Characterization and thermal degradation kinetics of poly(l‐lactide) nanocomposites with carbon nanotubes

The purpose of this research was to study the thermal degradation kinetics of nanocomposites of poly(l ‐lactide) (PLLA) with carbon nanotubes (CNT) in order to provide further insight into their thermal stability. Nanocomposites were prepared by solvent casting with 1, 3, and 5% by weight of pristine CNT (P‐CNT) or functionalized CNT (F‐CNT), and were characterized using infrared spectroscopy, transmission electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and dynamic‐mechanical‐thermal analysis. The kinetic parameters of thermal decomposition were determined employing Coats‐Redfern method to calculate the reaction order and E₂ function model to calculate the activation energy (Ea). We found no major changes in PLLA glass transition temperatures due to CNT presence, but melt‐crystallization temperature increased slightly in some composites. In general, composites consisting of 3% or 5% of F‐CNT had superior thermal stability than did pure polymer or P‐CNT composites. This improved thermal stability was revealed by slightly higher degradation and onset temperatures, and Ea obtained from kinetic analysis. In addition, 3% or 5% of F‐CNT in PLLA composites slightly enhanced the storage modulus above the glass transition. Therefore, functionalization promoted, in some extent, better morphology and dispersion of CNT into the matrix, which was responsible for improved thermal stability and thermomechanical performance of composites at higher temperatures relative to pure polymer. POLYM. ENG. SCI., 55:710–718, 2015. © 2014 Society of Plastics Engineers     

On the use of ball milling to develop PHBV–graphene nanocomposites (I)—Morphology,thermal properties,and thermal stability

In the first part of this work, novel nanocomposites based on poly (3‐hydroxybutyrate co‐3‐hydroxyvalerate) (PHBV) and functionalized graphene nanosheets (FGS) were prepared through ball milling. As revealed by morphological characterization, this blending methodology was able to allow proper nanofiller dispersion and distribution into the matrix. Thermal properties were studied under non‐isothermal and isothermal conditions and the addition of FGS into PHBV matrix, although no changes in crystallization mechanism were observed, it modified the crystallization kinetics leading to increased crystallinity. Thermal stability analysis revealed that FGS affected the mechanism of oxidative thermal degradation and had no effect on thermal degradation by pyrolysis. Furthermore, an analysis of isothermal degradation kinetics showed that FGS speeded up the degradation rate. The Sestak‐Berggren model was used as a model to explain the isothermal degradation behavior of the obtained materials in good agreement with the experimental data. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42101.     

BMP9-Induced Survival Effect in Liver Tumor Cells Requires p38MAPK Activation

The study of bone morphogenetic proteins (BMPs) role in tumorigenic processes, and specifically in the liver, has gathered importance in the last few years. Previous studies have shown that BMP9 is overexpressed in about 40% of hepatocellular carcinoma (HCC) patients. In vitro data have also shown evidence that BMP9 has a pro-tumorigenic action, not only by inducing epithelial to mesenchymal transition (EMT) and migration, but also by promoting proliferation and survival in liver cancer cells. However, the precise mechanisms driving these effects have not yet been established. In the present work, we deepened our studies into the intracellular mechanisms implicated in the BMP9 proliferative and pro-survival effect on liver tumor cells. In HepG2 cells, BMP9 induces both Smad and non-Smad signaling cascades, specifically PI3K/AKT and p38MAPK. However, only the p38MAPK pathway contributes to the BMP9 growth-promoting effect on these cells. Using genetic and pharmacological approaches, we demonstrate that p38MAPK activation, although dispensable for the BMP9 proliferative activity, is required for the BMP9 protective effect on serum withdrawal-induced apoptosis. These findings contribute to a better understanding of the signaling pathways involved in the BMP9 pro-tumorigenic role in liver tumor cells.     

