High resolution NMR study of tropical fruit seed starches

The nuclear magnetic resonance spectroscopy (NMR) studies of starches obtained by fruit seeds such as melon and watermelon were carried out as an analytical methodology to understand the molecular dynamic behavior. This study was also accompanied by the conventional X‐ray diffraction and thermal analysis. The NMR results give us a complete behavior of the samples at the molecular level. Thus, the information obtained from NMR will complement the data obtained from X‐ray and thermal analysis allowing us having responses on samples structure and dynamical behavior. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Characterization of Extra Virgin Olive Oil from Southern Brazil

Six olive oils extracted from the cultivars Arbequina, Arbosana, Coratina, Frantoio, Koroneiki, and Picual from 2017 and 2018 harvests, cultivated in Pinheiro Machado, Rio Grande do Sul, Brazil, are evaluated for standard oil composition parameters and bioactive constituents (pigments, tocopherols, and phenolic compounds). Multivariate principal component analysis (PCA) and univariate ANOVA and Fisher's LSD test are used to verify the effect of cultivar and harvest year on oil composition. Olive oil composition met extra virgin olive oil (EVOO) standard parameters and is influenced by both cultivar and harvest year. EVOO produced in 2018 has greater chlorophyll, caffeic acid, ligstroside aglycone, hydroxyoleuropein aglycone, syringic acid, and hydroxytyrosol acetate contents than the EVOOs from 2017. Linoleic acid, ferulic acid, ligstroside aglycone, and hydroxytyrosol acetate are the variables whose contents most contributed to the differentiation of oils by cultivar in both harvest years. Chemical characterization analyses allow for the differentiation of oil composition based on harvest year and cultivar. Metabolic quality data obtained here support the establishment of a local EVOO profile and the compounds that most contributed to treatment differentiation may serve as markers that can be utilized in determining origin, cultivar, and harvest year. Practical Applications: Olive production in Brazil is recent and is based on European cultivars which have not been bred for the local environmental conditions. Therefore, the measurement of olive oil metabolic quality will determine cultivar adaptability to local edaphoclimatic conditions as well as assist in the establishment of a standard of identity for the product and promote the development of its market. Olive oil produced in Southern Brazil shows high quality, and is especially rich in phenolic compounds. Although harvest year influences oil composition, oil from both harvests meet EVOO standards and cultivar specific metabolic markers are observed. This study provides the foundation for olive producers in Southern Brazil to seek authentication of the geographical origin of olive oil.     

Core–shell polypyrrole nanoparticles obtained by atmospheric pressure plasma polymerization

Polypyrrole hollow nanoparticles were prepared by atmospheric pressure plasma polymerization. The structure of the nanoparticles was studied using Fourier transform infrared and X‐ray photoelectron spectroscopies, thermogravimetric analysis, scanning and transmission electron microscopies and atomic force microscopy. In contrast to low‐pressure plasma polymerization of pyrrole, which can produce films and solid nanoparticles, we obtained two types of hollow nanoparticles: a fraction with single spherical core and another with a core composed of small bubbles. Thermal characterization allowed us to determine that the nanoparticles are composed of highly crosslinked polymer. A mechanism that explains the formation of both types of hollow nanoparticles as well as solid nanoparticles is proposed. Chemical characterization shows that, in addition to the expected chemical structures due to pyrrole polymerization, the high energy of the plasma at atmospheric pressure produces intense dehydrogenation and oxidation processes. The fluorescence spectrum of the nanoparticles, however, shows a peak at 482 nm indicating that some degree of π‐conjugation is present in the material. © 2014 Society of Chemical Industry     

Incorporation of Alpha‐Linolenic Acid and Enhancement of n‐3 Fatty Acids in Nile Tilapia: a Factorial Design

A 2² factorial design (two factors at two levels, in triplicate) was performed to investigate the influence of factors A (time of treatment, 15 and 30 days) and B (chia oil content in a supplemented diet, at 2.1 and 4.2 %) in three responses of interest referring to: (a) the incorporation of alpha‐linolenic acid (LNA) in lipids of Nile tilapia fillet; (b) the enhancement of n‐3 fatty acids; and (c) the decrease in the omega‐6/omega3 (n‐6/n‐3) ratio in fish. Factors A and B were significant in the three regression models obtained and the interaction AB was a significant contributor to the LNA and n‐6/n‐3 ratio. Analysis of variance suggested three significant and predictive mathematical models. Response surfaces analyses from designs indicated higher LNA and n‐3 contents and a lower n‐6/n‐3 ratio using both factors A and B in the higher levels (30 days of treatment and 4.2 % of chia oil in the diet for fish) chosen for this study.     

Synthesis of a PPV‐fluorene derivative: Applications in luminescent devices

Synthesis of a polyfluorene/poly(p‐phenylene vinylene) derivative, the Poly [(9,9′‐di‐hexylfluorenediylvinylene‐alt‐1,4‐phenylenevinylene)‐co‐((9,9′‐(3‐t‐butylpropanoate) fluorene‐1,4‐phenylene)] (LaPPS 42) was performed following Wittig and Suzuki routes. Polyfluorenes and derivatives have been used in electroluminescent devices, and the synthesis described here has the advantage in pave the way to get distinct structures having different emission spectra. An extensive study of its electrochemical, thermomechanical, optical, and structural properties was carried out, as well as its application in electroluminescent devices. Polymer light‐emitting diodes (PLEDs) and polymer light‐emitting electrochemical cells (PLECs) were built using LaPPS 42 as active layer, and their electric and optical characterizations confirm they have a potential as active element in electroluminescent devices. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42579.     

