High pressure CO2 solubility in N-methyl-2-hydroxyethylammonium protic ionic liquids

The use of ionic liquids for CO₂ capture and natural gas sweetening is being object of intense research. Within the enormous group of existing ionic liquids, those based on conjugate bases of carboxylic acids seem to be particularly promising. This work addresses the study of the high pressure CO₂ solubility (up to 80 MPa) in two protic ionic liquids, N-methyl-2-hydroxyethylammonium formate and N-methyl-2-hydroxyethylammonium acetate, in a wide range of temperatures (293-353 K). A thermodynamic model based on the Peng-Robinson equation of state with the Wong-Sandler mixing rule, using the NRTL model for the activity coefficients, was here adopted to describe and evaluate the thermodynamic consistency of the experimental data. Furthermore, the study of a ternary mixture of CO₂ + CH₄ + N-methyl-2-hydroxyethylammonium acetate was investigated showing a high selectivity from the IL towards these solutes.     

Development of novel peptidomimetics containing a vinyl sulfone moiety as proteasome inhibitors

Proteasome inhibition is a topic of great interest in anticancer research. The proteolytic activity of this multicatalytic complex relies on three subunits, β1, β2 and β5, containing a caspase-like, a trypsin-like and a chymotrypsin-like active site, respectively. Several studies have demonstrated that, of the three activities, the chymotrypsin-like activity was the most necessary for cell viability and protein processing. Thus, most efforts towards the development of proteasome inhibitors have focused on the selective inhibition of the β5 subunit active site. Herein, we report the design and synthesis of a series of conformationally constrained tripeptidyl vinyl sulfones were determined to be good inhibitors of the chymotrypsin-like activity of proteasome, with K(I) values in the sub-micromolar to micromolar range. These compounds were also tested against bovine pancreatic α-chymotrypsin and human cathepsin B and L, revealing a good selectivity for the target enzyme over these related enzymes.     

New approaches to clarify antinociceptive and anti-inflammatory effects of the ethanol extract from Vernonia condensata leaves

The present study was aimed at evaluating the antinociceptive and anti-inflammatory effects of the ethanol extract from Vernonia condensata leaves in animal models, in order to afford a better understanding of these properties. The extract reduced the number of abdominal contortions at doses of 100 (51.00 ± 3.00), 200 (42.00 ± 2.98) and 400 mg/kg (39.00 ± 4.00). In formalin tests, a significant reduction in the licking time (p < 0.01) was observed in the first phase by 25.14 (200 mg/kg = 51.50 ± 4.44) and 31.15% (400 mg/kg = 48.00 ± 4.37). The doses of 100 (43.37 ± 5.15), 200 (34.62 ± 4.16) and 400 mg/kg (28.37 ± 3.98) inhibited (p < 0.001) the second phase. After 60 and 90 min of treatment, a dose of 400 mg/kg (10.13 ± 0.39 and 11.14 ± 1.33, respectively) increased the latency time. Doses of 200 and 400 mg/kg potentiated the sleeping time induced by diazepam, pentobarbital and meprobamate. The extracts (100, 200 and 400 mg/kg) showed anti-inflammatory effects by a decrease in paw edema. The extracts also reduced the exudate volume at the doses of 200 and 400 mg/kg. The leukocyte migration had significant effect (p < 0.001) at doses of 100, 200 and 400 mg/kg. The completion of additional experiments in the investigation of the antinociceptive and anti-inflammatory activities of V. condensata allowed a better understanding of the central and peripheral mechanisms involved.     

Hepatic Δ9, Δ6, and Δ5 desaturations in non-insulin-dependent diabetes mellitus eSS rats