Potential of selected Portuguese cultivars for the production of high quality monovarietal virgin olive oil

The effect of cultivar and ripeness stage on the potential nutritional value of monovarietal extra virgin olive oils (MEVOOs) obtained from Cordovil, Carrasquinha, Verdeal, and Negrinha do Freixo cultivars was investigated. MEVOOs produced were characterized by high oleic acid (72–83%), tocopherol (182–530 mg/kg), and phenolic compounds (326–1110 mg/kg) content and by a similar polyphenolic profile. 1‐Penten‐3‐one was found to be the compound with the highest contribution for the aroma of the four MEVOO, related to bitter, pungent, and leaf attributes. MEVOO from Verdeal cultivar showed the best performance in terms of the composition: the highest yield of oil, the highest content of oleic acid, high tocopherol, polyphenol and sterol content, and the lowest content of linoleic acid. These characteristics give to these MEVOO not only a great oxidative stability but also interesting properties from the health point of view. MEVOO obtained with fruits at the maturity index of around 4 were in general richer in beneficial minor compounds. MEVOO produced were discriminated by variety and ripeness stage, using a stepwise linear discriminant analysis. This discrimination will in the future enable the prevention of adulteration of these monovarietal olive oils with specific nutritional composition with other olive oils. Practical implications: High‐quality MEVOOs have recently been introduced in the market, which for growers is a practical way to differentiate and increase the commercial value of extra virgin olive oil. The quantification of major and minor olive oil compounds in monovarietal olive oils represents an objective way of predicting the sensory characteristics, stability, and potential health benefits of the oils, as well as preventing their adulteration with other olive oils. This study will help in the selection of olive varieties during the maintenance or development of new olive orchards and also to select optimum harvest period for these varieties, in order to obtain MEVOOs with the maximum quality and health benefits for consumers.     

Removal of sulfamethoxazole from waters and wastewaters by conductive‐diamond electrochemical oxidation

BACKGROUND: Sulfamethoxazole (SMX, used as a model bacteriostatic antibiotic) is persistent to conventional biological treatments of wastewaters. In this work, conductive‐diamond electrochemical oxidation (CDEO) was found to be an effective technology for its removal from the effluents of conventional wastewater treatment plants. RESULTS: The use of CDEO has been evaluated for the removal of the antibiotic SMX from water and wastewaters. The results show that CDEO can reduce the concentration of this organic pollutant to values below 0.1 µg dm^?3. The variation of the SMX concentration during electrolysis shows a complex shape with a plateau zone that increases in size with the initial concentration of SMX. This complex trend is not observed in the changes of TOC, which seems to indicate that the CDEO of SMX solutions does not lead directly to the generation of carbon dioxide as a final product. A tentative reaction pathway has been proposed based on a thorough analysis of the reaction mixture, in which the main intermediate products were identified. The use of liquid chromatography time‐of‐flight mass spectrometry (LC‐TOFMS) allowed the identification of nine organic intermediates (with M_w 98, 108, 172, 173, 197, 203, 227, 269 and 287) during the electrolysis and the concentration of these compounds depends on the initial SMX concentration and on the current density applied. CONCLUSIONS: CDEO is able to reduce the concentration of the organic pollutant below 0.1 mg dm^?3. SMX removal is faster than that of TOC. This fact indicates the formation of reaction intermediates. Analytical techniques show that nine reaction intermediates are generated in the system, and that their concentration depends on the initial SMX concentration and on the current density used. Copyright © 2012 Society of Chemical Industry     

Electrospun nanofibers of a degradable poly(ester amide). Scaffolds loaded with antimicrobial agents

Electrospinning conditions were evaluated to prepare micro/nanofibers of a biodegradable poly(ester amide) constituted by L-alanine, 1,12-dodecanediol and sebacic acid. 1,1,1,3,3,3-Hexafluroroisopropanol appeared as the most appropriate solvent to obtain fibers in a wide range of electrospinning conditions that allowed tuning the final diameter size. Fiber diameter increased with the flow, distance between the needle tip and the collector and decreasing voltage, which made it possible to obtain homogeneous fibers in the 1700–320 nm range. Fibers were loaded with antimicrobial agents like silver and chlorohexidine, and the influence of agent concentration in the electrospinning solutions on the fiber diameter size was determined. The polymer was able to crystallize during the electrospinning process, giving rise to a structure slightly different from that obtained by solution crystallization and related to that attained after crystallization from the melt state. Addition of antimicrobial agents had little effect on the degree of crystallinity, although it decreased slightly when chlorhexidine was employed. Scaffolds prepared from the silver and chlorhexidine loaded samples supported cell adhesion and proliferation. Furthermore, a clear and well differentiated antimicrobial effect against both Gram-positive (e.g. M. luteus) and Gram-negative (e.g. E. coli) bacteria was demonstrated.     

