Microbial imprinted polypyrrole/poly(3-methylthiophene) composite films for the detection of Bacillus endospores

The fabrication of Bacillus subtilis endospore imprinted conducting polymer films and subsequent electrochemical detection of bound spores is reported. Imprinted films were prepared by absorbing spores on the surface of glassy carbon electrodes upon which a polypyrrole, followed by a poly(3-methylthiophene), layer were electrochemically deposited. Spore template release was achieved through soaking the modified electrode in DMSO. Binding of endospores to imprinted films could be detected via impedance spectroscopy by monitoring changes in Y' (susceptance) using Mn(II)Cl2 (0.5M pH 3) as the supporting electrolyte. Here, the change in Y' could be correlated to spore densities between 10(4) and 10(7)cfu/ml. More sensitive detection of absorbed spores was achieved by following endospore germination via changes in film charge as measured using cyclic voltammetry. Here, imprinted films were submerged in spore suspensions to permit absorption, heat activated at 70 degrees C for 10 min prior to transferring to an electrochemical cell containing germination activators. By using the assay format it was possible to detect 10(2)cfu/ml. The observed changes in film charge could be attributed to the interaction of the supporting conducting polymer with dipicolinic acid (DPA) and other constituents released from the core in the course of germination. In all cases, it was not possible to regenerate the imprinted films without losing electrode response. In summary, the study has provided proof-of-concept for fabricating microbial imprinted films using conducting polymers.     

Electrochemical sensor for sensitive detection of paracetamol based on novel multi-walled carbon nanotubes-derived organic–inorganic material

A new electrochemical sensor based on a novel organic–inorganic material (PNFCTs) was proposed for detection of paracetamol in this paper. First, PNFCTs were prepared with multi-walled carbon nanotubes (MWNTs) and a derivative of 3,4,9,10-perylenetetracarboxylic dianhydride (PTC-NH₂) via cross-linking method. Then, PNFCTs were coated onto the surface of the glassy carbon electrode (GCE) to form porous organic conducting polymer films (PNFCTs/GCE), which could not only increase the loading of paracetamol efficiently but also provide an interface with exceptional electrical conductivity for paracetamol. Finally, gold nanoparticles (GNPs) were attached to the electrode surface through electrodepositing method, which obtained GNPs/PNFCTs/GCE electrode. The electrochemical behavior of paracetamol on GNPs/PNFCTs/GCE was explored by cyclic voltammetrys (CVs) and differential pulse voltammograms (DPVs). The results showed that the GNPs/PNFCTs/GCE exhibited excellent electrocatalytic activity to paracetamol, which should be attributed to remarkable properties of the new composite nanomaterials with porous nanostructure and exceptional electrical conductivity. The wide liner range and detection limit were 0.3–575 and 0.1 μM, respectively. Finally, it was successfully used to detect paracetamol in dilution human serum and commercial tablets. The sensor shows great promise for simple, sensitive, and selective detection paracetamol and provides a promising approach in paracetamol clinical research and overdose diagnostic applications.     

Organic plasma process for simple and substrate-independent surface modification of polymeric BioMEMS devices

A polymeric bio micro electromechanical systems (BioMEMS) device was fabricated using organic plasma polymerization, by which the surface of a polymeric substrate could easily be modified through vapor-phase deposition of organic thin films. This technique, capable of polymeric deposition of any kind of monomer, can serve the purpose of anti-fouling coating, wettability control, or layer-to-layer interface creation, on the surface of any given chemically-inert polymeric substrate without involving cumbersome surface organic reactions. A prototype device was fabricated to have an array of electrochemical glucose biosensors with the three electrode configuration, each of which has a microfluidic channel (500 μm×800 μm) for capillary-action-driven sample delivery and the concerned enzymatic reaction. Stressing the advantages of the plasma polymerization process using a polymeric substrate together with some additional features accomplished in our device fabrication, new possibilities in the field of polymeric BioMEMS are discussed.     

