trans Fatty Acids in Colostrum,Mature Milk and Diet of Lactating Adolescents

The purpose of this study was to investigate the trans fatty acids (TFA) content and distribution in colostrum, mature milk, and diet of adolescent mothers, after TFA declaration in food labels became mandatory in Brazil. Participants were healthy adolescents (n 54, 15–19 years, 1–90 days postpartum) practicing exclusive breastfeeding. Milk samples were collected 3 days after delivery (colostrum) and in the third month postpartum (mature milk) by hand expression. The fatty acid composition of the milk samples was determined by gas chromatography. TFA intake corresponded to 1.23 % of total energy value. Total 18:2 TFA accounted for less than 0.5 % of the energy intake. The amount of total 18:1 TFA (mean ± SEM) was 1.9 % ± 0.14 in colostrum and 1.5 % ± 0.2 in mature milk. The total content of n‐3 PUFA was inversely correlated with the total content of 18:1 TFA in colostrum. Both in colostrum and in mature milk, vaccenic acid (11t‐18:1) was found to be the most abundant 18:1 trans isomer, followed by elaidic acid (9t‐18:1), whereas rumenic acid (9c,11t‐18:2 CLA) was the predominant 18:2 trans isomer. In conclusion, the levels of TFA of industrial sources found in the mother's diet and breast milk (colostrum and mature milk) showed a decrease in relation to those observed in studies conducted prior to the TFA labeling resolution in Brazil. However, the current low intake levels of n‐3 LCPUFA and DHA content in the milk of lactating adolescents may be insufficient for supporting adequate neurological development of the infants.     

Mechanistic Studies of the Solvolyses of Carbamoyl Chlorides and Related Reactions

Carbamoyl chlorides are important intermediates, both in the research laboratory and in industrial scale syntheses. The most studied and used are the disubstituted derivatives, incorporating either aryl or alkyl groups (Ar₂NCOCl or R₂NCOCl). Sometimes, the groups are tied back to give a ring and piperidino- and morpholino-derivatives are commonly encountered. Some studies have been made with two different groups attached. Solvolyses tend to occur at the carbonyl carbon, with replacement of the chloride ion. Studies of both rate and products are reviewed and the solvolysis reactions are usually S_N1, although addition of an amine leads to a superimposable bimolecular component. Many of the studies under solvolytic conditions include the application of the extended Grunwald–Winstein equation. The monosubstituted derivatives (ArNHCOCl or RNHCOCl) are less studied. They are readily prepared by the addition of HCl to an isocyanate. In acetonitrile, they decompose to set up and reach equilibrium with the isocyanate (ArNCO or RNCO) and HCl. Considering that the structurally related formyl chloride (HOCOCl) is highly unstable (with formation of HCl + CO₂), the unsubstituted carbamoyl chloride (H₂NCOCl) is remarkably stable. Recommended synthetic procedures require it to survive reaction temperatures in the 300–400 °C range. There has been very little study of its reactions.     

Isothermal crystallization kinetics of poly(lactic acid)/synthetic mica nanocomposites

The isothermal crystallization kinetics of PLA/fluoromica nanocomposites was studied. Three types of synthetic mica at three concentrations (2.5, 5.0, and 7.5 wt % mica) were used and the effect of these micas on the crystallization and thermal properties of PLA was investigated by differential scanning calorimetry (DSC). The Avrami and Hoffman‐Weeks equations were used to describe the isothermal crystallization kinetics and melting behavior. Addition of these micas to the PLA matrix increased the crystallization rate, and this effect depended on the mica type and concentration. While the nonmodified Somasif ME‐100 exerted the smallest effect, the effect observed for the organically modified Somasif MPE was the most pronounced. The lower half‐time of crystallization t_1/2 was around 3 min for the PLA/Somasif MPE nanocomposites containing 7.5 wt % of filler at 90°C, which is about 16 min below that found for neat PLA. The equilibrium melting temperature ( ) of PLA were estimated for these systems, showing an increase in the composites and an increase with increasing loading, except for PLA/Somasif MPE, in which the increase of the mica content decreased about 5°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40322.     

Impact of oxygen concentration during the deposition of window layers on lowering the metastability effects in Cu(In,Ga)Se2/CBD Zn(S,O) based solar cell

The purpose of the present paper is to focus on the impact of oxygen gas partial pressure during the sputtering of i‐ZnO and ZnMgO on the transient behavior of Cu(In,Ga)Se₂ (CIGSe) based solar cells parameters when a CBD‐Zn(S,O) buffer layer is used. Based on electrical characterization of cells, it is observed that the effect of light soaking is different on J–V characteristics depending on whether oxygen is or is not present during the first deposition time of the i‐ZnO or ZnMgO layers. In fact, when cells are prepared with standard i‐ZnO, the efficiencies are very low and a pronounced transient behavior is observed. However, when the first 10 nm of i‐ZnO or ZnMgO is formed by sputtered layer without adding oxygen during the process, depending on the thickness of the buffer layer, the transient effects strongly decreases. It is then possible to get stable cells reaching efficiencies quite similar to the CdS reference cells, especially with ZnMgO, without any post‐treatments. Copyright © 2015 John Wiley & Sons, Ltd.     