Vitamin C Enhances Vitamin E Status and Reduces Oxidative Stress Indicators in Sea Bass Larvae Fed High DHA Microdiets

Docosahexaenoic acid (DHA) is an essential fatty acid necessary for many biochemical, cellular and physiological functions in fish. However, high dietary levels of DHA increase free radical injury in sea bass (Dicentrarchus labrax) larvae muscle, even when vitamin E (α-tocopherol, α-TOH) is increased. Therefore, the inclusion of other nutrients with complementary antioxidant functions, such as vitamin C (ascorbic acid, vitC), could further contribute to prevent these lesions. The objective of the present study was to determine the effect of vitC inclusion (3,600?mg/kg) in high DHA (5?% DW) and α-TOH (3,000?mg/kg) microdiets (diets 5/3,000 and 5/3,000?+?vitC) in comparison to a control diet (1?% DHA DW and 1,500?mg/kg of α-TOH; diet 1/1,500) on sea bass larvae growth, survival, whole body biochemical composition and thiobarbituric acid reactive substances (TBARS) content, muscle morphology, skeletal deformities and antioxidant enzymes, insulin-like growth factors (IGFs) and myosin expression (MyHC). Larvae fed diet 1/1,500 showed the best performance in terms of total length, incidence of muscular lesions and ossification degree. IGFs gene expression was elevated in 5/3,000 diet larvae, suggesting an increased muscle mitogenesis that was confirmed by the increase in the mRNA copies of MyHC. vitC effectively controlled oxidative damages in muscle, increased α-TOH larval contents and reduced TBARS content and the occurrence of skull deformities. The results of the present study showed the antioxidant synergism between vitamins E and C when high contents of DHA are included in sea bass larvae diets.     

Enantioselective Organocatalytic Michael Addition of Cyclobutanones to Nitroalkenes

Synthetic applications of cyclobutanones other than ring expansion and fragmentation reactions are rare. Herein, highly efficient diastereo‐ and enantioselective organocatalytic Michael additions of 2‐substituted cyclobutanone derivatives to nitroalkenes are reported allowing the stereocontrolled creation of ‘all‐carbon’ quaternary centers. The approach relies on both the use of Brønsted base/hydrogen‐bond donor bifunctional organocatalysts, and importantly, the specific stabilization and activation of cyclobutanone with a secondary amide moiety. The reaction was found to nicely accommodate a broad scope of substrates, allowing the control of up to three contiguous stereogenic centers. This work has opened new synthetic opportunities.     

Dry Fractionation of Cupuassu (Theobroma grandiflorum) Fat: Physical–Chemical Properties and Polymorphic Behavior

Physical chemical properties of cupuassu fat were modified by dry fractionation. Stearin and olein fractions were obtained at 29, 26, and 24 °C. Polymorphic behavior of unfractionated cupuassu fat (UCF) and its fractions were studied in situ by small-angle (SAXS) and wide-angle (WAXS) X-ray scattering using synchrotron light. Polymorphic transitions were followed in real time tempering samples with a thermal cycle. For UCF, the main polymorphic form crystallized under selected conditions was the β’₂. α and β’₁-forms appeared in trace amounts. β₂-form was obtained after storage at 25 °C for 3 months. Stearins obtained at 26 (S-26) and 24 °C (S-24) showed a similar polymorphic behavior. However, S-26 with improved physical properties might be more suitable for chocolate production or as a trans-fat alternative than UCF. Stearin fraction obtained at 29 °C (S-29) had a complex polymorphic behavior. The α-form was the first polymorphic form detected followed by β’₂-form. There was a polymorphic transition from α to β’₁-form but no transition between β’-forms. They were independent to each other showing fractionation in two different solid solutions. Increased contents of the triacylglycerols (TAG) SOA and SOB together with lower contents of SOO compared to UCF led to co-crystallization because there was no complete compatibility among all TAG present in S-29. β₁-form crystallized after storage forming crystals with a double-layer arrangement and a characteristic morphology. This form could be useful for accelerating crystallization process in melted liquid systems.