Amperometric glucose biosensor based on multilayer films via layer-by-layer self-assembly of multi-wall carbon nanotubes, gold nanoparticles and glucose oxidase on the Pt electrode

A novel amperometric glucose biosensor based on the nine layers of multilayer films composed of multi-wall carbon nanotubes (MWCNTs), gold nanoparticles (GNp) and glucose oxidase (GOD) was developed for the specific detection of glucose. MWCNTs were chemically modified with the H₂SO₄–HNO₃ pretreatment to introduce carboxyl groups which were used to interact with the amino groups of poly(allylamine) (PAA) and cysteamine via 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide cross-linking reaction, respectively. A cleaned Pt electrode was immersed in PAA, MWCNTs, cysteamine and GNp, respectively, followed by the adsorption of GOD, assembling the one layer of multilayer films on the surface of Pt electrode (GOD/GNp/MWCNTs/Pt electrode). Repeating the above process could assemble different layers of multilayer films on the Pt electrode. PBS washing was applied at the end of each assembly deposition for dissociating the weak adsorption. Film assembling and characterization were studied by transmission electron microscopy and quartz crystal microbalance, and properties of the resulting glucose biosensors were measured by electrochemical measurements. The marked electrocatalytic activity of Pt electrode based on multilayer films toward H₂O₂ produced during GOD enzymatic reactions with glucose permitted effective low-potential amperometric measurement of glucose. Taking the sensitivity and selectivity into consideration, the applied potential of 0.35 V versus Ag/AgCl was chosen for the oxidation detection of H₂O₂ in this work. Among the resulting glucose biosensors, the biosensor based on nine layers of multilayer films was best. It showed a wide linear range of 0.1–10 mM glucose, with a remarkable sensitivity of 2.527 μA/mM, a detection limit of 6.7 μM estimated at a signal-to-noise ratio of 3 and fast response time (within 7 s). Moreover, it exhibited good reproducibility, long-term stability and the negligible interferences of ascorbic acid, uric acid and acetaminophen. The study can provide a feasible approach on developing new kinds of oxidase-based amperometric biosensors, and can be used as an illustration for constructing various hybrid structures.     

Impedance studies of a nano-structured conducting polymer and its application to the design of reliable scaffolds for impedimetric biosensors

Electrochemical impedance spectroscopy (EIS) as a powerful, non-invasive and informative technique was used to obtain important information about kinetics of doping process in conducting polymers. Polypyrrole (PPy) and its derivatives can form conducting polymer films which represent excellent charge transfer behaviors during doping processes. It can also have a wide range of applications in bioelectrochemistry. In the present study the conducting polymer of alpha-carboxy pyrrole (alpha-COOH-PPy), appended onto the underlying film of PPy, was prepared by electrochemical methods and its behavior was analyzed using EIS. From highly accurate fitting of impedance results it was found that the charging mechanism is governed by the diffusion process. In addition, the impedance analyses provided values for the bulk polymer parameters including diffusion coefficient (D), equilibrium capacitance (C(0)) and diffusion resistance (R(0)). The surface morphology of the polymeric film was characterized using scanning electron microscopy (SEM). The film was then used to immobilize the cytochrome C (cyt-C) and to perform its electrochemical studies. The modified cyt-C/alpha-COOH-PPy electrode was used for electrocatalytic reduction of H(2)O(2) in solution and its viability as a new impedimetric biosensor was examined. Based on the calibration curve obtained for the proposed impedimetric biosensor, the limit of detection and relative standard deviation were evaluated as 0.25mumolL(-1) and 7%, respectively. Finally, the prolonged stability test was performed and high stability and reproducibility of the new biosensor was confirmed.     

Growth of thin processable films of poly(pyrrole) using phosphomolybdate clusters

Facile control over the chemical polymerization of pyrrole from solutions of pyrrole-phosphomolybdic acid has allowed processibility of conducting poly(pyrrole). This approach has allowed thin conducting films of poly(pyrrole) to be deposited in a single step, and in contrast to electrochemical polymerization methods, is not limited to electrically conducting substrates. For example, 40–100 nm thick poly(pyrrole) films with conducivities in the range of 15 to 30 S cm⁻¹ have been spin coated onto insulating glass substrates. Insight into the mechanism of polymerization has been obtained with cyclic voltammetry and UV-Vis spectroscopy.     

