (P3MeT), as well as poly(3,4-ethylenedioxythiophene) (PEDOT) and noble metal nanoparticles including platinum (Pt), gold (Au), and silver (Ag) have been examined. The Pt nanoparticles were electrochemically deposited on a pre-coated PPy film surface by reducing a platinum precursor (PtCl62-) at a constant potential. Both current and scanning electron microscopic images of the film showed the presence of Pt islands. The Au and Ag nanoparticles were dispersed on the P3MeT and PEDOT film surfaces simply by dipping the polymer films into colloid solutions containing Au or Ag particles for specified periods (5 to approximately 10 min). The deposition of Au or Ag particles resulted from either their physical adsorption or chemical bonding between particles and the polymer surface depending on the polymer. When compared with PPy, P3MeT and PEDOT showed a stronger binding to Au or Ag nanoparticles when dipped in their colloidal solutions for the same period. This indicates that Au and Ag particles are predominantly linked with the sulfur atoms via chemical bonding. Of the two, PEDOT was more conductive at the sites where the particles are connected to the polymer. It appears that PEDOT has better aligned sulfur atoms on the surface and is strongly bonded to Au and Ag nanoparticles due to their strong affinity to gold and silver. The current-voltage curves obtained at the metal islands demonstrate that the contacts between these metal islands and polymers are ohmic.     

Inspired by Grape Seed and Wine: Tannic Acid as a Modified Coating for Fabricating Highly Flexible,Transparent and Conductive Film

The application of transparent conductive films in flexible electronics has shown promising prospects recently. Tannic acid(TA) was successfully applied to modifying the surface of polydimethylsiloxane(PDMS) to fhbricate highly flexible, transparent and conductive Ag nanowires(NWs) based films. TA modification transformed the PDMS surface from hydrophobicity into hydrophilicity without decreasing the transparence. A sheet resistance(Rs) of 80 Ω/cm^2 with an optical transmittance of 94% was achieved, which was superior to that of indium tin oxide(ITO) films. More importantly, the TA layer enhanced the interaction between Ag NWs and the PDMS substrate. The Ag NWs films on TA modified PDMS substrate exhibited excellent stability in Rs when subjected to a bending test.     

Chemical wiring and soldering toward all-molecule electronic circuitry

Key to single-molecule electronics is connecting functional molecules to each other using conductive nanowires. This involves two issues: how to create conductive nanowires at designated positions, and how to ensure chemical bonding between the nanowires and functional molecules. Here, we present a novel method that solves both issues. Relevant functional molecules are placed on a self-assembled monolayer of diacetylene compound. A probe tip of a scanning tunneling microscope is then positioned on the molecular row of the diacetylene compound to which the functional molecule is adsorbed, and a conductive polydiacetylene nanowire is fabricated by initiating chain polymerization by stimulation with the tip. Since the front edge of chain polymerization necessarily has a reactive chemical species, the created polymer nanowire forms chemical bonding with an encountered molecular element. We name this spontaneous reaction "chemical soldering". First-principles theoretical calculations are used to investigate the structures and electronic properties of the connection. We demonstrate that two conductive polymer nanowires are connected to a single phthalocyanine molecule. A resonant tunneling diode formed by this method is discussed.     

Selective formation of a latticed nanostructure with the precise alignment of DNA-templated gold nanowires

A very efficient method is introduced to selectively align and uniformly separate λ-DNA molecules and thus DNA-templated gold nanowires (AuNW's) using a combination of molecular combing and surface-patterning techniques. By the method presented in this work, it is possible to obtain parallel and latticed nanostructures consisting of DNA molecules and thus DNA-templated AuNW's aligned at 400 nm intervals. DNA-templated AuNW's are uniformly formed with an average height of 2.5 nm. This method is expected to hold potential for the integration of nanosized building blocks applicable to nanodevice construction.     

One-step electrodeposition of Ag-decorated ZnO nanowires

A new route for synthesizing Ag-decorated ZnO nanowires (NWs) on conductive glass substrates using a one-step electrodeposition technique is described here. The structural, optical, and photoelectrochemical properties of Ag-decorated ZnO nanowires were studied in detail using techniques such X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, UV-visible spectroscopy, photoluminescence, and photoelectrochemical measurements. Both pure and Ag-decorated ZnO nanowires were found to crystallize in the wurtzite structure, irrespective of their Ag contents. Increasing the Ag content from pure ZnO NWs to 3% Ag ZnO NWs decreases the photoluminescence intensity, shifts the optical band gap to the red, and increases the photocurrent up to threefold. This behavior was attributed to the surface plasmon resonance effect induced by the Ag nanoparticles, which inhibits charge recombination and improves charge transport on the ZnO surface.     

