Multifunctional micro-/nanoscaled structures based on polyaniline: an overview of modern emerging devices

With the advent of Materials Science-based technological advances, the fabrication of materials that could simultaneously exhibit both mechanical and processing properties of polymers and unique electrical characteristics of metals is a requirement with prior mandate. With the development of conducting polymers, great opportunities have been established, and novel devices with the significant features have emerged. Polyaniline (PANI) and its derivatives have attracted immense attention because of their fascinating properties, including high conductivity, inexpensiveness of starting material, unique redox behavior, facile synthesis, tunable properties, appropriate electrochemical and environmental stability, and strong bimolecular interactions. Nanostructures based on PANI have shown improved functionalities in various applications. In this article, different synthesis strategies such as interfacial polymerization, microwave-assisted polymerization, and sonochemical polymerization among others have been summarized. Besides, PANI-based nanocomposites and their various industrial, as well as biomedical applications in supercapacitors, batteries, gas vapor sensors, printable electronics, electrochromics, actuators, electrostatic dissipation, electromagnetic interference shielding, corrosion protection, filtration membranes, microbial fuel cell, biosensors, tissue engineering, and drug delivery systems, have been discussed in detail.     

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.     

Electrochemical biosensors based on Ti3C2Tx MXene: future perspectives for on-site analysis

MXenes are recently developed two-dimensional layered materials composed of early transition metal carbides and/or nitrides that provide unique characteristics for biosensor applications. This review presents the recent progress made on the usage and applications of MXenes in the field of electrochemical biosensors, including microfluidic biosensors and wearable microfluidic biosensors, and highlights the challenges with possible solutions and future needs. The multilayered configuration and high conductivity make these materials as an immobilization matrix for the biomolecule immobilization with activity retention and to be explored in the fabrication of electrochemical sensors, respectively. First, how the MXene nanocomposite as an electrode modifier affects the sensing performance of the electrochemical biosensors based on enzymes, aptamer/DNA, and immunoassays is well described. Second, recent developments in MXene nanocomposites as wearable biosensing platforms for the biomolecule detection are highlighted. This review pointed out the future concerns and directions for the use of MXene nanocomposites to fabricate advanced electrochemical biosensors with high sensitivity and selectivity. Specifically, possibilities for developing microfluidic electrochemical sensors and wearable electrochemical microfluidic sensors with integrated biomolecule detection are emphasized.     

Polyaniline-coated carbon particles and their electrode behavior in organic carbonate electrolyte

In an attempt to increase the interface stability of carbon used in Li-ion batteries, a thin conducting polyaniline (PANI) film was fabricated on the surface of carbon by in situ chemical polymerization. The chemical and electrochemical properties of the composite material were characterized using X-ray diffraction, Raman spectroscopy, scanning electron microscope, cyclic voltammetry, and electrochemical impedance spectroscopy. It was confirmed that the PANI film has an obvious effect on the morphology and the electrochemical performance of carbon. The results could be attributed to the electronic and electrochemical activity of the conducting PANI films.     

Printing polyaniline for sensor applications

In recent years, much research has focused on the development of low-cost, printed electrochemical sensor platforms for environmental monitoring and clinical diagnostics. Much effort in this area has been based on utilising the redox properties of conducting polymers, particularly polyaniline (PANI). In tackling the inherent lack of processability exhibited by these materials, several groups have examined various mass-amenable fabrication approaches to obtain suitable thin films of PANI for sensing applications. Specifically, the approaches investigated over the years include the in situ chemical synthesis of PANI, the use of sulphonated derivatives of PANI and the synthesis of aqueousbased nano-dispersions of PANI. Nano-dispersions have shown a great deal of promise for sensing applications, given that they are inkjet-printable, facilitating the patterning of conducting polymer directly to the substrate. We have shown that inkjet-printed films of PANI can be finely controlled in terms of their two-dimensional pattern, thickness, and conductivity, highlighting the level of precision achievable by inkjet printing. Utilising these nanomaterials as inkjet-printable inks opens novel, facile, and economical possibilities for conducting polymer-printed electronic applications in areas of sensing, but also many other application areas such as energy storage, displays, organic light-emitting diodes. Given that inkjet-printing is a scalable manufacturing technique, it renders possible the large-scale production of devices such as sensors for a range of applications. Several successes have emerged from our work and from the work of others in the area of applying PANI in low-cost sensor applications, which is the focus of this review.     