Controlled Synthesis and Energy Applications of One‐Dimensional Conducting Polymer Nanostructures: An Overview

The past decade has witnessed increasing attention in the synthesis, properties, and applications of one‐dimensional (1D) conducting polymer nanostructures. This overview first summarizes the synthetic strategies for various 1D nanostructures of conjugated polypyrrole (PPy), polyaniline (PANI), polythiophene (PTh), poly(p‐phenylenevinylene) (PPV) and derivatives thereof. By using template‐directed or template‐free methods, nanoscale rods, wires/fibers, belts/ribbons, tubes, arrays, or composites have been successfully synthesized. With their unique structures and advantageous characteristics (e.g., high conductivity, high carrier mobility, good electrochemical activity, large specific surface area, short and direct path for charge/ion transportation, good mechanical properties), 1D conducting polymer nanostructures are demonstrated to be very useful for energy applications. Next, their applications in solar cells, fuel cells, rechargeable lithium batteries, and electrochemical supercapacitors are highlighted, with a strong emphasis on recent literature examples. Finally, this review ends with a summary and some perspectives on the challenges and opportunities in this emerging area of research.     

Imprinted polymer-modified hanging mercury drop electrode for differential pulse cathodic stripping voltammetric analysis of creatine

The molecularly imprinted polymer [poly(p-aminobenzoicacid-co-1,2-dichloroethane)] film casting was made on the surface of a hanging mercury drop electrode by drop-coating method for the selective and sensitive evaluation of creatine in water, blood serum and pharmaceutical samples. The molecular recognition of creatine by the imprinted polymer was found to be specific via non-covalent (electrostatic) imprinting. The creatine binding could easily be detected by differential pulse, cathodic stripping voltammetric signal at optimised operational conditions: accumulation potential −0.01 V (versus Ag/AgCl), polymer deposition time 15 s, template accumulation time 60 s, pH 7.1 (supporting electrolyte ≤ 5 × 10⁻⁴ M NaOH), scan rate 10 mV s⁻¹, pulse amplitude 25 mV. The modified sensor in the present study was found to be highly reproducible and selective with detection limit 0.11 ng mL⁻¹ of creatine. Cross-reactivity studies revealed no response to the addition of urea, creatinine and phenylalanine; however, some insignificant magnitude of current was observed for tryptophan and histidine in the test samples.     

Reagentless biosensors based on co-entrapment of a soluble redox polymer and an enzyme within an electrochemically deposited polymer film

A novel biosensor architecture, which is based on the combination of a manual and a non-manual deposition technique for sensor components on the electrode surface is reported. A water-soluble Os-poly(vinyl-imidazole) redox hydrogel is deposited on a graphite electrode by drop-coating (i.e. manually) followed by the electrochemically-induced deposition of an enzyme-containing non-conducting polymer film. The local polymer deposition is initiated by electrochemical generation of H(3)O(+) exclusively at the electrode surface causing a pH-shift to be established in the diffusion zone around the electrode (i.e. non-manually). This pH-shift leads to the protonation of a dissolved polyanionic polymer which in consequence changes significantly its solubility and is hence precipitating on the electrode surface. In the presence of a suitable enzyme, such as quinohemoprotein alcohol dehydrogenase (QH-ADH), the polymer precipitation leads to an entrapment of the redox enzyme within the polymer film. Simultaneously, the water-soluble Os-poly(vinyl-imidazole) redox hydrogel, which is slowly dissolving from the electrode surface after addition of the electrolyte, is co-entrapped within the precipitating polymer layer. This provides the pre-requisite for an efficient electron-transfer pathway from the redox enzyme via the polymer-bound redox centres to the electrode surface. The sensor preparation protocol has been optimised aiming on a high mediator concentration in the polymer film and an effective electron transfer.     

Efficient Polymer Solar Cells on Opaque Substrates with a Laminated PEDOT:PSS Top Electrode

Solution processed polymer:fullerene solar cells on opaque substrates have been fabricated in conventional and inverted device configurations. Opaque substrates, such as insulated steel and metal covered glass, require a transparent conducting top electrode. We demonstrate that a high conducting (900 S cm^?1) PEDOT:PSS layer, deposited by a stamp‐transfer lamination technique using a PDMS stamp, in combination with an Ag grid electrode provides a proficient and versatile transparent top contact. Lamination of large size PEDOT:PSS films has been achieved on variety of surfaces resulting in ITO‐free solar cells. Power conversion efficiencies of 2.1% and 3.1% have been achieved for P3HT:PCBM layers in inverted and conventional polarity configurations, respectively. The power conversion efficiency is similar to conventional glass/ITO‐based solar cells. The high fill factor (65%) and the unaffected open‐circuit voltage that are consistently obtained in thick active layer inverted geometry devices, demonstrate that the laminated PEDOT:PSS top electrodes provide no significant potential or resistive losses.     

