Correlation between polyethylene topology and melt flow instabilities by determining in-situ pressure fluctuations and applying advanced data analysis

Using three high sensitive pressure transducers located inside a slit-die of a capillary rheometer and applying a set of advanced mathematical tools to process the acquired time dependent pressure signals, we are able to detect in-situ pressure fluctuations associated with sharkskin instabilities. Other distortions, as spurt and gross melt fracture, can also be in-situ detected. This originates from a factor of 10³ and 10² improvement in terms of time and pressure resolution achieved using the new set-up and data analysis that it will be described in detail in this article. Our approach quantifies the effect of polymer topology and shear rate on the characteristic frequency and amplitude of these pressure fluctuations inside the die. Depending on the polymer structure and the shear rate, different instabilities with large deviation in their main properties at melt-state, can be determined. Based on our results, a polymer-independent power law relationship between the characteristic frequency of the instability and the apparent shear stress has been found. Combining this new technique with the advanced mathematical analysis used, clear evidences concerning the origin and location of these instabilities, could be established. According to our analysis, the spurt instability starts in the entrance of the die and it propagates downstream while increasing its velocity along the die. This was confirmed by non-zero-time-lags in the cross-correlation function between the transducers located inside the slit-die. In case of sharkskin instability, pressure fluctuations inside the die indicate that its origin could also be already inside the die instead of being exclusively located at the die-exit region, as stated in earlier investigations.     

Steroid bioconversion: Towards green processes

There is an increasing trend towards reducing the use of organic solvents in industry due to environmental constraints and the adoption of green chemistry guidelines. To overcome the low volumetric productivity of aqueous bioconversion systems involving sparingly water soluble hydrophobic compounds, processes are being developed and designed to incorporate green solvent such as supercritical fluids, ionic liquids and natural oils, and liquid polymers, among others as an alternative to organic solvents. Moreover, processes are developed and redesigned to use/reuse chemicals and reagents derived from waste or renewable feed stocks in order to diminish E-factors.In this work, the use of green solvents as key components in the bioconversion media for a multi-step microbial bioconversion was assessed in a suspended whole cell system, combined with the use of by-products as raw materials, ultimately used as carbon source for cell growth and as sterol substrate for bioconversion. The model system is the selective cleavage of the side-chain of β-sitosterol performed by free resting cells of Mycobacterium sp. NRRL B-3805, a well-established industrial multi-enzymatic process involving the use of nine catabolic enzymes in a 14-step metabolic pathway.Bioconversion yields in silicone media were higher than the ones obtained in polyethylene glycol (PEG), polypropylene glycol (PPG) and ionic liquids, as well as in dioctyl phthalate (DOP), an organic solvent that has previously been shown to allow high conversion yields. Total conversion of 12 mM substrate in silicone media was consistently obtained at the end of 120-h bioconversion runs. Similar bioconversion profiles were attained during a 50-fold scale-up, maintaining constant the power consumption per unit of volume.     

Synthesis of Benzophenones and in vitro Evaluation of Their Anticancer Potential in Breast and Prostate Cancer Cells

Breast and prostate cancers are frequently treated with chemotherapy. Several novel chemicals are being reported for this purpose, particularly synthetic and natural benzophenones. This work reports the synthesis of substituted 2-hydroxybenzophenones through 1,4-conjugate addition/intramolecular cycloaddition/dehydration of nitromethane on key intermediate chromones. Structures were extensively studied by means of 2D NMR spectroscopy and single-crystal XRD. Their cytotoxicity was evaluated in vitro in two breast cancer cell lines (MDA-MB-231 and T47-D) and one prostate cancer cell line (PC3). The most potent compound exhibited good cytotoxic effects against the three cancer cell lines (IC₅₀ values ranging from 12.09 to 26.49 μm ) and induced cell-cycle retardation only on prostate cancer cells, which suggested that it might exert cell-type-specific effects.     

