Synthesis and characterization of hybrid films from hyperbranched polyester using a sol–gel process

Hybrid organic/inorganic materials were prepared by an in situ sol–gel process using tetraethoxysilane (TEOS) in the presence of hyperbranched polyester. The influences of hyperbranched polyester molar mass as well as the amount of TEOS were examined. The condensation degree was characterized by solid state ²⁹Si NMR. The combination of solubility tests, calcination tests, SAXS and dynamic mechanical analysis allowed us to investigate the hybrid material nanostructure. The results show high compatibility between the inorganic silica phase and the organic polymer phase, due to the spherical shape of the hyperbranched polymer and its numerous hydroxyl groups. As a consequence, a continuous inorganic phase was formed even with a low silica precursor content without any macroscopic phase separation. These hybrid materials have a high T_g and high storage modulus even at an elevated temperature combined with improved thermal stability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39830.     

Synthesis and properties of polyamides from 2,5‐furandicarboxylic acid

The aim of this study is to investigate the synthesis of 2,5‐furandicarboxylic acid (FDCA)‐based copolyamides. Indeed, FDCA monomer may be a potential bio‐based alternative to phthalic acids. A series of polyamides and copolyamides, PA 6‐I(x)/6‐F(y), are synthesized in a pilot scale reactor by melt polycondensation of salts based on FDCA, isophthalic acid (IPA), and 1,6‐hexamethylenediamine. The chemical structure and composition of the resulting copolymers are extensively characterized by NMR (¹H, ¹³C, and 2D), MALDI‐TOF as well as size exclusion chromatography and solution viscosimetry. Their thermal properties are studied by differential scanning calorimetry and TGA and also by a molecular modeling technique. It is pointed out that, during the synthesis, FDCA‐rich polymers overcome a massive decarboxylation of FDCA, preventing the production of high molar mass polymers. It is also found that all polymers are amorphous and that the glass transition temperatures decrease as the amount of FDCA in the polymer increases. This is confirmed by the results from molecular dynamics. In addition, it is observed that the copolymers become more hygroscopic when the amount of FDCA in the copolyamides increases. However, the water uptake of PA 6‐I(x)/6‐F(y) with 90 > x > 50 is lower than those of PA6 and PA 66 polyamides. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45901.     

Lipid Emulsions Differentially Affect LPS-Induced Acute Monocytes Inflammation: In Vitro Effects on Membrane Remodeling and Cell Viability

The aim of this study was to assess how lipid emulsions for parenteral nutrition affect lipopolysaccharide (LPS)‐induced acute monocyte inflammation in vitro. An 18 h long LPS induced human monocyte leukemia cell stimulation was performed and the cell‐growth medium was supplemented with three different industrial lipid emulsions: Intralipid^®, containing long‐chain triglycerides (LCT—soybean oil); Medialipid^®, containing LCT (soybean oil) and medium‐chain triglycerides (MCT—coconut oil); and SMOFlipid^®, containing LCT, MCT, omega‐9 and ‐3 (soybean, coconut, olive and fish oils). Cell viability and apoptosis were assessed by Trypan blue exclusion and flow cytometry respectively. Monocyte composition and membrane remodeling were studied using gas chromatography and NR12S staining. Microparticles released in supernatant were measured by prothrombinase assay. After LPS challenge, both cellular necrosis and apoptosis were increased (threefold and twofold respectively) and microparticle release was enhanced (sevenfold) after supplementation with Medialipid^® compared to Intralipid^®, SMOFlipid^® and monocytes in the standard medium. The monocytes differentially incorporated fatty acids after lipid emulsion challenge. Finally, lipid‐treated cells displayed microparticles characterized by disrupted membrane lipid order, reflecting lipid remodeling of the parental cell plasma membrane. Our data suggest that lipid emulsions differentially alter cell viability, monocyte composition and thereby microparticle release. While MCT have deleterious effects, we have shown that parenteral nutrition emulsion containing LCT or LCT and MCT associated to n‐3 and n‐9 fatty acids have no effect on endotoxin‐induced cell death and inflammation.     

Structural heterogeneities and mechanical properties of vinyl/dimethacrylate networks synthesized by thermal free radical polymerisation

Dimethacrylate based networks usually have a poor impact resistance. In this work, we have tried to understand the origin of this brittleness. Two systems based on a same dimethacrylate monomer polymerised with styrene and divinylbenzene comonomers, respectively, have been chosen to correlate structural parameters with mechanical properties. The increase of structural heterogeneity, characterized by the width of relaxation time distribution, was measured as a function of double bonds conversion using dynamic mechanical tests. Atomic force microscopy observations of network structure after laser ablation show that the heterogeneity of networks is spacially organised due to the formation of microgels and their agglomeration. The presence of microgels strongly affects the polymerisation kinetics and controls the mechanical behaviour. Results show that the more densely crosslinked the network, the more heterogeneous is its structure. The impact resistance is shown to be related to the level of networks heterogeneities.     

