Optimized Drop-Casted Polyaniline Thin Films for High-Sensitivity Electrochemical and Optical pH Sensors.

Conducting polymers used in chemical sensors are attractive because of their ability to confer reversible properties controlled by the doping/de-doping process. Polyaniline (PANI) is one of the most prominent materials used due to its ease of synthesis, tailored properties, and higher stability. Here, PANI thin films deposited by the drop-casting method on fluorine-doped tin oxide (FTO) substrates were used in electrochemical and optical sensors for pH measurement. The response of the devices was correlated with the deposition parameters; namely, the volume of deposition solution dropped on the substrate and the concentration of the solution, which was determined by the weight ratio of polymer to solvent. The characterisation of the samples aimed to determine the structure-property relationship of the films and showed that the chemical properties, oxidation states, and protonation level are similar for all samples, as concluded from the cyclic voltammetry and UV-VIS spectroscopic analysis. The sensing performance of the PANI film is correlated with its relative physical properties, thickness, and surface roughness. The highest electrochemical sensitivity obtained was 127.3 ± 6.2 mV/pH, twice the Nernst limit-the highest pH sensitivity reported to our knowledge-from the thicker and rougher sample. The highest optical sensitivity, 0.45 ± 0.05 1/pH, was obtained from a less rough sample, which is desirable as it reduces light scattering and sample oxidation. The results presented demonstrate the importance of understanding the structure-property relationship of materials for optimised sensors and their potential applications where high-sensitivity pH measurement is required.

Understanding the Effect of Deposition Technique on the Structure-Property Relationship of Polyaniline Thin Films Applied in Potentiometric pH Sensor.

The comprehension of potentiometric pH sensors with polymeric thin films for new and advanced applications is a constant technological need. The present study aimed to explore the relationship between the sensitivity and correlation coefficient of potentiometric pH sensors and the structure-property relationship of polyaniline thin films. The effect of the deposition method on the sample's properties was evaluated. Galvanostatically electrodeposited and spin-coated polyaniline thin films were used as the sensing stage. Samples were electrodeposited with a current density of 0.5 mA/cm2 for 300, 600, and 1200 s and were spin coated for 60 s with an angular velocity of 500, 1000, and 2000 rpm. The electrodeposited set of films presented higher average sensitivity, 73.4 ± 1.3 mV/pH, compared to the spin-coated set, 59.2 ± 2.5 mV/pH. The electrodeposited films presented higher sensitivity due to their morphology, characterized by a larger roughness and thickness compared to spin-coated ones, favoring the potentiometric response. Also, their oxidation state, evaluated with cyclic voltammetry and UV-VIS spectroscopy, corroborates their sensing performance. The understanding of the structure-property relationship of the polymeric films affecting the pH detection is discussed based on the characteristics of the deposition method used.

Nanostructured Conducting Polymers and Their Applications in Energy Storage Devices.

Due to the energy requirements for various human activities, and the need for a substantial change in the energy matrix, it is important to research and design new materials that allow the availability of appropriate technologies. In this sense, together with proposals that advocate a reduction in the conversion, storage, and feeding of clean energies, such as fuel cells and electrochemical capacitors energy consumption, there is an approach that is based on the development of better applications for and batteries. An alternative to commonly used inorganic materials is conducting polymers (CP). Strategies based on the formation of composite materials and nanostructures allow outstanding performances in electrochemical energy storage devices such as those mentioned. Particularly, the nanostructuring of CP stands out because, in the last two decades, there has been an important evolution in the design of various types of nanostructures, with a strong focus on their synergistic combination with other types of materials. This bibliographic compilation reviews state of the art in this area, with a special focus on how nanostructured CP would contribute to the search for new materials for the development of energy storage devices, based mainly on the morphology they present and on their versatility to be combined with other materials, which allows notable improvements in aspects such as reduction in ionic diffusion trajectories and electronic transport, optimization of spaces for ion penetration, a greater number of electrochemically active sites and better stability in charge/discharge cycles.

Formation of a Conducting Polymer by Different Electrochemical Techniques and Their Effect on Obtaining an Immunosensor for Immunoglobulin G.