Direct electrochemical sensor for fast reagent-free DNA detection

A novel reagentless direct electrochemical DNA sensor has been developed using ultrathin films of the conducting polymer polypyrrole doped with an oligonucleotide probe. Our goal was to develop a prototype electrochemical DNA sensor for detection of a biowarfare pathogen, variola major virus. The sensor has been optimized for higher specificity and sensitivity. It was possible to detect 1.6 fmol of complementary oligonucleotide target in 0.1 ml in seconds by using chronoamperometry. The sensitivity of the developed sensor is comparable to indirect electrochemical DNA sensors, which use electrochemical labels and reagent-intensive amplification. The developed sensing electrode is reusable, highly stable and suitable for storage in solution or in dry state.     

Electrochemical deposition and surface-initiated RAFT polymerization: protein and cell-resistant PPEGMEMA polymer brushes

This paper introduces a novel and versatile method of grafting protein and cell-resistant poly(poly ethylene glycol methyl ether methacrylate) (PPEGMEMA) brushes on conducting Au surface. The process started with the electrochemical deposition and full characterization of an electro-active chain transfer agent (CTA) on the Au surface. The electrochemical behavior of the CTA was investigated by cyclic voltammetry (CV) while the deposition and stability of the CTA on the surface were confirmed by ellipsometry, contact angle, and X-ray photoelectron spectroscopy (XPS). The capability of the electrodeposited CTA to mediate surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) polymerization on both the polymethyl methacrylate (PMMA; model polymer) and PPEGMEMA brushes was demonstrated by the increase in thicknesses of the films after polymerization. Contact angles also decreased with the incorporation of the more hydrophilic brushes. Significant changes in the morphologies of the films before and after polymerization were also observed with atomic force microscopy (AFM) analyses. Furthermore, XPS results showed an increase in the O 1s peak intensity relative to C 1s after polymerizations, which confirmed the grafting of polyethyleneglycol (PEG) bearing brushes. The ability of the PPEGMEMA-modified Au surface to resist nonspecific adhesion of proteins and cells was monitored and confirmed by XPS, ellipsometry, contact angle, AFM, and fluorescence imaging. The new method presented has potential application as robust protein and cell-resistant coatings for electrically conducting electrodes and biomedical devices.     

Amperometric glucose biosensor based on polymerized ionic liquid microparticles

A glucose amperometric biosensor based on the immobilization of glucose oxidase (GOx) in microparticles prepared by polymerization of the ionic liquid 1-vinyl-3-ethyl-imidazolium bromide (ViEtIm⁺Br⁻) using the concentrated emulsion polymerization method has been developed. The polymerization of the emulsion dispersed phase, in which the enzyme was dissolved together with the ionic liquid monomer, provides poly(ViEtIm⁺Br⁻) microparticles with entrapped GOx. An anion-exchange reaction was carried out for synthesizing new microparticles of poly(ViEtIm⁺(CF₃SO₂)₂N⁻) and poly(ViEtIm⁺BF₄⁻). The enzyme immobilization method was optimized for biosensor applications and the following optimal values were determined: pH 4.0 for the synthesis medium, 1.23 M monomer concentration and 3.2% (w/w) cross-linking content. The performance of the biosensor as a function of some analytical parameters such as pH and temperature of the measuring medium, and enzymatic load of the microparticles was also investigated. The effect of the substances which are present in serum samples such as uric and ascorbic acid was eliminated by using a thin Nafion layer covering the electrode surface. The biosensor thus prepared can be employed in aqueous and in non-aqueous media with satisfactory results for glucose determination in human serum samples. The useful lifetime of this biosensor was 150 days.     