Extended ceftiofur therapy for treatment of experimentally-induced Streptococcus uberis mastitis in lactating dairy cattle

Streptococcus uberis is an important cause of mastitis in dairy cows throughout the world, particularly during the dry period, the period around calving, and during early lactation. Strategies for controlling Strep. uberis mastitis are poorly defined and are currently inadequate. Objectives of the present study were to evaluate efficacy of ceftiofur, a new broad-spectrum cephalosporin antibiotic, for treatment of experimentally induced Strep. uberis intramammary infections (IMI) in lactating dairy cows during early lactation and to determine whether extended therapy regimens enhanced efficacy of ceftiofur. Efficacy of extended ceftiofur intramammary therapy regimens was investigated in 37 mammary quarters of 23 dairy cows that developed clinical mastitis following experimental infection with Strep. uberis during early lactation. Cows that developed clinical mastitis during the challenge period were allocated randomly to 3 groups representing 3 different ceftiofur treatment regimens: 2-d (n = 7 mammary quarters), 5-d (n = 16 mammary quarters), and 8-d (n = 14 mammary quarters) treatment regimens. For all groups, 125 mg of ceftiofur hydrochloride was administered via intramammary infusion. A bacteriological cure was defined as an experimentally infected quarter that was treated and was bacteriologically negative for the presence of Strep. uberis at 7, 14, 21, and 28 d posttreatment. Percentage of Strep. uberis IMI eliminated was 43, 88, and 100% for the 2-, 5-, and 8-d ceftiofur treatment regimens, respectively. Both the 5- and 8-d ceftiofur extended therapy treatment regimens had significantly higher bacterial cure rates than the standard 2-d ceftiofur treatment regimen. The bacterial cure rate of the 8-d ceftiofur extended therapy group was marginally better (P = 0.052) than the 5-d ceftiofur extended therapy group. Results of this study indicate that ceftiofur therapy was effective for eliminating Strep. uberis experimental IMI, and 5- and 8-d extended ceftiofur therapy regimens were more effective than the standard 2-d treatment.     

Occurrence of Aflatoxins and Ochratoxin A in Baby Foods in Portugal

Infants have a more restricted diet and they generally consume more food on a body weight basis than adults. Therefore, the significance and potential health risk of any contaminant in foods consumed by infants is increased and diligent attention must be paid to this particular area. The present study aims to determine the occurrence of aflatoxin M₁ (AFM₁), aflatoxin B₁ (AFB₁) and ochratoxin A (OTA) in processed cereal-based foods (flours) and infant formulae (milk powder) available in the Portuguese market, both sold as conventional and organic origin. Mycotoxin determination was carried out using a method previously applied to duplicate diet samples. This method employed chloroform extraction, liquid–liquid extraction, immunoaffinity column (IAC) cleanup and HPLC analysis with fluorescence detection after post-column derivatisation. Quantification limits were 0.014, 0.004 and 0.028 μg kg⁻¹ for AFM₁, AFB₁ and OTA, respectively. These toxins could only be quantified in 12 of 27 analysed samples (15 positive results): two samples with AFM₁, two samples with AFM₁ and OTA, one sample with AFB₁ and OTA and seven samples with OTA. Positive results concerned four for AFM₁ (26%), one for AFB₁ (7%) and ten for OTA (67%). For these samples, contents ranged between 0.017–0.041 μg AFM₁ kg⁻¹, 0.034–0.212 μg OTA kg⁻¹, and one sample had a value of 0.009 μg AFB₁ kg⁻¹. Considering the presented results, we could provisionally conclude that the presence of these mycotoxins in baby foods does not constitute a public health problem. These are the first results concerning the occurrence of mycotoxins in marketed baby foods in Portugal and this is the first study using the HPLC method, proposed for duplicate diets, in baby food sample analysis.     

Influence of powder particle injection velocity on the microstructure of Al-12Si/SiCp coatings produced by laser cladding

The influence of powder particle injection velocity on the microstructure of coatings consisting of an Al-Si matrix reinforced with SiC particles prepared by laser cladding from mixtures of powders of Al-12 wt.% Si alloy and SiC was investigated both experimentally and by modeling. At low injection velocities SiC particles react with the molten aluminum alloy. Only a small fraction of SiC remains in the microstructure, which contains large amounts of particles of the reaction products Al₄SiC₄ and Si dispersed in the α-Al + Si eutectic matrix. By contrast, at high injection velocities chemical reactions between SiC and molten aluminum are almost entirely suppressed and the resulting microstructure consists only of SiC particles dispersed in the matrix. To investigate whether this behavior could be explained by the different temperatures reached by the injected particles as they fly through the laser beam, a physical-mathematical model describing the interaction between the laser beam and the powder stream in the off-axis blown powder laser cladding process was developed and applied to calculate the temperature attained by the powder particles as a result of their interaction with an Nd:YAG laser beam (λ = 1.06 µm). At an injection velocity of 1 m/s the maximum temperature attained by SiC and Al-12Si particles is 3150 and 180 ºC, respectively. This result demonstrates that particle injection velocity is a major parameter affecting the microstructure of coatings produced by laser cladding, and must be carefully controlled.     