In this work, a conducting polymer (CP) was obtained through three electrochemical procedures to study its effect on the development of an electrochemical immunosensor for the detection of immunoglobulin G (IgG-Ag) by square wave voltammetry (SWV). The glassy carbon electrode modified with poly indol-6-carboxylic acid (6-PICA) applied the cyclic voltammetry technique presented a more homogeneous size distribution of nanowires with greater adherence allowing the direct immobilization of the antibodies (IgG-Ab) to detect the biomarker IgG-Ag. Additionally, 6-PICA presents the most stable and reproducible electrochemical response used as an analytical signal for developing a label-free electrochemical immunosensor. The different steps in obtaining the electrochemical immunosensor were characterized by FESEM, FTIR, cyclic voltammetry, electrochemical impedance spectroscopy, and SWV. Optimal conditions to improve performance, stability, and reproducibility in the immunosensing platform were achieved. The prepared immunosensor has a linear detection range of 2.0-16.0 ng·mL-1 with a low detection limit of 0.8 ng·mL-1. The immunosensing platform performance depends on the orientation of the IgG-Ab, favoring the formation of the immuno-complex with an affinity constant (Ka) of 4.32 × 109 M-1, which has great potential to be used as point of care testing (POCT) device for the rapid detection of biomarkers.

Thin Films of Polyaniline-Based Nanocomposites with CeO2 and WO3 Metal Oxides Applied to the Impedimetric and Capacitive Transducer Stages in Chemical Sensors.

There is a recognized need for the development of cost-effective, stable, fast, and optimized novel materials for technological applications. Substantial research has been undertaken on the role of polymeric nanocomposites in sensing applications. However, the use of PANI-based nanocomposites in impedimetric and capacitive electrochemical sensors has yet to be understood. The present study aimed to explore the relationship between the sensitivity and linearity of electrochemical pH sensors and the composition of nanocomposites. Thin films of PANI/CeO2 and PANI/WO3 were deposited via spin coating for characterization and application during the electrochemical impedance and capacitance spectroscopy (EIS and ECS) transduction stages. The findings showed that the optimized performance of the devices was extended not only to the sensitivity but also to the linearity. An increase of 213% in the ECS sensitivity of the PANI/CeO2 compared to the metal oxide and an increase of 64% in the ECS linearity of the PANI/WO3 compared to the polymeric sensitivity were reported. This study identified the structure-property relationship of nanocomposite thin films of PANI with metal oxides for use in electrochemical sensors. The developed materials could be applied in devices to be used in different fields, such as food, environment, and biomedical monitoring.

A facile approach for tuning optical and surface properties of novel biobased Alginate/POTE handleable films via solvent vapor exposure.

Novel biobased films consisting of alginate blends with poly (octanoic acid 2-thiophen-3-yl-ethyl ester) (POTE), a conducting polymer, were prepared by solution casting, and their optical, morphological, thermal, and surface properties were studied. Using UV-visible spectroscopy, atomic force microscopy (AFM), and scanning electron microscopy (SEM), the effects of tetrahydrofuran solvent vapors on the optical properties and surface morphology of biobased films with different POTE contents were studied. Results indicate that morphological rearrangements of POTE take place during the process of solvent exposure. Specifically, the solvent vapor induced the formation of POTE small crystalline domains, which allows envisioning the potential of tuning UV-visible absorbance and wettability behavior of biobased films. Finally, theoretical electronic calculations (specifically frontier molecular orbitals analysis) provided consistent evidence on POTE's preferential orientation and selectivity toward the THF-vapor medium.

Polypyrrole-coated electrospun polystyrene films as humidity sensors.

We report the preparation of flexible polystyrene/polypyrrole (PS/PPy) mats and their successful use as a resistive humidity sensor. These composite membranes were prepared by first obtaining PS films through the electrospinning technique, and then incorporating PPy chains by an in situ chemical polymerization of the pyrrole monomer. The PS fibers were homogeneously distributed, with diameters that obeyed a normal distribution with an average value of (1.04 ± 0.12) µm. The deposition of conducting PPy chains on the surface of the PS fibers was confirmed after characterizing the PS/PPy mats by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), contact angle measurements, and electrochemical impedance spectroscopy (EIS). When used as humidity sensors, the PS/PPy mats exhibited a sensor response of 128.6%, with fast response ((54.9 ± 3.5)s) and recovery times ((76.8 ± 11.1)s), and stable response under different humidity conditions over several days. These performance characteristics compare favorably to those of previous resistive humidity sensors discussed in the literature.

Doped Poly(3-hexylthiophene) Coatings onto Chitosan: A Novel Approach for Developing a Bio-Based Flexible Electronic.

