Doping Polypyrrole Films with 4-N-Pentylphenylboronic Acid to Enhance Affinity towards Bacteria and Dopamine.
ABSTRACT: Here we demonstrate the use of a functional dopant as a fast and simple way to tune the chemical affinity and selectivity of polypyrrole films. More specifically, a boronic-functionalised dopant, 4-N-Pentylphenylboronic Acid (PBA), was used to provide to polypyrrole films with enhanced affinity towards diols. In order to prove the proposed concept, two model systems were explored: (i) the capture and the electrochemical detection of dopamine and (ii) the adhesion of bacteria onto surfaces. The chemisensor, based on overoxidised polypyrrole boronic doped film, was shown to have the ability to capture and retain dopamine, thus improving its detection; furthermore the chemisensor showed better sensitivity in comparison with overoxidised perchlorate doped films. The adhesion of bacteria, Deinococcus proteolyticus, Escherichia coli, Streptococcus pneumoniae and Klebsiella pneumoniae, onto the boric doped polypyrrole film was also tested. The presence of the boronic group in the polypyrrole film was shown to favour the adhesion of sugar-rich bacterial cells when compared with a control film (Dodecyl benzenesulfonate (DBS) doped film) with similar morphological and physical properties. The presented single step synthesis approach is simple and fast, does not require the development and synthesis of functional monomers, and can be easily expanded to the electrochemical, and possibly chemical, fabrication of novel functional surfaces and interfaces with inherent pre-defined sensing and chemical properties.
Project description:The understanding of oxidized species derived from the neurotransmitter dopamine (DA) is a relevant topic for both the medical field (Parkinson’s disease) as well as for the field of materials science where the formation process of polydopamine (PDA) films is an active area of research. Polymers that interact strongly with almost all surfaces but have a low electrical conductivity have been obtained by the chemical oxidation of DA. Since electrical conductivity is a desired property for several applications, deposition alternatives such as electrochemical PDA synthesis have been proposed, but the results are still insufficient. In this context, we propose a new PDA chemical–electrochemical deposition process on glassy carbon electrodes. The chemical oxidation step that converts dopamine into dopamine-o-quinone previous to the electrochemical deposition was crucial to decrease the precursor concentration to the micromolar range. The PDA-like films synthesized by this method had high adhesion and low charge-transfer resistance, which was evidenced by impedance measurements and the successful electrodeposition of a polypyrrole coating on top of a PDA-like film. In addition, we observed that anodization of GC surfaces increases sensitivity toward six electroactive couples derived from DA oxidation in the pH regimes studied. These results show the complexity of the intermediates formed during the electrochemical polymerization of PDA.
Project description:A study on the propane gas-sensing properties of Cu-doped ZnO thin films is presented in this work. The films were deposited on glass substrates by sol-gel and dip coating methods, using zinc acetate as a zinc precursor, copper acetate and copper chloride as precursors for doping. For higher sensitivity values, two film thickness values are controlled by the six and eight dippings, whereas for doping, three dippings were used, irrespective of the Cu precursor. The film structure was analyzed by X-ray diffractometry, and the analysis of the surface morphology and film composition was made through scanning electron microscopy (SEM) and secondary ion mass spectroscopy (SIMS), respectively. The sensing properties of Cu-doped ZnO thin films were then characterized in a propane atmosphere, C₃H₈, at different concentration levels and different operation temperatures of 100, 200 and 300 °C. Cu-doped ZnO films doped with copper chloride presented the highest sensitivity of approximately 6 × 10⁴, confirming a strong dependence on the dopant precursor type. The results obtained in this work show that the use of Cu as a dopant in ZnO films processed by sol-gel produces excellent catalysts for sensing C₃H₈ gas.
