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In this study, we evaluated the impact of incorporating diblock and triblock amphiphilic copolymers, as well as cholesterol into DPPC liposomes on the release of a model molecule, calcein, mediated by exogenous phospholipase A2 activity. Our findings show that calcein release slows down in the presence of copolymers at low concentration, while at high concentration, the calcein release profile resembles that of the DPPC control. Additionally, calcein release mediated by exogenous PLA2 decreases as the amount of solubilized cholesterol increases, with a maximum between 18 mol% and 20 mol%. At concentrations higher than 24 mol%, no calcein release was observed. Studies conducted on HEK-293 and HeLa cells revealed that DPPC liposomes reduced viability by only 5% and 12%, respectively, after 3 hours of incubation, while DPPC liposome in presence of 33 mol% of Cholesterol reduced viability by approximately 11% and 23%, respectively, during the same incubation period. For formulations containing copolymers at low and high concentrations, cell viability decreased by approximately 20% and 40%, respectively, after 3 hours of incubation. Based on these preliminary results, we can conclude that the presence of amphiphilic copolymers at low concentration can be used in the design of new DPPC liposomes, and together with cholesterol, they can modulate liposome stabilization. The new formulations showed low cytotoxicity in HEK-293 cells, and it was observed that calcein release depended entirely on PLA2 activity and the presence of calcium ions.

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The search to deliver added value to industrialized biobased materials, such as cellulose derivatives, is a relevant aspect in the scientific, technological and innovation fields at present. To address these aspects, films of cellulose acetate (CA) and a perylene derivative (Pr) were fabricated using a solution-casting method with two different compositions. Consequently, these samples were exposed to dimethylformamide (DMF) solvent vapors so that its influence on the optical, wettability, and topographical properties of the films could be examined. The results demonstrated that solvent vapor could induce the apparent total or partial preferential orientation/migration of Pr toward the polymer-air interface. In addition, photocatalytic activities of the non-exposed and DMF vapor-exposed films against the degradation of methylene blue (MB) in an aqueous medium using light-emitting diode visible light irradiation were comparatively investigated. Apparently, the observed improvement in the performance of these materials in the MB photodegradation process is closely linked to the treatment with solvent vapor. Results from this study have allowed us to propose the fabrication and use of the improved photoactivity "all-organic" materials for potential applications in dye photodegradation in aqueous media.

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In this work, we report the obtaining of new hybrid nanocomposites with catalytic activity formed by nanofibers of polymer blends and gold nanoparticles. The nanofibers were obtained by electrospinning blends of a poly (ionic liquid) (PIL) and its precursor polymer, poly (4-vinyl pyridine) (P4VPy). The characteristics of the nanofibers obtained proved to be dependent on the proportion of polymer in the blends. The nanofibers obtained were used to synthesize, in situ, gold nanoparticles on their surface by two-step procedure. Firstly, the adsorption of precursor ions on the nanofibers and then their reduction with sodium borohydride to generate gold nanoparticles. The results indicated a significant improvement in the performance of PIL-containing nanofibers over pure P4VPy NFs during ion adsorption, reaching a 20% increase in the amount of adsorbed ions and a 6-fold increase in the respective adsorption constant. The catalytic performance of the obtained hybrid systems in the reduction reaction of 4-nitrophenol to 4-aminophenol was studied. Higher catalytic conversions were obtained using the hybrid nanofibers containing PIL and gold nanoparticles achieving a maximum conversion rate of 98%. Remarkably, the highest value of kinetic constant was obtained for the nanofibers with the highest PIL content.

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In this work, polymethacrylates containing sulfonyl and nitrile functional groups were successfully prepared by conventional radical polymerization and reversible addition-fragmentation chain-transfer polymerization (RAFT). The thermal and dielectric properties were evaluated, for the first time, considering differences in their molecular weights and dispersity values. Variations of the aforementioned properties do not seem to substantially affect the polarized state of these materials, defined in terms of the parameters ε'r, ε"r and tan (δ). However, the earlier appearance of dissipative phenomena on the temperature scale for materials with lower molecular weights or broader molecular weight distributions, narrows the range of working temperatures in which they exhibit high dielectric constants along with low loss factors. Notwithstanding the above, as all polymers showed, at room temperature, ε'r values above 9 and loss factors below 0.02, presenting higher dielectric performance when compared to conventional polymer materials, they could be considered as good candidates for energy storage applications.

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In the present work, we show how amphipathic diblock copolymers affect the physicochemical properties of the lipid bilayer of DPPC liposome. Diblock copolymers proposed for this study are focused in the difference between PLA and PCL hydrophobic block, because PLA and PCL differ in their glass transition temperature, where a higher ratio of PLA, lowers the flexibility of the diblock copolymer. On the contrary, a greater proportion of PCL makes the diblock copolymer more flexible. This flexibility difference between hydrophobic block would affect the physicochemical properties of lipid bilayer of DPPC. The difference of rigidity or flexibility of hydrophobic block and their interaction with DPPC large unilamellar vesicles (LUVs) was evaluated at low and high copolymers concentration. The copolymer concentrations used were chosen based on their respective cmc. We measure (a) Thermotropic behavior from GP of Laurdan and fluorescence anisotropy of DPH; (b) Relation between wavelength excitation and generalized polarization of Laurdan; (c) Time-resolved fluorescence anisotropy of DPH; (d) Water outflow through the lipid bilayer and (e) calcein release from DPPC LUVs. Furthermore, large unilamellar vesicles in the absence and in the presence of different copolymers were characterized by size and zeta-potential. The results show that the diblock copolymer at high PLA/PCL ratio, that is, greater rigidity of hydrophobic block produces an increase of the phase transition temperature (Tm). For DPPC LUVs, Tm increase 3.5 °C at low and about 4.5 °C at high copolymers concentration, sensed by Laurdan and DPH fluorescent probes, although the DPPC/copolymers molar ratio for Cop4 is higher than Cop3, Cop2 and Cop1. In addition, we observed a decrease in the polarity of microenvironments in the bilayer and an increase in the order of the acyl chains in the bilayer to a high proportion of PLA. Furthermore, the presence of diblock copolymer with high proportion of PLA, decreases water outflow from DPPC liposome and water efflux is slower; leading to a decrease in calcein release from DPPC liposomes. Our results clearly show that the greater the stiffness of the hydrophobic block, greater degree of packaging of the lipid bilayer, greater the order of the acyl chains, and greater retention of water and calcein inside the liposome. Therefore, the presence of AB-type diblock copolymers with a more rigid hydrophobic block, stabilizes the lipid bilayer and would allow a more controlled release of water, and encapsulated molecules inside of the DPPC liposome.