Conductive and flexible bio-based materials consisting of chitosan films coated with conductive poly(3-hexylthiophene) (P3HT) were prepared. Thermal, optical, mechanical, morphological, wettability, and conductive properties were analyzed. In a very simple and effective method of chitosan film modification, a controlled volume of a P3HT solution was deposited onto a previously formed chitosan film, assisted by the spin coating method. Later, P3HT-coated chitosan films were doped by simple contact with an aqueous solution of HAuCl4. The use of HAuCl4 becomes attractive because the reports on the doping process in this type of material using this reagent are still scarce and recent to date. In addition, since this acid is a well-known metal nanoparticle precursor, its use opens new future perspectives for these materials into new applications. The effect of P3HT concentration and doping times on film properties was studied. Attenuated total reflectance spectroscopy and UV-Vis spectroscopy allowed us to demonstrate that the presence of the P3HT coating and its doping induce significant changes in the vibrational modes and optoelectronic properties of samples. Additionally, the images obtained by scanning electron microscopy showed a well-distributed and homogeneous coating on the surface of chitosan films. Measured conductivity values of doped film samples fall in the range from 821.3 to 2017.4 S/m, representing, to the best of our knowledge, the highest values reported in the literature for chitosan/chitin-based materials. Indeed, these values are around or even higher than those obtained for some materials purely consisting of conductive polymers.

Enzymatically functionalized polyaniline thin films produced with one-step electrochemical immobilization and its application in glucose and urea potentiometric biosensors.

Glucose and urea enzymatic biosensors were fabricated. One-step electrochemical immobilization process was used to produce thin polyaniline films with entrapped enzymes. Chronopotentiometric analysis, scanning electron microscopy, electrochemical impedance spectroscopy and optical reflectance spectroscopy were used to determine the structure-property relationship of the functionalized polymeric thin films. The device has a recognition stage connected to a potentiometric field-effect-transistor stage and is based on the measurement of microenvironment pH variation or locally produced ions. Optimization of biosensor fabrication and effective measurement conditions were performed. The optimized films presented sensitivity, linearity and detection range to glucose of 14.6 ± 0.4 mV/decade, 99.8% and from 10-4 M to 10-1 mol/L. Two different biosensors were produced based on the enzymatic reaction of urea with selectivity to ammonium or hydroxyl ions. For ammonium ion selective film, the sensor's parameters were 14.7 ± 0.9 mV/decade, 98.2% and from 10-5 to 10-1 mol/L. For the hydroxyl ion selective film, the same parameters were 7.4 ± 0.5 mV/decade, 98.1% and from 10-5 to 10-1 mol/L. The change in the oxidation state of the polymeric matrix explains: i) the large loss of functionality of glucose biosensor in time, ii) the conservation of functionality to the hydroxyl ions for urea biosensor and iii) the selectivity variation of the ammonium ion selective urea biosensor. The results indicate that the polymeric matrix has indeed changeable selectivity, what can be applied in different situations for biosensors production.

Electrochemical Immunosensing Platform for the Determination of the 20S Proteasome Using an Aminophenylboronic/Poly-indole-6-carboxylic Acid-Modified Electrode.

The first electrochemical immunosensor for the determination of the 20S proteasome (P20S) was developed, entailing the immobilization of an antibody on an aminophenylboronic/poly-indole-6-carboxylic acid-modified electrode. The proposed electrochemical bioplatform is a simple and feasible analytical tool applicable for the determination of P20S in human plasma, considering its high clinical and biological relevance. Cyclic voltammetry, electrochemical impedance spectroscopy, and square wave voltammetry (SWV) were used to determine the optimal step-by-step process to obtain the electrochemical immunosensor. The interaction of P20S with the recognition layer of the immobilized antibody on the nanostructured surface took place by incubating the electrode in a P20S solution at 20 °C for 2 h. Using SWV as an electro-analytical technique, this immunosensor can quantify P20S. The current was linear with the P20S concentration within two dynamic concentration ranges from 20.0 to 80.0 and 80.0 to 200.0 ng·mL-1 (r2 = 0.992 and 0.98, respectively) with a limit of detection and quantification of 6 and 18 ng·mL-1, respectively. Moreover, the immunosensor showed considerable repeatability and reproducibility, when the determination was done in human serum, which confirms that it is a promising alternative for direct detection of P20S in biological fluids with minimal interference.

