An investigation of the synergistic effect between magnetite nanoparticles and polypyrrole in nanostructured layer-by-layer films

In this paper, we report the controlled fabrication of layer-by-layer (LbL) films deposited on gold substrates with three different supramolecular architectures using polypyrrole (Ppy) and magnetite nanoparticles (Fe₃O₄-np), besides conventional poly(allylamine hydrochloride) (PAH) e poly(vinyl sulfonic acid) (PVS) polyelectrolytes, demonstrating the synergistic effect between Ppy and Fe₃O₄-np such as a result of their interaction. Modified gold electrodes were analyzed by contact angle (wettability), surface plasmon resonance (SPR), raman spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The (Fe₃O₄-np/Ppy)₃ architecture was also evaluated by scanning electron microscopy. The modified gold electrodes present more homogeneous covering, higher electron transfer and a decrease of resistance with the incorporation of the nanostructured materials such as Ppy and Fe₃O₄-np forming (Fe₃O₄-np/Ppy)₃ LbL film. The results carried out in this study suggest that the (Fe₃O₄-np/Ppy)₃ LbL film can be applied as a possible electrochemical or optical non-enzymatic sensor for analytical detection.     

Polyaniline coatings on aluminium alloy 6061-T6: Electrosynthesis and characterization

The production of polyaniline films on aluminium alloy 6061-T6 in sulphuric acid was carried out by electrodeposition, using cyclic voltammetry and potentiostatic polarization. The films obtained were characterized by SEM and XPS analysis. Electrochemical techniques were also used to assess the anticorrosive properties of the coatings.The choice of the upper potential limits for potential cycling and of the fixed potential for potentiostatic production should take in consideration the balance between their effect on the minimum number of cycles (or time) needed to produce the film and on the rate of overoxidation.Polarization curves show a slight increase of the corrosion potential for polyaniline coated substrate as compared with bare metal, indicating that no significant protection is achieved by the polymer coating. The Bode diagrams show low impedance values for the alloy covered with polyaniline when compared with the results obtained for the bare metal. This can be attributed to the conductive character of the polyaniline films.     

Mid‐infrared spectroscopy as a tool for real‐time monitoring of ethanol absorption in glycols

Fast, simple, accurate, and inexpensive methods for obtaining analyte concentration data are desirable in the industrial sector. In the present study, the use of Fourier transform mid‐infrared (FT‐MIR) spectroscopy, combined with partial least squares (PLS) regression, was investigated as a tool for real‐time monitoring of processes of ethanol absorption in glycols. Calibration was performed using simple synthetic samples containing ethanol, water, and monoethylene glycol (MEG) or diethylene glycol (DEG). The PLS models presented excellent performance, with correlation coefficients (R²) close to unity and root‐mean‐square errors of cross‐validation (RMSECV) and prediction (RMSEP) lower than 2% of the calibration data ranges for both analytes (ethanol and water) in both absorbents (MEG and DEG). The monitoring technique developed has potential to be applied in absorption processes and could also be used in other large‐scale unit operations, providing information in real time and enhancing process control.     

Contributing to Understand the Crosstalk between Brain and Periphery in Methylmercury Intoxication: Neurotoxicity and Extracellular Vesicles

Human exposure to methylmercury (MeHg) is currently high in regions such as the Amazon. Understanding the molecular changes associated with MeHg-induced neurotoxicity and the crosstalk with the periphery is essential to support early diagnoses. This work aimed to evaluate cellular and molecular changes associated with behavioral alterations in MeHg acute exposure and the possible changes in extracellular vesicles (EVs) number and S100β content. Adults male Wistar rats were orally treated with 5 mg/kg for four days. Behavioral performance, molecular and histological changes in the cerebellum, and plasma EVs were assessed. MeHg-intoxicated animals performed significantly worse in behavioral tests. MeHg increased the number of GFAP+ cells and GFAP and S100β mRNA expression in the cerebellum but no change in NeuN+ or IBA-1+ cells number was detected. The number of exosomes isolated from plasma were decreased by the metal. S100B mRNA was detected in circulating plasma EVs cargo in MeHg exposure. Though preliminary, our results suggest astrocytic reactivity is displaying a protective role once there was no neuronal death. Interestingly, the reduction in exosomes number could be a new mechanism associated with MeHg-induced neurotoxicity and plasma EVs could represent a source of future biomarkers in MeHg intoxication.     