Assuntos

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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.

Assuntos

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Fourth generation polyamidoamine dendrimer (PAMAM, G4) modified with fluorescein units (F) at the periphery and Pt nanoparticles stabilized by L-ascorbate were prepared. These dendrimers modified with hydrophobic fluorescein were used to achieve self-assembling structures, giving rise to the formation of nanoaggregates in water. The photoactive fluorescein units were mainly used as photosensitizer units in the process of the catalytic photoreduction of water propitiated by light. Complementarily, Pt-ascorbate nanoparticles acted as the active sites to generate H2. Importantly, the study of the functional, optical, surface potential and morphological properties of the photosensitized dendrimer aggregates at different irradiation times allowed for insights to be gained into the behavior of these systems. Thus, the resultant photosensitized PAMAM-fluorescein (G4-F) nanoaggregates (NG) were conveniently applied to light-driven water photoreduction along with sodium L-ascorbate and methyl viologen as the sacrificial reagent and electron relay agent, respectively. Notably, these aggregates exhibited appropriate stability and catalytic activity over time for hydrogen production. Additionally, in order to propose a potential use of these types of systems, the in situ generated H2 was able to reduce a certain amount of methylene blue (MB). Finally, theoretical electronic analyses provided insights into the possible excited states of the fluorescein molecules that could intervene in the global mechanism of H2 generation.

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Materials that have high dielectric constants, high energy densities and minimum dielectric losses are highly desirable for use in capacitor devices. In this sense, polymers and polymer blends have several advantages over inorganic and composite materials, such as their flexibilities, high breakdown strengths, and low dielectric losses. Moreover, the dielectric performance of a polymer depends strongly on its electronic, atomic, dipolar, ionic, and interfacial polarizations. For these reasons, chemical modification and the introduction of specific functional groups (e.g., F, CN and R-S(=O)2-R´) would improve the dielectric properties, e.g., by varying the dipolar polarization. These functional groups have been demonstrated to have large dipole moments. In this way, a high orientational polarization in the polymer can be achieved. However, the decrease in the polarization due to dielectric dissipation and the frequency dependency of the polarization are challenging tasks to date. Polymers with high glass transition temperatures (Tg) that contain permanent dipoles can help to reduce dielectric losses due to conduction phenomena related to ionic mechanisms. Additionally, sub-Tg transitions (e.g., γ and ß relaxations) attributed to the free rotational motions of the dipolar entities would increase the polarization of the material, resulting in polymers with high dielectric constants and, hopefully, dielectric losses that are as low as possible. Thus, polymer materials with high glass transition temperatures and considerable contributions from the dipolar polarization mechanisms of sub-Tg transitions are known as "dipolar glass polymers". Considering this, the main aspects of this combined strategy and the future prospects of these types of material were discussed.

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A novel method to obtain catalytic bio-nanocomposites based on chitosan containing different amounts of gold nanoparticles generated in situ is reported. The formation of gold nanoparticles takes place in solid phase assisted by a heating induced process. This method only involves the use of chitosan biopolymer and a gold salt precursor. Unlike other methods the addition of external reducing and stabilizing agents to generate gold nanoparticles, is not needed because these roles are played by chitosan. Therefore, the striking properties of chitosan (e.g., high functionality, biodegradability and biocompatibility) are profited, in order to design a facile and green route of synthesis. Additionally, the described method allows to vary the amount and size of the gold nanoparticles contained in the bio-nanocomposite by using different gold ion compositions and temperatures of heating process. Finally, the bio-nanocomposite performance as heterogeneous catalyst on the reduction of p-nitrophenol (4-NP) to p-aminophenol (4-AP) as a model system was assessed. The results showed a significant catalytic effect that increases as the content of gold nanoparticles in the bio-nanocomposite also increases.

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This work presents the synthesis of new poly(itaconate)s containing sulfone or nitrile pendant groups through conventional radical polymerization together with their characterization and comparison with poly(methacrylate)s containing identical groups. Structural and thermal characterization has been carried out in terms of Fourier transform infrared spectroscopy, differential scanning calorimetry, nuclear magnetic resonance, and thermogravimetric analysis. Characterized by broad band dielectric spectroscopy (BDS), all polymers showed dielectric constant values between 7 and 10 (at 25 °C and 1 kHz) and relative low dielectric loss values (≈0.02). BDS measurements showed, for all the polymers analyzed, notorious subglass transitions even at temperatures below -100 °C, resulting in a broad temperature interval in which these polymers exhibit high dielectric constant and could work without high losses. Therefore, these materials seem to be good candidates for dielectric applications such as energy storage, among others.