RESUMO

Poly(p-anisidine) (PPA) is a polyaniline derivative presenting a methoxy (-OCH3) group at the para position of the phenyl ring. Considering the important role of conjugated polymers in novel technological applications, a systematic, combined experimental and theoretical investigation was performed to obtain more insight into the crystallization process of PPA. Conventional oxidative polymerization of p-anisidine monomer was based on a central composite rotational design (CCRD). The effects of the concentration of the monomer, ammonium persulfate (APS), and HCl on the percentage of crystallinity were considered. Several experimental techniques such as X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), multifractal analysis, Nuclear Magnetic Resonance (13C NMR), Fourier-transform Infrared spectroscopy (FTIR), and complex impedance spectroscopy analysis, in addition to Density Functional Theory (DFT), were employed to perform a systematic investigation of PPA. The experimental treatments resulted in different crystal structures with a percentage of crystallinity ranging from (29.2 ± 0.6)% (PPA1HT) to (55.1 ± 0.2)% (PPA16HT-HH). A broad halo in the PPA16HT-HH pattern from 2θ = 10.0-30.0° suggested a reduced crystallinity. Needle and globular-particle morphologies were observed in both samples; the needle morphology might have been related to the crystalline contribution. A multifractal analysis showed that the PPA surface became more complex when the crystallinity was reduced. The proposed molecular structures of PPA were supported by the high-resolution 13C NMR results, allowing us to access the percentage of head-to-tail (HT) and head-to-head (HH) molecular structures. When comparing the calculated and experimental FTIR spectra, the most pronounced changes were observed in ν(C-H), ν(N-H), ν(C-O), and ν(C-N-C) due to the influence of counterions on the polymer backbone as well as the different mechanisms of polymerization. Finally, a significant difference in the electrical conductivity was observed in the range of 1.00 × 10-9 S.cm-1 and 3.90 × 10-14 S.cm-1, respectively, for PPA1HT and PPA16HT-HH.

Assuntos

RESUMO

Bromelain has potential as an analgesic, an anti-inflammatory, and in cancer treatments. Despite its therapeutic effects, this protein undergoes denaturation when administered orally. Microencapsulation processes have shown potential in protein protection and as controlled release systems. Thus, this paper aimed to develop encapsulating systems using sodium alginate as a carrier material and positively charged amino acids as stabilizing agents for the controlled release of bromelain in in vitro tests. The systems were produced from the experimental design of centroid simplex mixtures. Characterizations were performed by FTIR showing that bromelain was encapsulated in all systems. XRD analyses showed that the systems are semi-crystalline solids and through SEM analysis the morphology of the formed systems followed a pattern of rough microparticles. The application of statistical analysis showed that the systems presented behavior that can be evaluated by quadratic and special cubic models, with a p-value < 0.05. The interaction between amino acids and bromelain/alginate was evaluated, and free bromelain showed a reduction of 74.0% in protein content and 23.6% in enzymatic activity at the end of gastric digestion. Furthermore, a reduction of 91.6% of protein content and 65.9% of enzymatic activity was observed at the end of intestinal digestion. The Lis system showed better interaction due to the increased stability of bromelain in terms of the amount of proteins (above 63% until the end of the intestinal phase) and the enzymatic activity of 89.3%. Thus, this study proposes the development of pH-controlled release systems aiming at increasing the stability and bioavailability of bromelain in intestinal systems.

Assuntos

RESUMO

A new systematic structural study was performed using the Atomic Force Microscopy (AFM) reporting statistical parameters of polymeric particles based on gelatin and poly-ε-caprolactone (PCL) containing essential oil from Lippia origanoides. The developed biocides are efficient alternative controlling agents of Conotrachelus humeropictus and Moniliophtora perniciosa, the main pests of Theobroma grandiflorum. Our results showed that the particles morphology can be successfully controlled by advanced stereometric parameters, pointing to an appropriate concentration of encapsulated essential oil according to the particle surface characteristics. For this reason, the absolute concentration of 1000 µg·mL-1 (P1000 system) was encapsulated, resulting in the most suitable surface microtexture, allowing a faster and more efficient essential oil release. Loaded particles presented zeta potential around (-54.3 ± 2.3) mV at pH = 8, and particle size distribution ranging from 113 to 442 nm. The hydrodynamic diameter of 90% of the particle population was found to be up to (405 ± 31) nm in the P1000 system. The essential oil release was evaluated up to 80 h, with maximum release concentrations of 63% and 95% for P500 and P1000, respectively. The best fit for the release profiles was obtained using the Korsmeyer-Peppas mathematical model. Loaded particles resulted in 100% mortality of C. humeropictus up to 48 h. The antifungal tests against M. perniciosa resulted in a minimum inhibitory concentration of 250 µg·mL-1, and the P1000 system produced growth inhibition up to 7 days. The developed system has potential as alternative controlling agent, due to its physical stability, particle surface microtexture, as well as pronounced bioactivity of the encapsulated essential oil.