Deepening our understanding of bioactive glass crystallization using TEM and 3D nano-CT

One key issue influencing a broader application of Bioglass 45S5 in tissue engineering is its inherent crystallization tendency, severely limiting the mechanical strength of 3D porous scaffolds. Despite numerous studies, Bioglass 45S5 crystallization is not yet fully understood with regard to the mechanisms involved or morphology of the crystal phases forming. Here we show how two cutting-edge imaging techniques, state-of-the-art transmission electron microscopy (TEM) with image correction including energy dispersive X-ray spectroscopy and X-ray nano-computed tomography (nano-CT), allowed us to visualize changes in microstructure from near-nucleation to almost full crystallization in bulk Bioglass 45S5. At early times of heat treatment at 660 °C the formation of phase-separated nano-droplets within the glassy matrix was observed. Later, besides surface crystallization, bulk crystallization of combeite spheres was predominant. The formation of the first combeite spheres, their coarsening with time and finally their merging at near full crystallization were recorded by in situ high-temperature optical microscopy videos. The 3D nature of these spheres was confirmed by nano-CT, while TEM showed that their internal structure was composed of sub-micron grains. X-ray diffraction analysis at early time points showed a much higher crystalline fraction in bulk samples compared to powder samples, highlighting the influence of processing and sample morphology. These results show the importance of using complementary techniques for gaining insight into the crystallization process in the volume. In addition, we show that TEM and nano-CT are suitable characterization techniques to visualize the crystallization even in fast crystallizing systems, such as bioactive glasses.     

Experimental Investigation of the Epsilon Phase in Pb–Bi System

The Pb–Bi (Lead–Bismuth) binary system has gained some prominence in recent years due to the possible use of eutectic alloys as primary-circuit coolant in generation IV nuclear reactors. Apart from the terminal solid solutions A1-Pb and A7-Bi, the system presents also one intermetallic phase with the hexagonal close-packed structure (A3), usually denoted ε phase. Due to the low temperatures involved in this system, attainment of equilibrium is difficult, and in addition, the proximity of x-ray scattering factors for both elements raises questions about a possible polymorphic transition. In the present work, three samples with compositions Pb–29 wt.%Bi, Pb–31 wt.%Bi and Pb–33 wt.%Bi were prepared and characterized by x-ray diffraction. The lattice parameters of ε are consistent with those reported in the literature, and their dependence on Bi content was determined as well. Only the hexagonal phase was identified in the 29 wt.%Bi sample, although the currently assessed Pb–Bi phase diagram predicts the presence of the Pb-rich A1 terminal solid solution in this composition. A 2-year annealing at room temperature was performed and the XRD characterization results for these samples are compared with the original data.     

Research of the physical-chemical properties of adhesive radiation-modified thermosetting materials based on polyolefins and their composites

The present paper surveys the investigation results of the adhesive behavior with steel of different polyethylenes (LDPE, HDPE) irradiated with γ-radiation in vacuum, oxygen, and air, using rheological, optical, thermomechanical and other methods. To study the adhesive contact, the technological parameters applicable to thermosetting polymer material were taken into consideration. The results show the suitable methods in order to obtain thermosetting polymer materials with improved adhesive and thermomechanical properties.     