Project description:Flexible poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/polypyrrole/paper (PEDOT:PSS/PPy/paper) thermoelectric (TE) nanocomposite films were prepared by a two-step method: first, PPy/paper nanocomposite films were prepared by an in situ chemical polymerization process, and second, PEDOT:PSS/PPy/paper TE composite films were fabricated by coating the as-prepared PPy/paper nanocomposite films using a dimethyl sulfoxide-doped PEDOT:PSS solution. Both the electrical conductivity and the Seebeck coefficient of the PEDOT:PSS/PPy/paper TE nanocomposite films were greatly enhanced from 0.06 S/cm to ~0.365 S/cm, and from 5.44 μV/K to ~16.0 μV/K at ~300 K, respectively, when compared to the PPy/paper TE nanocomposite films. The thermal conductivity of the PEDOT:PSS/PPy/paper composite film (0.1522 Wm-1K-1 at ~300 K) was, however, only slightly higher than that of the PPy/paper composite film (0.1142 Wm-1K-1 at ~300 K). As a result, the ZT value of the PEDOT:PSS/PPy/paper composite film (~1.85 × 10-5 at ~300 K) was significantly enhanced when compared to that of the PPy/paper composite film (~4.73 × 10-7 at ~300 K). The as-prepared nanocomposite films have great potential for application in flexible TE devices.
Project description:Tungsten doped titanium dioxide films with both transparent conducting oxide (TCO) and photocatalytic properties were produced via aerosol-assisted chemical vapor deposition of titanium ethoxide and dopant concentrations of tungsten ethoxide at 500?°C from a toluene solution. The films were anatase TiO2, with good n-type electrical conductivities as determined via Hall effect measurements. The film doped with 2.25 at.% W showed the lowest resistivity at 0.034??.cm and respectable charge carrier mobility (14.9?cm(3)/V.s) and concentration (×10(19)?cm(-3)). XPS indicated the presence of both W(6+) and W(4+) in the TiO2 matrix, with the substitutional doping of W(4+) inducing an expansion of the anatase unit cell as determined by XRD. The films also showed good photocatalytic activity under UV-light illumination, with degradation of resazurin redox dye at a higher rate than with undoped TiO2.
Project description:A controllable electrochemical synthesis to convert reduced graphene oxide (rGO) from graphite flakes was introduced and investigated in detail. Electrochemical reduction was used to prepare rGO because of its cost effectiveness, environmental friendliness, and ability to produce rGO thin films in industrial scale. This study aimed to determine the optimum applied potential for the electrochemical reduction. An applied voltage of 15 V successfully formed a uniformly coated rGO thin film, which significantly promoted effective electron transfer within dye-sensitized solar cells (DSSCs). Thus, DSSC performance improved. However, rGO thin films formed in voltages below or exceeding 15 V resulted in poor DSSC performance. This behavior was due to poor electron transfer within the rGO thin films caused by poor uniformity. These results revealed that DSSC constructed using 15 V rGO thin film exhibited high efficiency (η = 1.5211%) attributed to its higher surface uniformity than other samples. The addition of natural lemon juice (pH ~ 2.3) to the electrolyte accelerated the deposition and strengthened the adhesion of rGO thin film onto fluorine-doped tin oxide (FTO) glasses.
Project description:Phosphorus doped tin(iv) oxide (P:SnO2) films have been synthesised by an aerosol assisted chemical vapour deposition route. Triethyl phosphate was used as the phosphorus dopant source. The phosphorus concentration in solution was found to be key to electrical properties, with concentrations between 0.25-0.5 mol% phosphorus giving the lowest resistivities of the deposited films. The conductivity of the films synthesised improved on doping SnO2 with phosphorus, with resistivity values of 7.27 × 10-4 Ω cm and sheet resistance values of 18.2 Ω □-1 achieved for the most conductive films. Phosphorus doping up to 1.0 mol% was shown to improve visible light transmission of the deposited films. The phosphorus doping also had a significant effect on film morphology, with varying microstructures achieved. The films were characterised by X-ray diffraction, scanning electron microscopy, UV/vis spectroscopy, Hall effect measurements and X-ray photoelectron spectroscopy. The data generated was used to build computational models of phosphorus as a dopant for SnO2, showing that the phosphorus acts as a shallow one-electron n-type donor allowing for good conductivities. Phosphorus does not suffer from self-compensation issues associated with other dopants, such as fluorine.
Project description:Electrode surfaces have been widely modified with electrically conductive polymers, including polypyrrole (PPY), to improve the performance of electrodes. To utilize conductive polymers for electrode modification, strong adhesion between the polymer films and electrode substrates should be ensured with high electrical/electrochemical activities. In this study, PPY films were electrochemically polymerized on electrodes (e.g., indium tin oxide (ITO)) with dopamine as a bio-inspired adhesive molecule. Efficient and fast PPY electrodeposition with dopamine (PDA/PPY) was found; the resultant PDA/PPY films exhibited greatly increased adhesion strengths of up to 3.7 ± 0.8?MPa and the modified electrodes had electrochemical impedances two to three orders of magnitude lower than that of an unmodified electrode. This electrochemical deposition of adhesive and conductive PDA/PPY offers a facile and versatile electrode modification for various applications, such as biosensors and batteries.
