Artificial neural networks in the modeling of the catalytic activity of a biosensor composed of conjugated polymers and urease.

Thin films of conjugated polymer and enzyme can be used to unravel the interaction between components in a biosensor. Using artificial neural networks (ANNs) improves data interpretability and helps construct models with great capacity for classifying and processing information. The present work used kinetic data from the catalytic activity of urease immobilized in different conjugated polymers to create ANN models using time, substrate concentration, and absorbance as input variables since the models had absorbance in a posterior instant as output value to explore the predictivity of the ANNs. The performance of the models was evaluated by Pearson's correlation coefficient (ρ) and mean squared error (MSE) values. After the learning process, a series of new experiments were performed to verify the generality of the models. As the main results, the best ANN model presented 0.9980 and 3.0736 × 10-5 for ρ and MSE, respectively. For the simulation step, intermediary values of substrate concentration were used. The mean absolute percentage error (MAPE) values were 3.34, 3.07, and 3.78 for 12 mM, 22 mM, and 32 mM concentrations, respectively. Overall, with the simulations, it was possible to ascertain the interpolatory capacity of the model, which has a learning mechanism based on absorbance and time as variables. Thus, the potential of ANNs would be in their use in pre-evaluations, helping to determine the substrate concentration at which there is higher catalytic activity or in determining the linear range of the sensor.

The Influence of Alkali Metals on the Doping of Poly(p-phenylene) Oligomers.

In this study, we report on crystallographic studies that were performed on Na- and K-doped terphenyl and quaterphenyl. The data obtained via X-ray scattering and transmission electron diffraction show that, for both K-doped terphenyl and quaterphenyl samples, there is an increase in the c parameter. However, in regard to Na-doped terphenyl, there is a c parameter decrease along with an a parameter increase, which may be accounted for by the polymerization of this oligomer. Moreover, in order to complete the crystallographic study, a Raman analysis was conducted to describe the localization of the radical anions and the local distortions induced by the electric charges during the doping process.

Langmuir and Langmuir-Blodgett Films of Poly[(9,9-dioctylfluorene)-co-(3-hexylthiophene)] for Immobilization of Phytase: Possible Application as a Phytic Acid Sensor.

In this work, the copolymer poly[(9,9-dioctylfluorene)-co-(3-hexylthiophene)] was employed as a matrix for immobilizing phytase, aiming at the detection of phytic acid. The copolymer was spread on the air-water interface forming Langmuir monolayers and phytase adsorbed from the aqueous subphase. The interactions between the copolymer and the enzyme components were investigated with surface pressure and surface potential-area isotherms, Brewster angle microscopy, and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS). The enzyme could be incorporated in the monolayers from the aqueous subphase, expanding the copolymer films and maintaining its secondary structure. The polymeric films presented a morphological heterogeneous pattern at the air-water interface because of the ability of their chains to fold and entangle, causing inherent defects in the organization as well as unbalanced lateral distribution at the air-water interface because of the formation of aggregates. The interfacial films were transferred to solid supports as Langmuir-Blodgett films and characterized by PM-IRRAS and scanning electronic microscopy, which showed not only the co-transfer of the enzyme but also the maintenance of their heterogeneous morphological pattern. The enzymatic activity of the blended film was analyzed by UV-vis spectroscopy and allowed the estimation of the value of the Michaelis constant (13.08 mM), demonstrating the feasibility of the system to selectively detect phytic acid for biosensing purposes.

Conjugated Polymers Blended with Lipids and Galactosidase as Langmuir-Blodgett Films To Control the Biosensing Properties of Nanostructured Surfaces.

The structure of enzymes must be conserved when incorporated in nanoelectronic devices because their activity determines the function of the device as sensors. Among the systems that can retain their conformational structures, Langmuir-Blodgett (LB) films can be useful to exploit the construction of bioelectronic devices organized at the molecular level because biological and polymeric materials can be coupled as ultrathin films for biosensors and actuators. In this paper, we immobilized a ß-galactosidase enzyme in the LB films of stearic acid and the conjugated polymer poly[(9,9-dioctylfluorene)- co-thiophene]. After the characterization of the floating films using tensiometry, vibrational spectroscopy, and Brewster angle microscopy, they were transferred to solid supports as LB films, and the catalytic activity of the enzyme could be preserved as analyzed using UV-vis spectroscopy. We noted that the presence of a supramolecular structure formed in the LB films not only conserved the enzyme activity but also exhibited regular and distinctive output signals in all molecular architectures employed in this work. These results are related to the synergism between the compounds on the active layer associated with a surface morphology that facilitated the analyte diffusion because of an adequate molecular accommodation of all components. This work then demonstrates the viability of employing LB films composed of lipids, enzymes, and synthetic polymers as devices for biosensing applications.