聚苯胺/二氧化钛复合薄膜的制备及其气敏性能

室温条件下, 运用静电力自组装和原位化学氧化聚合相结合的方法制备了聚苯胺/纳米二氧化钛(PANI/TiO2)复合薄膜和聚苯胺(PANI)薄膜, 并通过XPS和SEM对薄膜进行了分析表征. 采用平面叉指电极式器件制备了PANI/TiO2复合薄膜和PANI薄膜气体传感器, 研究了其在常温下对有毒气体NH3和CO 的敏感性能. 结果表明, PANI/TiO2复合薄膜较PANI薄膜具有更优的灵敏度和响应恢复特性.     

Doping polyaniline with pristine carbon nanotubes into electroactive nanocomposite in neutral and alkaline media

This study describes a facile but effective route to synthesis of electroactive polyaniline (PANI) in the neutral and alkaline media simply with pristine single-walled carbon nanotubes (SWNTs) as the dopant. Cyclic voltammetry (CV) studies reveal that the SWNT/PANI nanocomposite processes a good electrochemical activity in the neutral and alkaline media. Control experiments with PANI mixed with heat-treated SWNTs imply that the electrochemical properties of the SWNT/PANI nanocomposite in the neutral and alkaline media do not result from the presence of carboxylic groups at SWNTs themselves, and in turn show that the pristine SWNTs can be potentially used as a new and effective dopant to preserve the electrochemical property of PANI in the neutral and alkaline media. This property of the SWNT/PANI nanocomposite is reasonably envisaged to be promising for electrochemical investigations and electroanalytical applications, especially for the development of electrochemical sensors, biosensors and biofuel cells.     

Carbon Nanotube and Gold‐Based Materials: A Symbiosis

Carbon nanotubes constitute a novel class of nanomaterials with potential applications in many areas. The attachment of metal nanoparticles to carbon nanotubes is new way to obtain novel hybrid materials with interesting properties for various applications such as catalysts and gas sensors as well as electronic and magnetic devices. Their unique properties such as excellent electronic properties, a good chemical stability, and a large surface area make carbon nanotubes very useful as a support for gold nanoparticles in many potential applications, ranging from advanced catalytic systems through very sensitive electrochemical sensors and biosensors to highly efficient fuel cells. Here we give an overview on the recent progress in this area by exploring the various synthesis approaches and types of assemblies, in which nanotubes can be decorated with gold nanoparticles and explore the diverse applications of the resulting composites.     

Preparation and characterization of composites that contain small carbon nano-onions and conducting polyaniline

Small multilayer fullerenes, also known as carbon nano-onions (CNOs; 5-6 nm in diameter, 6-8 shells), show higher reactivity than other larger carbon nanostructures. Here we report the first example of an in situ polymerization of aniline on phenyleneamine-terminated CNO surfaces. The green, protonated, conducting emeraldine polyaniline (PANI) was directly synthesized on the surface of the CNO. The functionalized and soluble CNO/PANI composites were characterized by TEM, SEM, DSC, Raman, and infrared spectroscopy. The electrochemical properties of the conducting CNO/PANI films were also investigated. In comparison with pristine CNOs, functionalized carbon nanostructures show dramatically improved solubility in protic solvents, thus enabling their easy processing for coatings, nanocomposites, and biomedical applications.     