RESUMO

The development of conjugated polymer-based nanocomposites by adding metallic particles into the polymerization medium allows the proposition of novel materials presenting improved electrical and optical properties. Polyaniline Emeraldine-salt form (ES-PANI) has been extensively studied due to its controllable electrical conductivity and oxidation states. On the other hand, tungsten oxide (WO3) and its di-hydrated phases, such as WO3·2H2O, have been reported as important materials in photocatalysis and sensors. Herein, the WO3·2H2O phase was directly obtained during the in-situ polymerization of aniline hydrochloride from metallic tungsten (W), allowing the formation of hybrid nanocomposites based on its full oxidation into WO3·2H2O. The developed ES-PANI-WO3·2H2O nanocomposites were successfully characterized using experimental techniques combined with Density Functional Theory (DFT). The formation of WO3·2H2O was clearly verified after two hours of synthesis (PW2 nanocomposite), allowing the confirmation of purely physical interaction between matrix and reinforcement. As a result, increased electrical conductivity was verified in the PW2 nanocomposite: the DFT calculations revealed a charge transfer from the p-orbitals of the polymeric phase to the d-orbitals of the oxide phase, resulting in higher conductivity when compared to the pure ES-PANI.

RESUMO

TiO2 time-dependent electrodeposited thin films were synthesized using an electrophoretic apparatus. The XRD analysis revealed that the films could exhibit a crystalline structure composed of ~81% anatase and ~6% rutile after 10 s of deposition, with crystallite size of 15 nm. AFM 3D maps showed that the surfaces obtained between 2 and 10 s of deposition exhibit strong topographical irregularities with long-range and short-range correlations being observed in different surface regions, a trend also observed by the Minkowski functionals. The height-based ISO, as well as specific surface microtexture parameters, showed an overall decrease from 2 to 10 s of deposition, showing a subtle decrease in the vertical growth of the films. The surfaces were also mapped to have low spatial dominant frequencies, which is associated with the similar roughness profile of the films, despite the overall difference in vertical growth observed. The electrical conductivity measurements showed that despite the decrease in topographical roughness, the films acquired a thickness capable of making them increasingly insulating from 2 to 10 s of deposition. Thus, our results prove that the deposition time used during the electrophoretic experiment consistently affects the films' structure, morphology, and electrical conductivity.

RESUMO

Gelatin/PCL bilayered particles loaded with Piper nigrum essential oil was synthesized aiming to access their morphological and surface dynamic patterns. Atomic force microscopy (AFM) was applied to investigate the 3D morphology and multifractal aspects of the particles surface. The AFM maps revealed spherical surfaces and well dispersed particles, besides a rougher surface on the loaded system. Minkowski functionals showed that shape of the rough peaks was similar in the unloaded and loaded systems; however, the presence of deep valleys on the loaded particles revealed their rougher pattern. Multifractal analysis revealed that unloaded and loaded particles presented multifractal behavior with different surface dynamics. The loaded surface presented a greater width of the multifractal spectrum and smaller difference of fractal dimensions, confirming their more vertically growing. These results can be useful in the development of novel polymeric-based particles loaded with essential oil. Their unique surface dynamics can provide enhanced physical properties and performance in emerging biotechnological applications.

Assuntos

RESUMO

Considerable efforts have been spent on environmentally friendly particles for the encapsulation of essential oils. Polymeric particles were developed to encapsulate the essential oil from Piper nigrum based on gelatin and poly-ε-caprolactone (PCL) carriers. Gas Chromatography ((Flame Ionization Detection (GC/FID) and Mass Spectrometry (GC/MS)), Atomic Force Microscopy (AFM), Nanoparticle Tracking Analysis (NTA), Confocal Laser Scanning Microscopy (CLSM), Attenuated Total Reflectance-Fourier-transform Infrared Spectroscopy (ATR-FTIR), and Ultraviolet-Visible (UV-VIS) spectroscopy were used for the full colloidal system characterization. The essential oil was mainly composed of ß-caryophyllene (~35%). The stability of the encapsulated systems was evaluated by Encapsulation Efficiency (EE%), electrical conductivity, turbidity, pH, and organoleptic properties (color and odor) after adding different preservatives. The mixture of phenoxyethanol/isotialzoni-3-one (PNE system) resulted in enhanced stability of approximately 120 and 210 days under constant handling and shelf-life tests, respectively. The developed polymeric system presented a similar controlled release in acidic, neutral, or basic pH, and the release curves suggested a pulsatile release mechanism due to a complexation of essential oil in the PCL matrix. Our results showed that the developed system has potential as an alternative stable product and as a controlling agent, due to the pronounced bioactivity of the encapsulated essential oil.