Bifunctional Conducting Polymer Coated CoP Core–Shell Nanowires on Carbon Paper as a Free‐Standing Anode for Sodium Ion Batteries

This study proposes a conformal surface coating of conducting polymer for protecting 1D nanostructured electrode material, thereby enabling a free‐standing electrode without binder for sodium ion batteries. Here, polypyrrole (PPy), which is one of the representative conducting polymers, encapsulated cobalt phosphide (CoP) nanowires (NWs) grown on carbon paper (CP), finally realizes 1D core–shell CoP@PPy NWs/CP. The CoP core is connected to the PPy shell via strong chemical bonding, which can maintain a Co–PPy framework during charge/discharge. It also possesses bifunctional features that enhances the charge transfer and buffers the volume expansion. Consequently, 1D core–shell CoP@PPy NWs/CP demonstrates superb electrochemical performance, delivering a high areal capacity of 0.521 mA h cm^?2 at 0.15 mA cm^?2 after 100 cycles, and 0.443 mA h cm^?2 at 1.5 mA cm^?2 even after 1000 cycles. Even at a high current density of 3 mA cm^?2, a significant areal discharge capacity reaching 0.285 mA h cm^?2 is still maintained. The outstanding performance of the CoP@PPy NWs/CP free‐standing anode provides not only a novel insight into the modulated volume expansion of anode materials but also one of the most effective strategies for binder‐free and free‐standing electrodes with decent mechanical endurance for future secondary batteries.     

Immobilization of tyrosinase in polysiloxane/polypyrrole copolymer matrices

Immobilization of tyrosinase in conducting copolymer matrices of pyrrole functionalized polydimethylsiloxane/polypyrrole (PDMS/PPy) was achieved by electrochemical polymerization. The polysiloxane/polypyrrole/tyrosinase electrode was constructed by the entrapment of enzyme in conducting matrices during electrochemical copolymerization. Maximum reaction rate (V(max)) and Michaelis-Menten constant (K(m)) were investigated for immobilized enzyme. Enzyme electrodes were prepared in two different electrolyte/solvent systems. The effect of supporting electrolytes, p-toluene sulfonic acid and sodium dodecyl sulfate on the enzyme activity and film morphology were determined. Temperature and pH optimization, operational stability and shelf-life of enzyme electrodes were also examined. Phenolic contents of green and black tea were determined by using enzyme electrodes.     

Overoxidized polypyrrole film directed single-walled carbon nanotubes immobilization on glassy carbon electrode and its sensing applications

In this paper, the films of overoxidized polypyrrole (PPyox) directed single-walled carbon nanotubes (SWNTs) have been electrochemically coated onto glassy carbon electrode (GCE). Electroactive monomer pyrrole was added into the solution containing sodium dodecyl sulfate (SDS) and SWNTs. Then, electropolymerization was proceeded at the surface of GCE, and a novel kind of conducting polymer/carbon nanotubes (CNTs) composite film with the orientation of CNTs were obtained correspondingly. Finally, this obtained polypyrrole (PPy)/SWNTs film modified GCE was oxidized at a potential of +1.8 V. It can be found that this proposed PPyox/SWNTs composite film modified GCE exhibited excellent electrocatalytic properties for some species such as nitrite, ascorbic acid (AA), dopamine (DA) and uric acid (UA), and could be used as a new sensor for practical applications. Compared with previous CNTs modified electrodes, SWNTs were oriented towards the outside of modified layer by PPyox and SDS, which made the film easily conductive. Moreover, this proposed film modified electrode was more stable, selective and applicable.     

Preliminary investigation of a bioelectrochemical sensor for the detection of phenol vapours

This work investigates the feasibility of constructing a bioelectrochemical sensor that can operate directly in gases. A series of experiments are described, resulting in a sensor that is responsive to phenol vapours. The sensor was based on ionically conducting films that incorporate a biological redox catalyst at the surface of an array of interdigitated microband electrodes. Exposure to phenol vapour drives the bioelectrochemical reaction, providing a basis for a current signal under constant potential conditions. Ionic materials included Nafion and films based on tetrabutylammonium toluene-4-sulphonate (TBATS). The quasi-reversible electrode reaction of potassium hexacyanoferrate (II) within TBATS was investigated as a function of drying time. E^o′ and K⁰ were determined at a TBATS modified microdisc electrode under steady-state conditions. Drying time (water loss) from the TBATS film had the effect of increasing the film ionic strength. It was shown that as the film ionic strength increased, E⁰′ for potassium hexacyanoferrate (II) shifts toward positive potentials (because of ion pairing) and there was a corresponding increase in the heterogeneous rate constant K⁰. The latter effect was attributed to increasing ion-ion (cation-ferrocyanide ion) interactions as the film dried and the enhancing effect this had on the prevention of surface poisoning reactions at the electrode. These factors are discussed in relation to sensor design.     

