Nanostructured poly(thiophene acetic acid)/Au/poly(methylene blue) interface for electrochemical immunosensing of p53 protein.

A poly(thiophene acetic acid)/Au/poly(methylene blue) nanostructured interface was electrochemically assembled step-by-step on screen-printed carbon electrodes (SPCE) for label-free detection of p53 protein. The initial electrical conductive properties of the polymeric interface were increased with an additional layer of poly(methylene blue) electropolymerized in the presence of gold nanoparticles. The nano-immunosensing architecture was prepared by covalent immobilization of anti-p53 antibodies as bioreceptors through the poly(thiophene acetic acid) moieties. The nano-immunosensor assembly was extensively characterized by ultraviolet-visible spectrophotometry, dynamic and electrophoretic light scattering, scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, atomic force microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. Under optimal conditions, p53 was specifically and selectively detected by square wave voltammetry in a linear range between 1 and 100 ng mL-1 with a limit of detection of 0.65 ng mL-1. In addition, the electrochemical nano-immunosensor detected p53 in spiked human serum samples and colorectal cancer cell lysates, and the results were validated with a standard spectrophotometric method using a paired samples t test, which did not exhibit significant differences between both methods. The resultant p53 nano-immunosensor is simple to assemble, robust, and has the potential for point-of-care biomarker detection applications.

Efficacy assessment of an intramammary formulation based on soluble polypyrrole in cows with experimentally induced mastitis / Avaliação da eficácia de uma formulação intramamária à base de polipirrol solúvel em vacas com mastite experimentalmente induzida

Considerando a necessidade de terapias alternativas para a mastite bovina, uma inflamação, normalmente de causa infecciosa, de alta prevalência e de alto impacto econômico nas fazendas leiteiras, avaliou-se a eficácia antimicrobiana, in vivo, de uma formulação intramamária à base de polipirrol (PPy) solúvel, um polímero condutor promissor para aplicações biomédicas, especialmente como potente antibacteriano. Neste ensaio, quartos mamários de vacas holandesas sadias (n = 8) foram inoculados com Staphylococcus aureus e tratados, por via intramamária, com formulação experimental à base de PPy solúvel (5%) e com formulação comercial à base de sulfato de gentamicina. O efeito desses tratamentos foi avaliado com a realização de lactoculturas, da Contagem Bacteriana Total (TBC), da Contagem de Células Somáticas (SCC) e da análise da composição do leite das amostras obtidas de quartos mamários, em sete momentos experimentais. Avaliação hematológica dos animais também foi realizada. A aplicação intramamária de três doses da formulação experimental à base de PPy solúvel resultou em maiores log/mL da TBC e da SCC quando comparadas ao grupo controle positivo e ao grupo que recebeu sulfato de gentamicina. A administração da formulação experimental não induziu alterações na composição do leite e nos parâmetros hematológicos. Alguns fatores farmacocinéticos e farmacodinâmicos do PPy solúvel podem ser atribuídos a ineficácia antimicrobiana da pomada experimental. Outras pesquisas devem ser realizados em prol do desenvolvimento de formulações que permitam a atuação antibacteriana do PPy solúvel no ambiente intramamário de vacas leiteiras.

Given the need for alternative therapies for bovine mastitis, an infectious disease of high prevalence and significant economic impact in dairy farms, this study evaluated the in vivo antimicrobial efficacy of an intramammary formulation based on soluble polypyrrole (PPy), a promising conductive polymer for biomedical applications, especially as an effective antimicrobial agent. In this assay, mammary quarters of healthy Holstein Friesian cows (n = 8) were inoculated with Staphylococcus aureus and treated, via the intramammary route, with an experimental formulation based on soluble PPy (5%) and a commercial formulation based on gentamicin sulfate. The effect of these treatments was evaluated based on milk cultures, Total Bacterial Count (TBC), Somatic Cell Count (SCC), and milk composition analysis of mammary quarter samples in seven experimental moments. In addition, hematological evaluations of the animals were also performed. The intramammary application of three levels of the experimental formulation based on soluble PPy resulted in higher log/mL of the TBC and SCC compared to a positive control group and a group that received gentamicin sulfate. The experimental formulation did not induce changes in milk composition or in hematological parameters. Certain factors related to pharmacokinetics, such as the type of carrier used in the formulation and the pharmacodynamics of soluble PPy, may have contributed to the antimicrobial ineffectiveness of the experimental formulation. The results of this study neither define nor decrease the antimicrobial potential of soluble PPy. Further research is required to develop formulations that enable the antibacterial action of soluble PPy in the intramammary environment of dairy cows.