Comparison of Methodologies for the Extraction of Bacterial DNA from Mussels—Relevance for Food Safety

The control of the microbiological quality of bivalve molluscs assumes particular importance because they are among the most produced seafood products and mostly consumed as a whole, raw, or lightly cooked. The composition of the bacterial community associated with bivalves depends mostly on the microbiology of the surrounding environment at growing sites. Once the relationship between microbiology of bivalves and environment is established, a better classification and monitoring of the shellfish beds and evaluation of depuration strategies can be achieved. In this work, we tested if the methods of DNA extraction commonly used for the culture-independent microbiological analysis of sediment and water could be used directly, or with modifications, for the analysis of bacteria in mussels. The commercial kits Genomic DNA Purification Kit (MBI Fermentas, Vilnius, Lithuania), UltraClean^TM Soil DNA Isolation Kit (MOBIO Laboratories, Inc., Carlsbad, CA) and the method described by Griffiths and collaborators for DNA/RNA co-extraction were compared. The efficiency of extraction was assessed by DNA fluorescence and the denaturing gradient gel electrophoresis gel patterns of 16S ribosomal RNA gene fragments were used to compare the reproducibility and representativeness of the extraction methods. Results showed that the DNA/RNA co-extraction method with modifications was the most suitable. However, the results must be interpreted in the light of the purpose of the study and the relevance of maximizing extraction yield or diversity estimate, without compromising reproducibility. To our knowledge, this was the first attempt to transpose the procedure currently used for DNA extraction from sediments or waters, to the analysis of whole mussels.     

HKT Transporters—State of the Art

The increase in soil salinity poses a serious threat to agricultural yields. Under salinity stress, several Na⁺ transporters play an essential role in Na⁺ tolerance in plants. Amongst all Na⁺ transporters, HKT has been shown to have a crucial role in both mono and dicotyledonous plants in the tolerance to salinity stress. Here we present an overview of the physiological role of HKT transporters in plant Na⁺ homeostasis. HKT regulation and amino acids important to the correct function of HKT transporters are reviewed. The functions of the most recently characterized HKT members from both HKT1 and HKT2 subfamilies are also discussed. Topics that still need to be studied in future research (e.g., HKT regulation) as well as research suggestions (e.g., generation of HKT mutants) are addressed.     

Structural Refinement and Photoluminescence Properties of MnWO4 Nanorods Obtained by Microwave-Hydrothermal Synthesis

Manganese tungstate (MnWO₄) nanorods were prepared at room temperature by the co-precipitation method and synthesized after processing in a microwave-hydrothermal (MH) system at 140 °C for 6–96 min. These nanorods were structurally characterized by X-ray diffraction (XRD), Rietveld refinements and Fourier transform (FT)-Raman spectroscopy. The growth direction, shape and average size distribution of nanorods were observed by means of transmission electron microscopy (TEM) and high resolution TEM (HR-TEM). The optical properties of the nanorods were investigated by ultraviolet visible (UV-vis) absorption and photoluminescence (PL) measurements. XRD patterns, Rietveld refinement data and FT-Raman spectroscopy indicate that the MnWO₄ precipitate is not a single phase structure while the nanorods synthesized by MH processing have a wolframite-type monoclinic structure without deleterious phases. FT-Raman spectra exhibited the presence of 17 Raman-active modes from 50 to 1,000 cm⁻¹. TEM and HR-TEM micrographs indicated that the nanorods are aggregated due to surface energy by Van der Waals forces and grow along the [100] direction. UV–vis absorption measurements confirmed non-linear values for the optical band gap (from 3.2 to 2.72 eV), which increased as the MH processing time increased. The structural characterizations indicated that the presence of defects in the MnWO₄ precipitate promotes a significant contribution to maximum PL emission, while MnWO₄ nanorods obtained by MH processing decrease the PL emission due to the reduction of defects in the lattice.