A descrição matemática do processo da detecção eletroquímica do ácido ascórbico sobre o polímero condutor, dopado pelo íon triiodeto / The mathematical description for the process of the electrochemical detection of ascorbic acid over a conducting polymer, doped by a triiodide ion

RESUMO O desempenho do polímero condutor, dopado pelo íon triiodeto, na detecção eletroquímica do ácido ascórbico foi avaliado matematicamente. O modelo matemático, correspondente ao sistema, foi desenvolvido e analisado mediante a teoria de estabilidade linear e de bifurcações. Verificou-se que o polímero condutor pode servir de excelente modificador de elétrodo para a detecção do ácido ascórbico, sendo o triiodeto a substância ativa, e o polímero condutor o mediador. O estado estacionário mantém-se estável facilmente, o que corresponde à vasta zona da linearidade da dependência entre a concentração do fármaco e o parâmetro eletroquímico. A possibilidade das instabilidades oscilatória e monotônica também foi verificada.

SUMMARY The function of the conducting polymer, doped by triiodide ion in the electrochemical determination of the ascorbic acid has been mathematically evaluated. The mathematical model, correspondent to the system, was developed and analyzed by linear stability theory and bifurcation analysis. It was confirmed that the conducting polymer might be an excellent electrode modifier for ascorbic acid determination. The triiodide ion acts as the active substance, and the conducting polymer, as a mediator. The stable steady-state is easy maintain, which is correspondent to the vast zone of the linear dependence between the drug concentration and electrochemical parameter The possibility of oscillatory and monotonic instabilities has also been verified.

Low-cost gas sensors produced by the graphite line-patterning technique applied to monitoring banana ripeness.

A low-cost sensor array system for banana ripeness monitoring is presented. The sensors are constructed by employing a graphite line-patterning technique (LPT) to print interdigitated graphite electrodes on tracing paper and then coating the printed area with a thin film of polyaniline (PANI) by in-situ polymerization as the gas-sensitive layer. The PANI layers were used for the detection of volatile organic compounds (VOCs), including ethylene, emitted during ripening. The influence of the various acid dopants, hydrochloric acid (HCl), methanesulfonic acid (MSA), p-toluenesulfonic acid (TSA) and camphorsulfonic acid (CSA), on the electrical properties of the thin film of PANI adsorbed on the electrodes was also studied. The extent of doping of the films was investigated by UV-Vis absorption spectroscopy and tests showed that the type of dopant plays an important role in the performance of these low-cost sensors. The array of three sensors, without the PANI-HCl sensor, was able to produce a distinct pattern of signals, taken as a signature (fingerprint) that can be used to characterize bananas ripeness.

Estudio teóricoppara evaluar la conductividad dl polifurano y el efecto de loss sustituyentes sobre la cadena polimérica / Theoretcal studyy to evaluate polyfuranelectrical conductivity and thee substituent effects on the polymeri cchain / Estud teorico paara avaliar a conductvidade do polifurano o e efeitoo dos substituintes sobre a cadeia polmmerica

Una serie de oligómeros de furano y furano sustituido fueron estudiados desde el punto de vista teórico con el objeto de conocer las propiedades electroconductoras de estos compuestos, y su respectiva extrapolación a polímeros, aprovechando la capacidad de la química computacional para proponer y diseñar nuevos materiales y sus posibles propiedades. Se relacionaron las propiedades electrónicas de estos oligómeros tales como la afinidad electrónica (AE), el potencial de ionización (PI), el band-gap (HOMOLUMO), y la relación de éstos con la conductividad; además, se demostró cómo cambia la longitud de los enlaces de los oligómeros al estar cargados; la longitud de los oligómeros de estudio fuer de dos, cuatro, seis y ocho anillos. En este estudio se realizaron cálculos a niveles AM1 y DFT/B3LYP/6-31G (d).

DFT/B3LYP/6-31G (d) calculations were carried out on a series of molecules of furan and substituted furan to observe the type of variables that affect the conductivity of these molecules. In order to propose and design new molecules and its possible properties. The Ionization potential (IP), band-gap (HOMO-LUMO), electronic affinity (EA), was related with its conductivity. It was also shown how change the length of the olygomers bond when the number of the rings is changed from two to four, six and eight.

Uma serie de oligômeros de furano y furano substituido foram estudados teoricamente com a intenção de conhecer as propriedades electro-conductoras desses compostos e sua respectiva extrapolação a polímeros, aproveitando a capacidade da química computacional para propor e desenhar novos materiais e suas possíveis propriedades. Relacionaram-se as propriedades eletrônicas destes oligômeros, tais como a afinidade eletrônica (AE), o potencial de ionização (PI), o band-gap (HOMO-LUMO) e a relação destes com a condutividade, também se demostrou a mudança do comprimento das ligações dos oligômeros ao estar carregados, o comprimento dos oligômeros em estudo foram de dois, quatro, seis e oito anéis. Em este estudo realizaram-se cálculos a níveis AM1 e DFT/B3LYP/6-31G (d).