Biomimetic Synthesis of PANI/Graphitic Oxidized Carbon Nitride for Supercapacitor Applications.

Polyaniline (PANI) composites have gained momentum as supercapacitive materials due to their high energy density and power density. However, some drawbacks in their performance remain, such as the low stability after hundreds of charge-discharge cycles and limitations in the synthesis scalability. Herein, we report for the first time PANI-Graphitic oxidized carbon nitride composites as potential supercapacitor material. The biomimetic polymerization of aniline assisted by hematin, supported by phosphorous and oxygen-modified carbon nitrides (g-POCN and g-OCN, respectively), achieved up to 89% yield. The obtained PAI/g-POCN and PANI/g-OCN show enhanced electrochemical properties, such as conductivity of up to 0.0375 S/cm, specific capacitances (Cs) of up to 294 F/g (at high current densities, 5 A/g) and a stable operation after 500 charge-discharge cycles (at 3 A/g). In contrast, the biomimetic synthesis of Free PANI, assisted by stabilized hematin in cosolvents, exhibited lower performance properties (65%). Due to their structural differences, the electrochemical properties of Free PANI (conductivity of 0.0045 S/cm and Cs of up to 82 F/g at 5 A/g) were lower than those of nanostructured PANI/g-POCN and g-OCN supports, which provide stability and improve the properties of biomimetically synthesized PANI. This work reveals the biomimetic synthesis of PANI, assisted by hematin supported by modified carbon nitrides, as a promising strategy to produce nanostructured supercapacitors with high performance.

Synthesis of a Smart Conductive Block Copolymer Responsive to Heat and Near Infrared Light.

A method for the synthesis of a linear block copolymer (PNIPAM-b-PANI), containing a thermoresponsive block (poly(N-isopropylacrylamide), PNIPAM) and a Near Infrared (NIR) light-absorbing block (polyaniline, PANI), is reported. The synthetic approach involves a two-step successive polymerization reaction. First, the radical polymerization of NIPAM is done using 4-aminothiophenol as a chain transfer agent for the obtention of thermosensitive block terminated with an aniline (ANI) moiety. Second, the oxidative polymerization of ANI is initiated in ANI moiety of thermosensitive block to grow the second conductive PANI block. 1H nuclear magnetic resonance (NMR) and FT-IR spectroscopy shows the characteristics peaks of both polymeric blocks revealing the successful copolymerization process. Static Light Scattering (SLS) and UV-Visible combined measurements allowed the determination of the Mw for PNIPAM-b-PANI macromolecule: 5.5 × 105 g mol-1. The resulting copolymer is soluble in water (8.3 g L-1) and in non-aqueous solvents, such as ethanol, formic acid, acetonitrile, and others. Both polymer blocks chains show the properties of the polymer chains. The block copolymer shows a lower critical solution temperature (LCST) at the same temperature (32-34 °C) than PNIPAM, while the copolymer shows pH dependent UV-vis-NIR absorption similar to PANI. The PNIPAM block suffers a coil to globule transition upon NIR light irradiation (785 nm, 100 mW), as shown by turbidimetry and Atomic Force Microscopy (AFM), due to local heating (more than 9 °C in 12 min) induced by the NIR absorption at the PANI block. Furthermore, the electrical conductivity of PNIPAM-b-PANI thin films is demonstrated (resistivity of 5.3 × 10-4 Ω-1 cm-1), indicating that the PANI block is present in its conductive form.