Mechanical properties of in situ composites based on partially miscible blends of polyetherimide and liquid crystalline polymers

Results related to the mechanical properties of in situ composites based on partially miscible blends of polyetherimide (Ultem) and liquid crystalline polymers (HX1000 and HX4000) are discussed. It is observed that, at least in terms of the tensile and flexural modulus, there is a positive deviation from the law of mixtures. These results are analyzed and an attempt is made to explain the origin of this synergistic behavior based upon morphological data. The behavior of these partially miscible systems is compared to that of an immiscible system (Ultem/Vectra) and also that of glass-reinforced Ultem. Using blends subjected to two passes through a single screw extruder, and thereby increasing the mixing history of the Ultem/HX4000 blend, led to improved dispersion but did not lead to any measurable improvement, within experimental error, in the tensile modulus or ultimate strength (though the toughness was enhanced). The dynamic creep compliance was measured and the creep behavior with composition and temperature is discussed. The data seem to suggest that a number of factors (including partial miscibility, the properties of the specific LCP chosen as the reinforcement and the final blend morphology) all interact in a complex and as yet undetermined manner to produce the enhanced mechanical properties.     

Characterization of novel thermoresponsive poly(butylene adipate-co-terephthalate)/poly(N-isopropylacrylamide) electrospun fibers

Polymer Bulletin - In this work, electrospun fibers of poly(butylene adipate-co-terephthalate) (PBAT) and poly(N-isopropylacrylamide) (PNIPAAm) blends, PBAT/PNIPAAm, with different mass ratios,...     

The grain-boundary resistance of CeO2 ceramics: A combined microscopy-spectroscopy-simulation study of a dilute solution

Weakly acceptor-doped ceria ceramics were characterized structurally and compositionally with advanced transmission electron microscopy (TEM) techniques and electrically with electrochemical impedance spectroscopy (EIS). The grain boundaries studied with TEM were found to be free of second phases. The impedance spectra, acquired in the range 703 ≤ T/K ≤ 893 in air, showed several arcs that were analyzed in terms of bulk, grain-boundary, and electrode responses. We ascribed the grain-boundary resistance to the presence of space-charge layers. Continuum-level simulations were used to calculate charge-carrier distributions (of acceptor cations, oxygen vacancies, and electrons) in these space-charge layers. The acceptor cations were assumed to be mobile at high (sintering) temperatures but immobile at the temperatures of the EIS measurements. Space-charge formation was assumed to be driven by the segregation of oxygen vacancies to the grain-boundary core. Comparisons of data from the simulations and from the EIS measurements yielded space-charge potentials and the segregation energy of vacancies to the grain-boundary core. The space-charge potentials from the simulations are compared with values obtained by applying the standard, analytical (Mott–Schottky and Gouy–Chapman) expressions. The importance of modelling space-charge layers from the thermodynamic level is demonstrated.     

Interface engineering of nanoceramic hematite photoelectrode for solar energy conversion

This work addresses the role of different modifiers on the overall photocurrent response, which allowed a dual material insertion, increasing the charge separation without compromise the surface catalysis. Sn-addition onto nanoceramic hematite photoelectrodes clearly increased flat band potential, promoting a good charge separation, and shifting the onset to a higher potential, attributed to the surface-trapping state created by this modification. Notoriously, Sn-hematite photoelectrodes loaded with NiFeO_x exhibited the highest photocurrent density, suggesting a partially recovered surface-trapping states created during the electrode designing. The well-known cocatalyst acted in the overall photoelectrocatalytic response with no significant effect on the turn-on voltage, in other words, with minor effect related to catalytic efficiency. The dual modification contributes to understand the role of different modifiers allowing to satisfactorily improve charge separation while maintaining the conductivity attributed to IV-group ions.     

Diporphyrin tweezer for multichannel spectroscopic analysis of enantiomeric excess

Chiral 1,1’-binaphthyl-linked diporphyrin ‘tweezers’ (R)-1/(S)-1 and the corresponding zinc(II) complexes (R)-2/(S)-2 were prepared as chiral host molecules, and their utility for chiral analyses (especially enantiomeric excess (ee) determinations) were evaluated. Tris(1-n-dodecyl)porphyrins were used for the first time as the interacting units. Host capabilities of the diporphyrin tweezers were investigated by titrations with (R,R)- and (S,S)-cyclohexane-1,2-diamine (CHDA). The host molecules could be used as multichannel probes of ee by using UV-vis, circular dichroism (CD), fluorescence emission and ¹H nuclear magnetic resonance (¹H-NMR) methods. Chiral configurations could also be differentiated using CD or ¹H-NMR spectroscopy. All three optical techniques give good resolution of ee with reasonable sensitivity considering the low concentrations used (ca. 10⁻⁶ mol·L⁻¹). The ee determination of CHDA enantiomers using NMR spectroscopy is also possible because of the reasonably well separated resonances in the case of (R,R)- and (S,S)-CHDA. Non-metallated (R)-1/(S)-1 hosts could not be used to detect chiral information in a strongly acidic chiral guest. This work demonstrates the utility of 1,1’-binapthyl-linked chiral hosts for chiral analysis of ditopically interacting enantiomers.     

The effects of initial imperfection and changing support conditions on the vibration of structural elements liable to buckling

The effects of initial imperfection and support conditions which change during the loading process on the vibration of structural elements liable to buckling are discussed. Typical experimental results reported in the literature are presented. Simplified one-degree-of-freedom models which reproduce stability characteristics of columns, plates and cylindrical shells are used. Damping is not included in the analysis.