Preparation and Characterization of Composites that Contain Small Carbon Nano‐Onions and Conducting Polyaniline

Small multilayer fullerenes, also known as carbon nano‐onions (CNOs; 5–6 nm in diameter, 6–8 shells), show higher reactivity than other larger carbon nanostructures. Here we report the first example of an in situ polymerization of aniline on phenyleneamine‐terminated CNO surfaces. The green, protonated, conducting emeraldine polyaniline (PANI) was directly synthesized on the surface of the CNO. The functionalized and soluble CNO/PANI composites were characterized by TEM, SEM, DSC, Raman, and infrared spectroscopy. The electrochemical properties of the conducting CNO/PANI films were also investigated. In comparison with pristine CNOs, functionalized carbon nanostructures show dramatically improved solubility in protic solvents, thus enabling their easy processing for coatings, nanocomposites, and biomedical applications.     

Conducting polymers in chemical sensors and arrays

The review covers main applications of conducting polymers in chemical sensors and biosensors. The first part is focused on intrinsic and induced receptor properties of conducting polymers, such as pH sensitivity, sensitivity to inorganic ions and organic molecules as well as sensitivity to gases. Induced receptor properties can be also formed by molecularly imprinted polymerization or by immobilization of biological receptors. Immobilization strategies are reviewed in the second part. The third part is focused on applications of conducting polymers as transducers and includes usual optical (fluorescence, SPR, etc.) and electrical (conductometric, amperometric, potentiometric, etc.) transducing techniques as well as organic chemosensitive semiconductor devices. An assembly of stable sensing structures requires strong binding of conducting polymers to solid supports. These aspects are discussed in the next part. Finally, an application of combinatorial synthesis and high-throughput analysis to the development and optimization of sensing materials is described.     

Nanocomposites of graphene and graphene oxides: Synthesis,molecular functionalization and application in electrochemical sensors and biosensors. A review

Functionalized nanocomposites based on various type of graphene nanomaterials including graphene, graphene oxides (GOs), and doped graphene (oxides) are widely used as materials for various sensors that can display high sensitivity, selectivity and stability. This review with 347 references summarizes advances in the preparation and functionalization of graphene nanocomposites for the application of electrochemical sensors and biosensors. Following a general introduction into the field, the article is divided into subsections on (a) the synthesis and functionalization of nanocomposites (made from graphene, various kinds of GOs, heteroatom-doped GOs), (b) on methods for functionalization of composites (with other carbon nanomaterials, metal nanoparticles, metal oxide and metal sulfide nanoparticles), (c) on functionalization with inorganic materials including polyoxometalates, hexacyanoferrates, minerals), (d) on functionalization with organic materials such as amino acids, surfactants, organic dyes, ionic liquids, macrocycles (including cyclodextrins, crown ethers and calixarenes), and (e) on functionalization with organometallics and with various other organic compounds, (f) on functionalizations with polymers such as conventional polymers, polyelectrolytes, conducting polymers, molecularly imprinted polymers, (g) on functionalization with biomolecules including proteins and nucleic acids. Other subsections cover flexible graphene and GO based nanocomposites and 3D composites. Application of graphene and GO nanocomposites are then covered in a in large section that comprises electrochemical sensors and biosensors (based on voltammetry, amperometry, potentiometry, impedimetry, electrochemiluminescence, photoelectrochemistry, field effect transistors, electrochemical immunosensors) with specific subsections on gas sensors, enzymatic biosensors and gene sensors. A concluding section covers current challenges and perspectives of graphene and GO based (bio)sensing.

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Graphical abstract Illustration of electroanalytical applications of graphene functionalized with various materials, including carbon nanotube (CNT), fullerene (C₆₀), nanodiamond (ND), nanoparticle (NP), polyoxometalate (POM), metal hexacyanoferrate (MHCF), metalphthalocyanine (MPc), cyclodextrin (CD), poly(sodium 4-styrenesulfonate) (PSS), chitosan (CHIT), DNA and enzyme.