Both diabetes mellitus type 1 and diabetes mellitus type 2 are widespread diseases that alter carbohydrate and lipid metabolism. e Stilmann-Salgado (eSS) rats are experimental animals that spontaneously evolve to a state similar to that of young people affected by non-insulin-dependent diabetes mellitus (NIDDM; type 2). Using 6-mon-old eSS rats that, according to the literature [Martinez, S.M., Tarrés, M.C., Montenegro, S, Milo, R., Picena, J.C., Figueroa, N., and Rabasa, S.R. (1988) Spontaneous Diabetes in eSS Rats, Acta Diabetol. Lat. 25, 303–313], had already developed insulin resistance, we investigated the changes evoked on Δ9, Δ6, and Δ5 liver desaturases. The abundance of mRNA and enzymatic activities were measured, as well as the FA composition of liver microsomal lipids. Compared to control rats, the mRNA content and activity of SCD-1 (stearoyl CoA-desaturase, isoform of the Δ9 desaturase) were significantly higher, urase, isoform of the Δ9 desaturase) were significantly higher, whereas the mRNA and activities of Δ6 and Δ5 desaturases were not significantly modified. Correspondingly, the proportion of 18∶1n−9 and the ratios of 18∶1n−9/18∶0 and 16∶1/16∶0 in lipids were significantly increased, whereas the proportion of 20∶4n−6 was unaltered. These effects were found while glycemia was constant or increased. The results are completely opposite those described in insulin-dependent diabetes mellitus (type 1), in which a depression of all the desaturases is found. They suggest that in eSS rats, the activities of the desaturases were not modified by an insulin-resistance effect. Moreover, we suggest that the enhancement of SCD-1 activity might be considered as another typical sign of the NIDDM syndrome, because it has also been found in other animal models of NIDDM, for example, the ones evoked by the sucrose-rich diet and in the Zucker rat.     

Effects of carbonaceous nanoparticles from low-emission and older diesel engines on human skin cells

Diesel exhaust particles (DEP) are major constituents of ambient air pollution and are associated with respiratory and cardiovascular diseases as well skin cell alterations in vitro. The epidermal cells are among the first cell populations exposed to chemical pollutants, including DEP, and are an important source of pro-inflammatory mediators. We evaluated the effects of carbonaceous soot particles from current low-emission (Euro IV) diesel engines on the oxidative and inflammatory response of normal human skin cells and compared the results with those induced by carbonaceous soot particles from an older diesel engine (BS) operating under black smoke conditions. We observed that both soot nanoparticles were spontaneously internalised by keratinocytes and distributed mostly around the cell nucleus. Moreover, at the same mass concentration, Euro IV soot particles exhibited a much higher oxidative, pro-fibrotic and toxic potential on these cell types than soot particles from the older diesel engine. These results are in agreement with and confirm our previous findings on human macrophage cells and strengthen the assumption that, at the same mass concentration, soot particles produced under low emission conditions are more cytotoxic than particles from the older diesel engine. This effect could be assigned to the defective surface structure of Euro IV diesel soot, rendering it highly active. Our findings highlight that the reduction of soot emission in terms of mass does not automatically lead to a reduction of the dangerous effects and show that soot particles from different diesel engines possess different biological behaviour towards human cells.     

Polymorphic transformation morphology of isotactic poly(1-butene)/poly(propylene-co-1-butene-co-ethylene) blends

The aim of this work was to investigate the polymorphic transformation morphology of isotactic poly(1-butene) (iPB-1) in blends with poly (propylene-co-1-butene-co-ethylene) (terPP). The blends were prepared by solution casting followed by compression-molding and were examined immediately after preparation as well as after aging for over 30 days. Morphological changes were firstly observed by polarized optical microscopy, which showed that the terPP promotes the reduction of the spherulite mean size during the crystallization of iPB-1 from the melt. Digital pulsed force microscopy provided data about the terPP interspersion between the interfibrilar and spherulitic regions of the iPB-1 crystals, causing iPB-1 spherulite deformation. However, a better distribution of the amorphous component on the iPB-1 crystals was observed after phase II to I transition, favored by the rearrangement of iPB-1 lamellae and lamellar stacks during phase transition.     

Sonocrystallization of Interesterified Fats with 20 and 30% of Stearic Acid at the sn-2 Position and Their Physical Blends

Physical blends (PB) of high oleic sunflower oil and tristearin with 20 and 30% stearic acid and their interesterified (IE) products where 20 and 30% of the fatty acids are stearic acid at the sn-2 position crystallized without and with application of high intensity ultrasound (HIU). IE samples were crystallized at supercooling temperatures (ΔT) of 12, 9, 6, and 3 °C while PB were crystallized at ΔT = 12 °C. HIU induced crystallization in PB samples, but not in the IE ones. Induction in crystallization with HIU was also observed at ΔT = 6 and 3 °C for IE C18:0 20 and 30% and at ΔT = 9 °C only for the 30% samples. Smaller crystals were obtained in all sonicated samples. Melting profiles showed that HIU induced crystallization of low melting triacylglycerols (TAGs) and promoted co-crystallization of low and high melting TAGs. In general, HIU significantly changed the viscosity, G′, and G″ of the IE 20% samples except at ΔT = 12 °C. While G′ and G″ of IE 30% did not increase significantly, the viscosity increased significantly at ΔT = 9, 6, and 3 °C from 1526 ± 880 to 6818 ± 901 Pa.s at ΔT = 3 °C. The improved physical properties of the sonicated IE can make them good contenders for trans-fatty acids replacers.     