以DNA为模板构造苯胺-DNA复合物纳米线和聚苯胺纳米导线

在溶液中, 以DNA为模板构造出了线性的苯胺-DNA复合物纳米线. 用压缩气流将得到的复合物纳米线拉直并固定到云母基底上. 用原子力显微镜(AFM)可观察到形貌规整的苯胺-DNA复合物纳米线. 苯胺单体在溶液中能从各个方向上组装到DNA分子上, 从而使DNA模板分子的表面包裹了一层苯胺. 以苯胺-DNA复合物纳米线为前驱体通过进一步化学氧化聚合得到了以DNA为模板的聚苯胺纳米导线.     

Electropolymerizable 2,2'-Carboranyldithiophenes. Structure-Property Investigations of the Corresponding Conducting Polymer Films by Electrochemistry, UV-Visible Spectroscopy and Conducting Probe Atomic Force Microscopy

Carborane-functionalized conducting polymer films have been electrogenerated in dichloromethane from the anodic oxidation of ortho- (1), meta- (3) and para-carborane (4) isomers linked to two 2-thienyl units. The corresponding electrochemical response was characterized by a broad reversible redox system corresponding to the p-doping/undoping of the polythiophene backbone, the formal potential of which increased in the order poly(1) < poly(3) < poly(4), from ca. 0.50 to 1.15 V vs Ag/Ag(+) 10(-2) M. From further UV-visible spectroscopy analysis, the optical band gap was estimated at 1.8, 2.0 and 2.2 eV for poly(1), poly(3) and poly(4), respectively. The more conjugated and electroconductive character of poly(1) is ascribed to a more planar conformation of the conjugated backbone resulting from an intramolecular β-β' cyclization reaction in the monomer, consequently yielding a fused conjugated polymer. Molecular modeling calculations using the DFT method support this hypothesis. The surface topography and maps of the conductive domains of the electropolymerized films were evaluated by conducting probe AFM. The three polymers exhibit fairly similar morphological characteristics and a surface roughness of ~2 nm. Current-voltage (I-V) characteristics of conducting AFM tip-carborane polymer-ITO junctions showed that poly(1) had the highest conductivity.     

Electromagnetic interference shielding by using conductive polypyrrole and metal compound coated on fabrics

Electromagnetic interference (EMI) shielding materials of complex type of conductive polypyrrole (PPy) as an intrinsically conducting polymer and silver‐palladium (AgPd) metal compound coated on woven or non‐woven fabrics are synthesized. From dc conductivity and SEM photographs of PPy/fabric complexes, we discuss charge transport mechanism and the homogeneity of coating on the fabrics. The EMI shielding efficiency of PPy/fabric and AgPd/fabric complexes is in the range of 8 ～ 80 dB depending on the conductivity and the additional Ag vacuum evaporation. The highest EMI shielding efficiency of PPy/fabric complexes vacuum‐evaporated by Ag is ～80 dB, indicating potential materials for military uses. We propose that PPy/fabrics are excellent RF and microwave absorber because of the relatively high absorbance and low reflectance of the materials. Copyright © 2002 John Wiley & Sons, Ltd.     

Characterization of protein-attached conducting polymer monolayer

Cytochrome c (cyt c)-immobilized monolayers and multiple monolayers of a conducting polymer [poly(terthiophene-3-carboxylic acid) polymer (poly-TTCA)] were prepared, where the monolayer of monomer precursor was fabricated with the Langmuir-Blogett technique. Covalent immobilization of cyt c was achieved by the formation of an amide bond between the carboxylic groups of the conducting polymer and amines groups of lysine in cyt c. The monolayer of poly-TTCA and poly-TTCA/cyt c was characterized by cyclic voltammetry, XPS, EQCM, Auger electron spectra (AES), and atomic force microscopy (AFM). The immobilization of cyt c on the polymer layer reveals the direct electron-transfer processes of cyt c. Cyclic voltammetry of the poly-TTCA/cyt c-modified electrode showed a pair of reversible peaks at approximately +212/+201 mV (Epa/Epc) versus Ag/AgCl in a 0.2 M phosphate buffer solution (pH 7.0). The peak separation and the redox peak current of the poly-TTCA/cyt c-modified electrodes were gradually increased by increasing the number of poly-TTCA/cyt c layers on the electrode. The heterogeneous electron-transfer rate constant (ks) of cyt c at the poly-TTCA/cyt c-monolayer-modified electrode was estimated to be 0.874 s(-1). The method provides a novel route for the fabrication of protein (cyt c)-immobilized and/or lipid (palmitoyloleoylphosphatidic acid)-immobilized monolayers and multiple monolayers of a conducting polymer. Cyt c bonded on the conductive polymer layers was applied for bioelectronic devices with unique functionality.     