Nanocomposite Films of Silver Nanoparticles and Conjugated Copolymer in Natural and Nano-Form: Structural and Morphological Studies.

The use of conjugated polymers (CPs) and metallic nanoparticles is an interesting way to form nanocomposites with improved optical properties. For instance, a nanocomposite with high sensitivity can be produced. However, the hydrophobicity of CPs may hamper applications due to their low bioavailability and low operability in aqueous media. This problem can be overcome by forming thin solid films from an aqueous dispersion containing small CP nanoparticles. So, in this work we developed the formation of thin films of poly(9,9-dioctylfluorene-co-3,4-ethylenedioxythiophene) (PDOF-co-PEDOT) from its natural and nano form (NCP) from aqueous solution. These copolymers were then blended in films with triangular and spherical silver nanoparticles (AgNP) for future applicability as a SERS sensor of pesticides. TEM characterization showed that the AgNP were adsorbed on the NCP surface, forming a nanostructure with an average diameter of 90 nm (value according to that obtained by DLS) and with a negative potential zeta. These nanostructures were transferred to a solid substrate, forming thin and homogeneous films with different morphology of PDOF-co-PEDOT films, as observed by atomic force microscopy (AFM). XPS data demonstrated the presence of the AgNP in the thin films, as well as evidence that films with NCP are more resistant to the photo-oxidation process. Raman spectra showed characteristic peaks of the copolymer in the films prepared with NCP. It should also be noted the enhancement effect of Raman bands observed on films containing AgNP, a strong indication of the SERS effect induced by the metallic nanoparticles. Furthermore, the different geometry of the AgNP influences the way in which the adsorption between the NCP and the metal surface occurs, with a perpendicular adsorption between the NCP chains and the surface of the triangular AgNP.

Conjugated polymers as Langmuir and Langmuir-Blodgett films: Challenges and applications in nanostructured devices.

Initially developed for classic systems composed of fatty acids and phospholipids, the Langmuir and Langmuir-Blodgett (LB) techniques allow the fabrication of nanometer-scale devices at self-assembly interfaces with high control over the thickness and molecular architecture. Their application in the research and production of new plastic materials has grown considerably over the past few decades due to the efficiency of conjugated polymers (CPs) for the production of light-emitting diodes, flexible displays, solar cells, and other photoelectronic devices. The structuring of polymers at different interfaces is not trivial as this class of macromolecules can undergo through different processes of folding/unfolding, which hinders the formation of stable Langmuir monolayers and, consequently, the production of Langmuir-Blodgett films. With these ideas in mind, the present article aims to review a series of elements related to the formation of stable Langmuir and Langmuir-Blodgett films of CPs, especially those based on poly(phenylene vinylene)s, polyfluorenes, and polythiophenes. This review is divided into two parts where we first discuss the formation of neat CP films, and then the strategies for the formation of stable CP films based on the co-immobilization with fatty acids, other polymers, and enzymes as mixed films.

Conjugated polymers nanostructured as smart interfaces for controlling the catalytic properties of enzymes.

The search for new molecular architectures to improve the efficiency of enzymes entrapped in ultrathin films is useful to enhance the effectiveness of biosensors. In this present work, conjugated polymers, based on thiophene and fluorine, were investigated to verify their suitability as matrices for the immobilization of urease. The copolymer poly[(9,9-dioctylfluorene)-co-thiophene], PDOF-co-Th was spread on the air-water interface forming stable Langmuir monolayers as determined by surface pressure-area isotherms, polarization-modulation reflection-absorption infrared spectroscopy (PM-IRRAS), and Brewster angle microscopy (BAM). Urease was incorporated in the floating monolayers being further transferred to solid supports as mixed Langmuir-Blodgett (LB) films. These films were then characterized with transfer ratio, fluorescence spectroscopy, PM-IRRAS and atomic force microscopy, confirming the co-transfer of the enzyme as well as its structuring in ß-sheets. The catalytic activity was detected for urease, with a lower reaction rate than that encountered for the homogeneous environment. This was attributed to conformational constraints imposed to the biomacromolecule entrapped in the polymeric matrix.