Chemo-enzymatic synthesis of amino acid-based surfactants

The application of lipases to the synthesis of amino acid-based surfactants was investigated. Low yields (2–9%) were obtained in the acylation of free amino acids, such as l-serine and l-lysine, as well as their ethyl esters and amides with fatty acids, owing in part to low miscibility of the reactants. When the N-carbobenzyloxy (Cbz)-l-amino acids were used in an effort to improve miscibility of the amino acid derivatives with the acyl donor, a dramatic improvement was observed for N-Cbz-l-serine (92% yield) but not for N _α-Cbz- or N _ζ-Cbz-l-lysine (7 and 2% yield, respectively). As an alternative, and efficient synthesis of N _ζ-acyl-l-lysines was developed, based on the regiospecific chemical acylation of copper(II) lysinate. In pursuit of a general route to amino acid-fatty acid surfactants, the utility of a polyol linker was investigated. Thus, the glycerol ester of N _α′ N _ζ-di-Cbz-l-lysine was prepared and evaluated as a substrate for acylation. As expected, this and other glycer-1-yl esters of N-protected amino acids were excellent substrates for lipase-catalyzed acylation. Their reaction with myristic acid in the presence of Novozyme resulted in the regioselective acylation of the primary hydroxyl group of the glycerol moiety to afford the corresponding 1-O-(N-Cbz-l-aminoacyl)-3-O-myris-toylglycerols with conversions of 50–90%. These were readily deprotected to give a range of 1-O-(aminoacyl)-3-O-myristoyl-glycerols with overall yields of 27–71%.     

Physicochemical and structural effects of electrolyte‐induced delamination on polyethylene teraphthalate‐coated steel plates

This research evaluated the in situ physicochemical changes and alterations occurring in an electrolytic chromium coated steel (ECCS), surface protected by polyethylene teraphthalate (PET) copolymer, after inducing a fracture on the coating in an acid acetic‐acetate medium. The delamination was characterized in the front of the failure by means of anodic and cathodic electrochemical mechanisms, and the resistance and degradation of the metal‐polymer composite's substrates were analyzed by means of Raman vibrational spectroscopy. The application of an electrochemical cell to generate in situ delamination, simulating the formation of pores or artificial defects, provided information on the activity inside the substrates of the PET‐coated ECCS composite as a result of the effect of the acetic acid. The anodic delamination mechanism is based on the diffusion of the electrolyte through the metal‐polymer interface and the pre‐existence of pores on the polymer layer. The cathodic delamination mechanism is based on the mechanical action of the gaseous hydrogen as a result of the reduction of H⁺. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Rotational molding of polyethylene composites based on agave fibers

In this study, agave fiber/linear medium density polyethylene composites were manufactured by rotational molding. A laboratory scale biaxial machine was used, where the internal air temperature during the processing cycle was measured. Two sizes of agave fibers (50 and 100 mesh) were used separately and mixed together (50/50) at concentrations varying between 0 and 15 wt%. The initial mixtures were obtained by dry blending, rotomolded under different operation conditions (oven temperature, processing cycle time, and rotational speeds), and the final pieces were compared. For each process condition, a complete morphological analysis was performed to relate with mechanical properties in terms of tensile, impact, and flexural strength. The results show that there is an optimum fiber concentration around 10%, and blending fiber sizes gave better tensile properties than using each size alone. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Characterization of a water-based paint for corrosion protection

Corrosion of steel rebars in reinforced concrete is one of the major problems in the construction industry. Carbonation reactions of concrete with carbon dioxide and, mainly, the chloride salts action are the main causes responsible for concrete degradation. Protective coatings help to improve the durability of concrete structures by acting as a physical barrier against the corrosion agents. Waterborne paints are usually used for concrete protection rather than solvent-based paints since they are less pollutant. The aim of this work is to investigate the influence of the pore size and porosity on the permeability of the paints films toward sodium chloride. Three characterization methods from membrane science were implemented to characterize paint coatings. The time-lag method was used to determine the permeability toward the sodium chloride and toward helium and argon, these for approximately 100% relative humidity. From the seven waterborne paints formulated, only one was found to be suitable for surface protection of reinforced concrete, since its permeability toward NaCl was smaller than 10⁻¹⁴ m² s⁻¹, the threshold value required by National Laboratory of Civil Engineering (LNEC) in Portugal. For the formulated paints, it was observed that the average pore size correlates well with the permeability toward sodium chloride. This is an important result since obtaining the permeability toward sodium chloride of corrosion protective paints is very time consuming, while the average pore size can be obtained in a much shorter time.     

Effect of physical aging on the shape-memory behavior of amorphous networks

This paper presents an experimental and modeling study of the effects of physical aging on the shape-memory performance of (meth)acrylate-based networks composed of tert-butyl acrylate (tBA) crosslinked by various concentrations of poly(ethylene glycol dimethacrylate) (PEGDMA). The experiments measured the unconstrained recovery response of samples stored at 20 °C (T_g ? 36 °C) for zero to 180 days and evaluated the effects of storage on the strain fixity, activation temperature, and initial recovery rate. A thermoviscoelastic model recently developed for amorphous networks near the T_g was applied to study the influence of structural and viscoelastic relaxation and the aging time and temperature on the recovery response. Results showed that the activation temperature and the initial recovery rate increased with the aging time, producing a sharper initial recovery response. The thermoviscoelastic model predicted that the magnitude of these effects depended on the aging temperature. There was an optimum aging temperature that maximized the initial recovery rate. These results suggest that physical aging can be manipulated to accelerate the recovery performance of shape-memory polymer devices.