     

Impedance study of thiolated polyaniline

Covalent attachment of thiolated probes to conducting polymers such as polyaniline (PANI) is a promising approach towards the development of electrochemical sensors and biosensors. However, thiolation alters the conjugated polymer backbone and influences the electrochemical behavior of the conducting polymer. PANI studied in this work was electropolymerized on glassy carbon (GC) electrodes from a solution of 0.1 M aniline in 0.5 or 1.0 M H₂SO₄. The GC/PANI electrodes were then functionalized by covalent attachment of 2-mercaptoethanol to the PANI backbone. The progress of thiolation was studied by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). Thiolation of PANI was found to cause an initial decrease in electroactivity at 0–0.25 V and an increase in electroactivity at 0.25–0.6 V. However, prolonged thiolation caused a loss of electroactivity of PANI, which could be seen from EIS measurements as a dramatic decrease in the bulk redox capacitance of PANI.     

Conductive elastomeric nanocomposites based on oxidation of aniline with silver nitrate via inverse emulsion polymerization

The present investigation describes a facile and rapid approach of conductive nanocomposites production and assesses the opportunity of their use as electro‐mechanical sensors. Hybrid materials containing silver and polyaniline nanoparticles reinforcing a thermoplastic elastomeric matrix were studied. The approach developed includes ultrasonically assisted in situ inverse emulsion polymerization of aniline oxidized by a weak oxidant and silver nitrate, and supported with a strong oxidant, ammonia peroxydisulfate. Aniline was doped with dodecylbenzene sulfonic acid in the presence of dissolved styrene–isoprene–styrene thermoplastic elastomer. While conventional polymerization of aniline with silver nitrate takes 2 weeks, by utilization of inverse emulsion polymerization, the reaction time reduces to 5 days. The assistance of a strong oxidant dramatically shortens the reaction time to 30 min. The technique developed results in uniform distribution of polyaniline/silver (PANI/Ag) conductive nanoparticles in the elastomeric matrix. The morphological studies of the films reveal spherically shaped 45 nm Ag particles. The presence of PANI/Ag in the styrene–isoprene–styrene elastomeric matrix enhances the electrical, thermal, and mechanical properties of the nanocomposites. The approach described provides an opportunity of the development of tunable structures and a remarkably distinctive architecture. A rapid electrical resistance response to an applied strain makes the nanocomposites developed useful as sensitive strain sensors. Copyright © 2014 John Wiley & Sons, Ltd.     

Electrochemical sensors based on metal and semiconductor nanoparticles

Metal and semiconductor nanoparticles exhibit unique optical, electrical, thermal and catalytic properties. Therefore, they have attracted considerable interest and have been employed for construction of various electrochemical sensors. This minireview gives a general view of recent advances in electrochemical sensor development based on metal and semiconductor nanoparticles covering genosensors, protein and enzyme-based sensors, gas sensors and sensor for other organic and inorganic substances. Different assay strategies based on metal and semiconductor nanoparticles for biosensor and bioelectronic applications are presented, including electrochemical, electrical, and magnetic signal transduction techniques. Electrochemical transduction principles provide signal changes in conductance, charge, potential and current. We have paid much attention to the potential-based and current-based sensors herein. Lastly, a brief introduction is given into advances concerning the role of nanoparticles, quantum dots and nanowires for nanomedicine, such as drug delivery and discovery.     

Application of Nanoparticles in Electrochemical Sensors and Biosensors

The unique chemical and physical properties of nanoparticles make them extremely suitable for designing new and improved sensing devices, especially electrochemical sensors and biosensors. Many kinds of nanoparticles, such as metal, oxide and semiconductor nanoparticles have been used for constructing electrochemical sensors and biosensors, and these nanoparticles play different roles in different sensing systems. The important functions provided by nanoparticles include the immobilization of biomolecules, the catalysis of electrochemical reactions, the enhancement of electron transfer between electrode surfaces and proteins, labeling of biomolecules and even acting as reactant. This minireview addresses recent advances in nanoparticle‐based electrochemical sensors and biosensors, and summarizes the main functions of nanoparticles in these sensor systems.     