Mechanistic studies on the formation of silver nanowires by a hydrothermal method

Silver (Ag) nanowires were fabricated from silver chloride (AgCl) by the hydrothermal method. The successful formation of Ag nanowires relied on the low solubility of AgCl as a precursor and the structural change of glucose to polymer on the Ag nanowire (protective layer). The Ag(+) ion concentration in the reaction solution containing AgCl was initially low, but after a reaction time of over 12 h, Ag(+) gradually reduced to Ag metal. Transmission electron microscope, Raman spectrometery, and X-ray photoelectron spectroscopy revealed that the surface of the obtained Ag nanowires possessed a carbon-rich layer with a carboxyl group, and the Ag(+) ion coordinated with the carboxyl group of this layer. The difference in the surface-free energy of Ag crystals changed the crystal growth rate that impelled the anisotropic growth of the Ag particles. By examining various reaction conditions, it was determined that the ratio of Cl(-) to Ag(+), reaction temperature, and reaction time are important factors for successful preparation of Ag nanowires. Under the reaction condition that the molar ratio of Cl(-) to Ag(+) at 160 °C for 24 h is above equimolar concentration, uniform Ag nanowires were successfully prepared.     

Thermal conductivity enhancement of Ag nanowires on an organic phase change material

One of the greatest challenges in the application of organic phase change materials (PCMs) is to increase their thermal conductivity while maintaining high phase change enthalpy. 1-Tetradecanol/Ag nanowires composite PCM containing 62.73 wt% (about 11.8 vol%) of Ag nanowires showed remarkably high thermal conductivity (1.46 W m⁻¹ K⁻¹) and reasonably high phase change enthalpy (76.5 J g⁻¹). This behavior was attributed to the high aspect ratio of Ag nanowires, few thermal conduct interfaces, and high interface thermal conductivity of Ag nanowires in the composite PCM. These results indicated that Ag nanowires might be strong candidates for thermal conductivity enhancement of organic PCMs.     

Polyaniline nanowires on Si surfaces fabricated with DNA templates

It is essential to put individual, free-standing nanowires onto insulating substrates and integrate them to useful devices. Here we report a strategy for fabrication of conducting polymer nanowires on thermally oxidized Si surfaces by use of DNA as templates. The direct use of stretched and immobilized DNA strands as templates avoids the agglomeration of DNA caused by shielding of charges on DNA when polyaniline/DNA complexes formed in solution. Most importantly, the oriented DNA strands immobilized on the Si surface predetermine the position and the orientation of the nanowires. The approach described here is the first step toward uniting the programmable-assembly ability of DNA with the unique electronic properties of conducting polymers for high-density functional nanodevices. The conductivity of the nanowires is very sensitive to the proton doping-undoping process, suggesting that the nanowires hold great promise for sensitive chemical sensor applications.     

Reactive Template Synthesis of Polypyrrole Nanotubes for Fabricating Metal/Conducting Polymer Nanocomposites

Unique nanocomposites of polypyrrole/Au and polypyrrole/Pt hybrid nanotubes are synthesized employing polypyrrole (PPy) nanotubes as an advanced support by solution reduction. The conducting polymer PPy nanotubes are fabricated by using pre‐prepared MnO₂ nanowires as the reactive templates. MnO₂ nanowires induce the 1D polymerization of pyrrole monomers and the simultaneous dissolution of the templates affords the hollow tube‐like structure. The loading content of metal nanoparticles in the nanocomposites could be adjusted by simply changing the amount of metal precursors. This work provides an efficient approach to fabricate an important kind of metal/conducting polymer hybrid nanotubes that are potentially useful for electrocatalyst and sensor materials.     

Electrolyte-gated transistors based on conducting polymer nanowire junction arrays

In this study, we describe the electrolyte gating and doping effects of transistors based on conducting polymer nanowire electrode junction arrays in buffered aqueous media. Conducting polymer nanowires including polyaniline, polypyrrole, and poly(ethylenedioxythiophene) were investigated. In the presence of a positive gate bias, the device exhibits a large on/off current ratio of 978 for polyaniline nanowire-based transistors; these values vary according to the acidity of the gate medium. We attribute these efficient electrolyte gating and doping effects to the electrochemically fabricated nanostructures of conducting polymer nanowires. This study demonstrates that two-terminal devices can be easily converted into three-terminal transistors by simply immersing the device into an electrolyte solution along with a gate electrode. Here, the field-induced modulation can be applied for signal amplification to enhance the device performance.