Project description:OBJECTIVE:Chitosan (CS) and polycaprolactone (PCL) were added into a nerve scaffold of poly(L-lactide acid) (PLLA)/polypyrrole (PPy)-based fibre films to solve the unmatch with the nerve strength and the aseptic inflammation from PLLA. METHODS:Poly (L-lactide acid)-polycaprolactone (PLLA/PCL) fibre films coated with chitosan (CS) and polypyrrole (PPy) were prepared by electrospinning of aligned PLLA/PCL fibres, electrochemical deposition of PPy nanoparticles and in situ doping of CS in PPy. PC12 cells were electrically stimulated with 100 mV for 2 hours every day via CS/PPy-PLLA/PCL fibre film to promote the neurite growth. RESULTS:The surface conductivity and tensile strength of CS/PPy-PLLA/PCL fibre films were 1.03 s/m and 13 MPa, respectively. CS content in fibre films was about 7.5 mg/cm2 , improving the pH value (reached to 5.1) of immersion solution of the fibre film at 16 days. Compared with PPy-PLLA/PCL fibre film, more and longer axons were grown out from PC12 cells cultured on CS/PPy-PLLA/PCL fibre film, indicating the positive effect of CS in fibre film on axon growth. The cell differentiation rate and neurite length on CS/PPy-PLLA/PCL fibre film reached to 38% and 75 ?m, respectively. These results suggest the promotion of electrical stimulation on neurite growth and alignment. CONCLUSIONS:A synergistic mechanism about the promotion of CS, electrical stimulation and aligned fibres on PC12 cells differentiation, axon outgrowth was proposed. These results indicated the potential application of CS/PPy-PLLA/PCL fibre film in the field of the nerve repair and regeneration.
Project description:Here we present the synthesis and characterization of two new conducting materials having a high electro-chemo-mechanical activity for possible applications as artificial muscles or soft smart actuators in biomimetic structures. Glucose-gelatin nanofiber scaffolds (CFS) were coated with polypyrrole (PPy) first by chemical polymerization followed by electrochemical polymerization doped with dodecylbenzensulfonate (DBS-) forming CFS-PPy/DBS films, or with trifluoromethanesulfonate (CF3SO3-, TF) giving CFS-PPy/TF films. The composition, electronic and ionic conductivity of the materials were determined using different techniques. The electro-chemo-mechanical characterization of the films was carried out by cyclic voltammetry and square wave potential steps in bis(trifluoromethane)sulfonimide lithium solutions of propylene carbonate (LiTFSI-PC). Linear actuation of the CFS-PPy/DBS material exhibited 20% of strain variation with a stress of 0.14 MPa, rather similar to skeletal muscles. After 1000 cycles, the creeping effect was as low as 0,2% having a good long-term stability showing a strain variation per cycle of -1.8% (after 1000 cycles). Those material properties are excellent for future technological applications as artificial muscles, batteries, smart membranes, and so on.
Project description:To implement large-area solution-processed graphene films in low-cost transparent conductor applications, it is necessary to have the control over the work function (WF) of the film. In this study we demonstrate a straightforward single-step chemical approach for modulating the work function of graphene films. In our approach, chemical doping of the film is introduced at the moment of its formation. The films are self-assembled from liquid-phase exfoliated few-layer graphene sheet dispersions by Langmuir-Blodgett technique at the water-air interfaces. To achieve a single-step chemical doping, metal standard solutions are introduced instead of water. Li standard solutions (LiCl, LiNO3, Li2CO3) were used as n-dopant, and gold standard solution, H(AuCl4), as p-dopant. Li based salts decrease the work function, while Au based salts increase the work function of the entire film. The maximal doping in both directions yields a significant range of around 0.7?eV for the work function modulation. In all cases when Li-based salts are introduced, electrical properties of the film deteriorate. Further, lithium nitrate (LiNO3) was selected as the best choice for n-type doping since it provides the largest work function modulation (by 400?meV), and the least influence on the electrical properties of the film.