Chemical Defenses Against Fish Predation in Three Brazilian Octocorals: 11β,12β-Epoxypukalide as a Feeding Deterrent in Phyllogorgia dilatata

The feeding-deterrence properties of crude extracts of three Brazilian octocoral species, Neospongodes atlantica Kükenthal (Alcyonacea, Nephtheidae), Plexaurella regia Castro (Gorgonacea, Plexauridae), and Phyllogorgia dilatata Esper (Gorgonacea, Gorgoniidae), were investigated. All the extracts were incorporated into food strips at the concentrations occurring in the living organisms. Crude extract and its ethyl acetate fraction obtained from P. dilatata collected in Armação dos Búzios (Rio de Janeiro State), when incorporated into artificial diets and tested in the habitat of origin, reduced consumption of food strips by fishes, relative to controls. Crude extracts from two octocoral species collected at the National Marine Park of Abrolhos (Bahia State), N. atlantica and P. regia, had no apparent feeding-deterrence properties; in fact, they seemed to stimulate feeding. Bioassay-guided fractionation of the bioactive P. dilatata crude extract revealed that the deterrent property was restricted to a medium polarity fraction. Field palatability experiments with two pure compounds isolated from this fraction revealed that the furanocembranolide 11,12-epoxypukalide is a potent feeding deterrent produced by P. dilatata against fish. Apparently, furanocembranolides are a particular class of compounds with feeding deterrent properties, protecting some octocorals from potential fish predator species in both tropical and temperate environments.     

Influence of Precipitation Changes on the SPI and Related Drought Severity. An Analysis Using Long-Term Data Series

Drought indices, such as the Standardized Precipitation Index (SPI) are used to quantify drought severity. Due to the SPI probabilistic and standardized nature, a given value of SPI computed in distinct time periods or locations indicates the same relative drought severity but corresponds to different amounts of precipitation. Thus, the present study aims at contributing for a comprehensive analysis of the influence of long-term precipitation variability on drought assessment by the SPI. Long records of monthly precipitation, spanning from 1863 to 2007 in several locations across Portugal, were divided into 30 years sub-periods and the SPI with 12-month time scale (SPI-12) was computed for each sub-period and for the entire period of records. The probability distributions adjusted to precipitation in those different time periods were compared envisaging to detect the SPI sensitivity to the reference period and, therefore, to changes in precipitation. Precipitation thresholds relative to the upper limits of SPI-12 drought categories were obtained and the influence of the time period was investigated. Results have shown that when SPI values derived from the full data record for a recent time period are lower/higher than the SPI values derived from data of the considered time period a recent downward/upward shift of precipitation has occurred. Coherently, a common pattern of drought aggravation from the initial until the more recent period was not detected. However, in southern locations, lower precipitation thresholds of the SPI drought categories were generally found in the more recent period, particularly for more severe drought categories, whereas in the northern locations Porto and Montalegre, an increase was detected. The impacts of the reference period on the computed SPI drought severity and frequency are shown, bringing to discussion the need for updating ´normal´ conditions when long term precipitation records are available and precipitation changes are observed.     

Computational Shelf-Life Dating: Complex Systems Approaches to Food Quality and Safety

Shelf-life is defined as the time that a product is acceptable and meets the consumers expectations regarding food quality. It is the result of the conjunction of all services in production, distribution, and consumption. Shelf-life dating is one of the most difficult tasks in food engineering. Market pressure has lead to the implementation of shelf-life by sensory analyses, which may not reflect the full quality spectra. Moreover, traditional methods for shelf-life dating and small-scale distribution chain tests cannot reproduce in a laboratory the real conditions of storage, distribution, and consumption on food quality. Today, food engineers are facing the challenges to monitor, diagnose, and control the quality and safety of food products. The advent of nanotechnology, multivariate sensors, information systems, and complex systems will revolutionize the way we manage, distribute, and consume foods. The informed consumer demands foods, under the legal standards, at low cost, high standards of nutritional, sensory, and health benefits. To accommodate the new paradigms, we herein present a critical review of shelf-life dating approaches with special emphasis in computational systems and future trends on complex systems methodologies applied to the prediction of food quality and safety.