PALS free volume and mechanical properties in dimethacrylate‐based thermosets

Dynamic mechanical thermal analysis, impact strength, bulk density and double‐bond conversion are reported for a series of dimethacrylate‐based networks in which the addition of styrene or/and divinylbenzene co‐monomer leads to variations in the morphology and crosslink density. The glass transition region was very broad for DVB‐rich networks and this was interpreted in terms of network heterogeneity. The mean size and the size distribution of free‐volume holes were estimated via analyses of positron annihilation lifetime spectroscopy (PALS) measurements at 22 °C and were found to be inversely correlated with the bulk density and dependent on the network heterogeneity. The PALS free volume was raised for DVB‐rich systems, due to the poor molecular packing in these highly crosslinked systems and because some regions in this heterogeneous network were in a rubbery state. The impact strength was found to be lower for the more highly crosslinked systems but was inversely correlated with the level of molecular mobility as measured by DMTA. Copyright © 2004 Society of Chemical Industry     

étude des composantes dépressives chez des adolescents à tendances suicidaires.

Studied symptoms of depression in adolescents with suicidal tendencies. Ss were 2,850 secondary school students (aged 12–18 yrs). Ss completed a questionnaire assessing sociodemographic variables, symptoms of depression, and suicidality. Results from the following subsamples were compared: (1) 105 Ss with suicidal ideation; (2) 206 Ss with suicidal ideation who had contemplated specific means of suicide; (3) 94 Ss who had attempted suicide; (4) 62 Ss with depression but without suicidal ideation; and (5) 336 age-, gender-, and grade-matched comparison Ss without suicidal ideation. The Dysphoria Scale by L. S. Radloff (1977) was used. (English abstract) (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Comparison between reconstituted and fresh skim milk chemical and electrochemical acidifications

The aim of this study was to compare the electrochemical and chemical acidification of reconstituted and fresh skim milk in terms of electrodialytic parameters, precipitation kinetics, chemical composition and physicochemical and functional properties of isolates produced by bipolar membrane electro acidification (BMEA). The electrodialytic parameters were not influenced by the type of milk when both milks were compared at a similar protein and salt content. The difference in precipitation kinetics observed between the two milks, whatever the acidification procedure, can be explained mainly by a difference in salt content. Isolates produced by BMEA showed similar physicochemical and functional properties (except for foaming capacity) to isolates produced chemically. The main factor affecting the composition and the physicochemical and functional properties was the pre‐treatment of milk prior to acidification: it had a higher impact on the functional properties than the acidification treatment itself. Copyright © 2002 Crown in the right of Canada. Published for SCI by John Wiley & Sons, Ltd     

Effect of mild autoclaving and deamidisation on the nutritive value of protein fractions

The nutritive value of zein, rapeseed 12S and α-casein was assessed by apparent digestibility coefficient (ADC) and net protein ratio (NPR). Protein fractions were suspended (100 g litre^?1) in 0.1M HCl or in water and autoclaved for 1 h. The degree of deamidisation following acid autoclaving was 14.0% for zein, 7.3% for rapeseed 12S and 8.9% for α-casein. Results indicate that autoclaving in water or in HCl improved the ADC of zein and rapeseed 12S. However, acid autoclaving increased (P<0.05) the NPR of rapeseed 12S (from 3.07 to 3.44) whereas it decreased (P<0.05) that of α-casein (from 4.21 to 3.57).     

Plasticizing and Reinforcing Features of Siloxane Domains in Amine‐Cured Epoxy/Silica Hybrids

Organic/inorganic hybrid materials comprising an amine‐epoxide network and siloxane domains are produced by the sol/gel method. The presence of both plasticizing flexible linear siloxane sequences and reinforcing nanosized silica particles and branched silsesquioxanes (SSQO) structures is confirmed by ²⁹Si NMR and SAXS analysis. The hybrids display simultaneously a monotonical reduction in T_g and an increase in rubbery plateau modulus with increasing siloxane content. At the same time, nanoindentation tests reveal an improved resistance to plastic deformation. The effect of siloxane content on the values of the rubbery plateau modulus is evaluated through the EBM model for blends and composites exhibiting the characteristic co‐continuity of the two constituent phases.