A school-based intervention improved dietary intake outcomes and reduced waist circumference in adolescents: a cluster randomized controlled trial

Background

In Ecuador, adolescents’ food intake does not comply with guidelines for a healthy diet. Together with abdominal obesity adolescent’s inadequate diets are risk factors for non-communicable diseases. We report the effectiveness of a school-based intervention on the dietary intake and waist circumference among Ecuadorian adolescents.

Methods

A pair-matched cluster randomized controlled trial including 1430 adolescents (12–14 years old) was conducted. The program aimed at improving the nutritional value of dietary intake, physical activity (primary outcomes), body mass index, waist circumference and blood pressure (secondary outcomes). This paper reports: (i) the effect on fruit and vegetable intake, added sugar intake, unhealthy snacking (consumption of unhealthy food items that are not in line with the dietary guidelines eaten during snack time; i.e. table sugar, sweets, salty snacks, fast food, soft drinks and packaged food), breakfast intake and waist circumference; and, (ii) dose and reach of the intervention. Dietary outcomes were estimated by means of two 24-h recall at baseline, after the first 17-months (stage one) and after the last 11-months (stage two) of implementation. Dose and reach were evaluated using field notes and attendance forms. Educational toolkits and healthy eating workshops with parents and food kiosks staff in the schools were implemented in two different stages. The overall effect was assessed using linear mixed models and regression spline mixed effect models were applied to evaluate the effect after each stage.

Results

Data from 1046 adolescents in 20 schools were analyzed. Participants from the intervention group consumed lower quantities of unhealthy snacks (?23.32 g; 95% CI: ?45.25,-1.37) and less added sugar (?5.66 g; 95% CI: ?9.63,-1.65) at the end of the trial. Daily fruit and vegetable intake decreased in both the intervention and control groups compared to baseline, albeit this decrease was 23.88 g (95% CI: 7.36, 40.40) lower in the intervention group. Waist circumference (?0.84 cm; 95% CI: ?1.68, 0.28) was lower in the intervention group at the end of the program; the effect was mainly observed at stage one. Dose and reach were also higher at stage one.

Conclusions

The trial had positive effects on risk factors for non-communicable diseases, i.e. decreased consumption of unhealthy snacks. The program strategies must be implemented at the national level through collaboration between the academia and policy makers to assure impact at larger scale.

Trial registration

ClinicalTrial.gov-NCT01004367.

     

Physical properties of shortenings with low‐trans fatty acids as affected by emulsifiers and storage conditions

The quality of shortenings, such as solid fat content (SFC) and texture, strongly depends on temperature fluctuations during storage and handling. The quality of a shortening might be affected not only by temperature fluctuations but also by its chemical composition and the presence of emulsifiers. The objective of this work was to investigate the effect of emulsifier addition and storage conditions on the texture, thermal behavior and SFC of low‐trans shortenings formulated with palm oil, palm kernel oil, and vegetable oils such as sunflower and soybean oils. Several conclusions can be drawn from this study: (a) The crystallization behavior of fat blends strongly depends on the type of emulsifier used and the chemical composition of the sample; (b) the addition of emulsifiers affects not only the type of crystals formed (fractionation) but also the amount of crystals obtained (enthalpy, SFC), inducing or delaying the crystallization process; (c) emulsifiers affect the texture of the crystalline structure formed by making it softer; (d) the storage conditions affect both the texture and the SFC of the materials. This study shows that samples that are highly super‐cooled during storage become harder while samples that are less super‐cooled become softer with storage conditions.     

Experimental Investigation of Microstructure and Phase Transitions in Ag-Cu-Zn Brazing Alloys

Microstructure and phase transitions of selected brazing alloys from the Ag-Cu-Zn ternary system were investigated. Four ternary alloys with silver content in the compositional range from 25 to 60 wt.% were studied using x-ray diffraction (XRD) and scanning electron microscopy coupled with the energy-dispersive spectroscopy (SEM–EDS). Phase transitions of the investigated alloys were measured using differential scanning calorimetry (DSC). Experimentally obtained results were compared with the results of a thermodynamic calculation of the phase equilibria according to the CALPHAD method. The experiments confirmed the optimized thermodynamic parameters for the calculations from the thermodynamic assessment in literature. Phase compositions, liquidus and solidus temperatures were confirmed by the EDS and DTA methods. Additionally, the calculated solidification paths and predicted phase transformations were in agreement with the SEM images.