Nanostructural Modification of PEDOT:PSS for High Charge Carrier Collection in Hybrid Frontal Interface of Solar Cells.

In this work, we propose poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) material to form a hybrid heterojunction with amorphous silicon-based materials for high charge carrier collection at the frontal interface of solar cells. The nanostructural characteristics of PEDOT:PSS layers were modified using post-treatment techniques via isopropyl alcohol (IPA). Atomic force microscopy (AFM), Fourier-transform infrared (FTIR), and Raman spectroscopy demonstrated conformational changes and nanostructural reorganization in the surface of the polymer in order to tailor hybrid interface to be used in the heterojunctions of inorganic solar cells. To prove this concept, hybrid polymer/amorphous silicon solar cells were fabricated. The hybrid PEDOT:PSS/buffer/a-Si:H heterojunction demonstrated high transmittance, reduction of electron diffusion, and enhancement of the internal electric field. Although the structure was a planar superstrate-type configuration and the PEDOT:PSS layer was exposed to glow discharge, the hybrid solar cell reached high efficiency compared to that in similar hybrid solar cells with substrate-type configuration and that in textured well-optimized amorphous silicon solar cells fabricated at low temperature. Thus, we demonstrate that PEDOT:PSS is fully tailored and compatible material with plasma processes and can be a substitute for inorganic p-type layers in inorganic solar cells and related devices with improvement of performance and simplification of fabrication process.

Underlying Physics of Conductive Polymer Composites and Force Sensing Resistors (FSRs). A Study on Creep Response and Dynamic Loading.

Force Sensing Resistors (FSRs) are manufactured by sandwiching a Conductive Polymer Composite (CPC) between metal electrodes. The piezoresistive property of FSRs has been exploited to perform stress and strain measurements, but the rheological property of polymers has undermined the repeatability of measurements causing creep in the electrical resistance of FSRs. With the aim of understanding the creep phenomenon, the drift response of thirty two specimens of FSRs was studied using a statistical approach. Similarly, a theoretical model for the creep response was developed by combining the Burger's rheological model with the equations for the quantum tunneling conduction through thin insulating films. The proposed model and the experimental observations showed that the sourcing voltage has a strong influence on the creep response; this observation-and the corresponding model-is an important contribution that has not been previously accounted. The phenomenon of sensitivity degradation was also studied. It was found that sensitivity degradation is a voltage-related phenomenon that can be avoided by choosing an appropriate sourcing voltage in the driving circuit. The models and experimental observations from this study are key aspects to enhance the repeatability of measurements and the accuracy of FSRs.

Underlying Physics of Conductive Polymer Composites and Force Sensing Resistors (FSRs) under Static Loading Conditions.

Conductive polymer composites are manufactured by randomly dispersing conductive particles along an insulating polymer matrix. Several authors have attempted to model the piezoresistive response of conductive polymer composites. However, all the proposed models rely upon experimental measurements of the electrical resistance at rest state. Similarly, the models available in literature assume a voltage-independent resistance and a stress-independent area for tunneling conduction. With the aim of developing and validating a more comprehensive model, a test bench capable of exerting controlled forces has been developed. Commercially available sensors-which are manufactured from conductive polymer composites-have been tested at different voltages and stresses, and a model has been derived on the basis of equations for the quantum tunneling conduction through thin insulating film layers. The resistance contribution from the contact resistance has been included in the model together with the resistance contribution from the conductive particles. The proposed model embraces a voltage-dependent behavior for the composite resistance, and a stress-dependent behavior for the tunneling conduction area. The proposed model is capable of predicting sensor current based upon information from the sourcing voltage and the applied stress. This study uses a physical (non-phenomenological) approach for all the phenomena discussed here.