Controllable deposition of a platinum nanoparticle ensemble on a polyaniline/graphene hybrid as a novel electrode material for electrochemical sensing

We demonstrate for the first time an interfacial polymerization method for the synthesis of high-quality polyaniline-modified graphene nanosheets (PANI/GNs), which represents a novel type of graphene/polymer heterostructure. The interfacial polymerization at a liquid-liquid interface allows PANI to grow uniformly on the surface of the GNs. An ultra-high loading of Pt nanoparticles was then controllably deposited on the surface of the PANI/GNs to form a Pt/PANI/GNs hybrid. The obtained composites were characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersive spectrometry, X-ray diffraction, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The Pt/PANI/GNs hybrid shows excellent electrocatalytic activity toward methanol oxidation and oxygen reduction. H(2)O(2) and glucose were used as two representative analytes to demonstrate the sensing performance of a Pt/PANI/GNs-modified electrode. It is found that this sensing element shows high sensitivity and a low detection limit for H(2)O(2) and glucose. The results demonstrate that the Pt/PANI/GNs hybrid may be an attractive and advanced electrode material with potential applications in the construction of electrochemical sensors and biosensors.     

Polyaniline‐Intercalated Molybdenum Oxide Nanocomposites: Simultaneous Synthesis and their Enhanced Application for Supercapacitor

A new and universal synthetic strategy to hybridize metal oxides and conduct polymer nanocomposites has been proposed in this work. The simultaneous reaction process, which includes the generation of metal oxide layers, the oxidation polymerization of monomers, and the in situ formation of polymer–metal oxides sandwich structure is successfully realized and results in the unique hybrid polyaniline (PANI)‐intercalated molybdenum oxide nanocomposites. The peroxomolybdate proved to play a dual role as the precursor of the inorganic hosts and the oxidizing agent for polymerization. The as‐obtained hybrid nanocomposites present a flexible lamellar structure by oriented assembly of conductive PANI chains in the MoO₃ interlayer, and thus inherit excellent electrical performance and possess the potential of active electrode materials for electrochemical energy storage. Such uniform lamellar structure together with the anticipated high conductivity of the hybrid PANI/MoO₃ nanocomposites afford high specific capacitance and good stability during the charge–discharge cycling for supercapacitor application.     

MnO2/PPy/PANI三元纳米管复合材料的合成及其电化学电容性能

在聚苯胺（PANI）和二氧化锰（MnO2）存在的条件下,以FeCl3/甲基橙为模板,通过化学氧化法聚合吡咯(Py)单体,制备MnO2/PPy/PANI纳米管复合材料。 利用X射线衍射、透射电子显微镜、红外光谱和电化学测试等多种测试技术对复合材料进行物性表征和电化学电容性能测试,并讨论了不同含量的PANI对复合物材料的结构和性能的影响。 结果表明,由于PANI、MnO2与PPy三者的相互协同作用,以及材料管状结构的大比表面积,使三元复合材料具有比二元复合材料要大的电化学活性。 所合成的三元复合材料最大比容量达到458.4 F/g。     

Electrochemical Sensor Platforms Based on Nanostructured Metal Oxides,and Zeolite‐Based Materials

Electrochemical sensors have drawn significant attention over the last couple of decades because of their ability to improve detection of organic and inorganic analytes found in the field of biotechnology, environmental sciences, medicine, and food quality control. This personal account summarizes the state‐of‐art research carried out in the construction and evaluation of nanostructured metal oxides and zeolite based electrochemical sensors. Metal oxides and zeolite‐based nanomaterials have many unique and extraordinary properties such as tunable redox activity, surface functionalization ability, optimum conductivity, large surface area, biocompatibility and so forth. In this personal account, the current advances in electrochemical sensor applications of metal oxides, zeolite‐based nanomaterials, and their nanocomposites are described for the single and simultaneous determination of organic & inorganic contaminants present in water bodies, physiological bio‐molecules present in human blood & urine samples, and organic contaminants present in food materials.Moreover, concluding section focuses discussion on the future developments and applications of these materials in various emerging technologies.