RESUMO

Poly(o-methoxyaniline) emeraldine-salt form (ES-POMA) was chemically synthesized using hydrochloric acid and subjected to a heat treatment (HT) process for 1 h at 100 °C (TT100) and 200 °C (TT200). The HT process promoted a progressive decrease in crystallinity. The Le Bail method revealed a decomposition from tetrameric to trimeric-folded chains after the HT process. The unheated POMA-ES presented a globular vesicular morphology with varied micrometric sizes. The heat treatment promoted a reduction in these globular structures, increasing the non-crystalline phase. The boundary length (S) and connectivity/Euler feature (χ) parameters were calculated from the SEM images, revealing that ES-POMA presented a wide distribution of heights. The TT100 and TT200 presented a narrow boundary distribution, suggesting smoother surfaces with smaller height variations. The UV-VIS analysis revealed that the transition at 343 nm (nonlocal π → π*) was more intense in the TT200 due to the electronic delocalization, which resulted from the reduced polymer chain caused by the HT process. In addition to the loss of conjugation, counter ion withdrawal reduced the ion-chain interaction, decreasing the local electron density. This result shows the influence of the chlorine counter ions on the peaks position related to the HOMO → LUMO transition, since the π → polaron transition occurs due to the creation of the energy states due to the presence of counter ions. Finally, the electrical conductivity decreased after the HT process from 1.4 × 10-4 S.cm-1 to 2.4 × 10-6 S.cm-1 as result of the polymer deprotonation/degradation. Thus, this paper proposed a systematic evaluation of the POMA molecular structure and crystallite size and shape after heat treatment.

Assuntos

RESUMO

Biodegradable particles were developed using poly-ε-caprolactone and gelatin carriers containing different concentrations of Allium sativum essential oil (EO) (360 µg/mL, 420 µg/mL, and 460 µg/mL). Atomic force microscopy was useful to evaluate the particles' surface based on morphological parameters. The particles' size varied from 150 nm to 300 nm. The diameter was related to the increase of the particles' height as a function of the EO concentration, influencing the roughness of the surface core values (from 20 to 30 nm) and surface irregularity. The spatial parameters Str (texture aspect ratio) and Std (texture direction) revealed low spatial frequency components. The hybrid parameters Sdq (root mean square gradient) and Sdr (interfacial area ratio) also increased as a function of the EO concentration, revealing fewer flat particles. On the other hand, the functional parameters (inverse areal material ratio and peak extreme height) suggested differences in surface irregularities. Higher concentrations of EO resulted in greater microtexture asperity on the particles' surface, as well as sharper peaks. The nanoscale morphological surface analysis allowed the determination of the most appropriate concentration of encapsulated EO, influencing statistical surface parameters.

RESUMO

In this work, the topographical effect of the scratching trajectory and the feed direction on the formation of lithographed lines on the (001) InP surface was investigated using an atomic force microscope (AFM) tip-based nanomachining approach. Nanoscratching tests were carried out using the sharp face of a diamond AFM tip in contact mode. From the topographic maps obtained by AFM, several morphological and fractal parameters were obtained and analyzed. Surface morphology presented a surface smoothing for surfaces with scratches produced in [011] and [001] directions. The height parameters confirmed this behavior because scratches in [001] direction exhibited lower roughness. Moreover, this scratch direction promoted the height distribution most symmetrical and platykurtic. The other morphological parameters revealed that this direction provided a more irregular surface (smaller Smc and Sxp ), peak distribution, denser and pointed, smaller portion of material in the core, less deep furrows, higher spatial frequency components, and high isotropy. Fractal parameters revealed that FRE90 has the highest spatial complexity, it is dominated by higher spatial frequencies, and has the lowest surface percolation. Furthermore, all samples exhibited high topographic uniformity.