Immobilization of tyrosinase and alcohol oxidase in conducting copolymers of thiophene functionalized poly(vinyl alcohol) with pyrrole

Immobilization of tyrosinase and alcohol oxidase is achieved in the copolymer of pyrrole with vinyl alcohol with thiophene side groups (PVATh-co-PPy) which is a newly synthesized conducting polymer. PVATh-co-PPy/alcohol oxidase and PVATh-co-PPy/tyrosinase electrodes are constructed by the entrapment of enzyme in conducting copolymer matrix during electrochemical copolymerization. For tyrosinase and alcohol oxidase enzymes, catechol and ethanol are used as the substrates, respectively. Kinetic parameters: maximum reaction rates (V(max)) and Michaelis-Menten constants (K(m)) are obtained. V(max) and K(m) are found as 2.75 micromol/(minelectrode) and 18 mM, respectively, for PVATh-co-PPy/alcohol oxidase electrode and as 0.0091micromol/(minelectrode) and 40 mM, respectively, for PVATh-co-PPy/tyrosinase electrode. Maximum temperature and pH values are investigated and found that both electrodes have a wide working range with respect to both temperature and pH. Operational and storage stabilities show that although they have limited storage stabilities, the enzyme electrodes are useful with respect to operational stabilities.     

A doubly amplified electrochemical immunoassay for carcinoembryonic antigen

An ultrasensitive electrochemical immunoassay (EIA) for the detection of carcinoembryonic antigen (CEA) is described in this report. The assay involves utilizing enzyme-catalyzed deposition of a redox polymer and electrocatalytic oxidation of ascorbic acid (AA) by the deposited redox polymer, a dual-amplification scheme to enhance analytical signals. Briefly, CEA capturing antibody and redox polymer anchoring agent were covalently immobilized on a gold electrode. After incubating with CEA, the electrode was treated in detection antibody-glucose oxidase conjugate solution. Thereafter, it was dipped into the redox polymer solution. Upon the addition of glucose, the redox polymer was enzymatically reduced and deposited on the electrode surface. The deposited redox polymer exhibits excellent electrocatalytic activity towards the oxidation of AA. Consequently, CEA could be quantified amperometrically. This electrochemical immunoassay combines the specificity of the immunological reaction with the sensitivity of the doubly amplified electrochemical detection.     

A Three‐Dimensionally Interconnected Carbon Nanotube–Conducting Polymer Hydrogel Network for High‐Performance Flexible Battery Electrodes

High‐performance flexible energy‐storage devices have great potential as power sources for wearable electronics. One major limitation to the realization of these applications is the lack of flexible electrodes with excellent mechanical and electrochemical properties. Currently employed batteries and supercapacitors are mainly based on electrodes that are not flexible enough for these purposes. Here, a three‐dimensionally interconnected hybrid hydrogel system based on carbon nanotube (CNT)‐conductive polymer network architecture is reported for high‐performance flexible lithium ion battery electrodes. Unlike previously reported conducting polymers (e.g., polyaniline, polypyrrole, polythiophene), which are mechanically fragile and incompatible with aqueous solution processing, this interpenetrating network of the CNT‐conducting polymer hydrogel exibits good mechanical properties, high conductivity, and facile ion transport, leading to facile electrode kinetics and high strain tolerance during electrode volume change. A high‐rate capability for TiO₂ and high cycling stability for SiNP electrodes are reported. Typically, the flexible TiO₂ electrodes achieved a capacity of 76 mAh g^–1 in 40 s of charge/discharge and a high areal capacity of 2.2 mAh cm^–2 can be obtained for flexible SiNP‐based electrodes at 0.1C rate. This simple yet efficient solution process is promising for the fabrication of a variety of high performance flexible electrodes.