Phototransformation of water-soluble polymers. Part II: photooxidation of poly(ethylene oxide) in aqueous solution

Poly(ethylene oxide) (PEO) was irradiated in aqueous solution under long wavelengths (λ>300 nm, 20 °C) and in presence of oxygen. The photooxidation of PEO was studied by IR spectrophotometry, viscometry and size exclusion chromatography. The formation of the oxidation photoproducts was studied by infrared analysis of films obtained by evaporation of aliquots of irradiated aqueous solutions. The photoproducts were identified by chemical derivatization treatments coupled with infrared measurements. Viscosimetry and SEC analysis showed that photooxidation was leading to a dramatic decrease of the molecular weights. The influence of the pH of the aqueous solutions was also examined. Unexpected results were obtained for the pH 12 solutions, indicating a strong inhibition of the oxidation.

Comparison with the results obtained in the case of PEO irradiated in the solid state showed that no direct transposition of the knowledge concerning the behavior of the solid polymer could be made.     

Surface modification and immobilization in poly(acrylic acid) of Ag/ZnO for photocatalytic degradation of endocrine‐disrupting compounds

Silver‐modified ZnO particles (Ag/ZnO) are effective catalysts for the photodegradation of water pollutants such as bisphenol‐A. However, until now, their use in continuous processes was back‐drawn because of difficulties associated with their recovery. To overcome this problem, the present work aimed at immobilizing Ag/ZnO in cross‐linked poly(acrylic acid) ‐PAA‐. Ag/ZnO was first silanized using (3‐glycidyloxypropyl)trimethoxysilane and thoroughly dispersed in a water‐acrylic acid solution. The suspension was then submitted to radical polymerization in presence of a cross‐linker (N,N′‐Methylenebisacrylamide). The resulting composites were characterized in terms of chemical structure, morphology, crystallinity, thermal properties, and photostability. Their analyses showed that the silanized particles were chemically anchored to PAA and homogeneously distributed in the matrix. UV‐assisted photocatalysis of bisphenol‐A aqueous solutions showed that immobilized Ag/ZnO can achieve photodegradation performances comparable to pure Ag/ZnO and allows its use in successive cycles and, consequently, in continuous processes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43528.     

The Lack of Cytotoxic Effect and Radioadaptive Response in Splenocytes of Mice Exposed to Low Level Internal β-Particle Irradiation through Tritiated Drinking Water in Vivo

Health effects of tritium, a β-emitter and a by-product of the nuclear industry, is a subject of significant controversy. This mouse in vivo study was undertaken to monitor biological effects of low level tritium exposure. Mice were exposed to tritiated drinking water (HTO) at 10 KBq/L, 1 MBq/L and 20 MBq/L concentrations for one month. The treatment did not result in a significant increase of apoptosis in splenocytes. To examine if this low level tritium exposure alters radiosensitivity, the extracted splenocytes were challenged in vitro with 2 Gy γ-radiation, and apoptotic responses at 1 and 24 h were measured. No alterations in the radiosensitivity were detected in cells from mice exposed to tritium compared to sham-treated mice. In contrast, low dose γ-irradiation at 20 or 100 mGy, resulted in a significant increase in resistance to apoptotic cell death after 2 Gy irradiation; an indication of the radioadaptive response. Overall, our data suggest that low concentrations of tritium given to mice as HTO in drinking water do not exert cytotoxic effect in splenocytes, nor do they change cellular sensitivity to additional high dose γ-radiation. The latter may be considered as the lack of a radioadaptive response, typically observed after low dose γ-irradiation.     

Hydrido‐Cobalt Catalyst as a Selective Tool for the Dimerisation of Arylacetylenes: Scope and Theoretical Studies

A simple hydrido‐cobalt complex efficiently catalyses the highly regio‐ and stereoselective dimerisation of various terminal arylacetylenes under mild conditions. The corresponding (E)‐1,4‐enynes are obtained as sole isomers with good to excellent yields. DFT calculations revealed that the reaction proceeds via a C H activation/hydrocobaltation pathway.

     

New backing layer for transdermal drug delivery systems: coatings based on fatty acid and beeswax on chitosan films

Fatty acids and beeswax are known to improve barrier properties of biodegradable materials. Thanks to their hydrophobic character, they can act as a barrier against water giving to the material more occlusive properties. This work was aimed at preparing fatty acid and beeswax coatings for a transdermal drug delivery system. In order to study occlusive properties of these coatings, water vapor permeability and contact angle measurements were carried out. The most homogeneous coatings were obtained from the beeswax mixture. Coatings made from emulsified beeswax exhibit high hydrophobic properties and relatively good mechanical properties compared to chitosan film without coatings.     

Reinforcement effects in fractal-structure-filled rubber

A quantitative morphological analysis has been performed using AFM and SAXS measurements in order to determine the spatial distribution of fillers in silica SBR composites. The proportion of fillers in agglomerates or aggregates of silica has thus been separated. Additional measurements have been carried out to quantify the amount of modified polymer in the vicinity of the filler surface, i.e. the bound rubber. It is shown that the reinforcing phase, constituting both silica particles and bound rubber, can be considered either as the dispersed or the continuous phase depending on the filler content.The linear dynamic mechanical properties of composites are then analysed. The variations of the shear modulus as a function of the filler content are then related to either the reinforcement effect induced by fillers or the development of specific additional interactions between phases, i.e. the interface effects. To separate the respective contribution of these effects from the overall dynamic behaviour of composites, micromechanical modelling is then performed. In a first step, the viscoelasticity of composites reinforced by 5.7 vol% of silica is predicted with the help of Christensen and Lo's model. For composites filled with 10 and 15 vol% of silica, self-consistent modelling, applied in a reverse mode, confirmed that the reinforcing phase, i.e. silica particles and bound rubber, acts as the continuous phase, in agreement with the morphological analysis. From the predicted dynamic mechanical properties of the reinforcing phase, the bound rubber behaviour is thus extracted as a function of the filler content and compared to that of unfilled SBR.     

Characterization of surface defects after flanging of metallic sheets

This paper deals with surface defects of automobile outer panels, which alter significantly the vehicle quality. Such defects occur during springback, after forming or flanging steps, and are characterized by concave depression of small amplitude over the convex shape of the part. The aim of this work is to reproduce at the laboratory scale a surface defect that occurs after flanging on a geometry similar to a door upper corner. A dedicated device has been designed in order to generate small size surface defects during flanging of metallic thin sheets. The outer surface of the sample was digitalized and the spatial geometry of the defect was evaluated from curvature change along 2D profiles. This study shows that the flanging height does not influence significantly the surface defect geometry whereas the flanging radius and the corner radius modify the defect depth. Finite element simulations were also performed to compare numerical depth of the defect with experiments and also to investigate the stress and strain states in the defect area. It was shown that the spatial location of the defect is well predicted but its depth was either over- or under-estimated. Moreover, strains remained very small in the defect area, and a compression state prevailed after flanging, whereas a stress gradient developed through the thickness after springback.     

Modeling the short-circuit current density of polymer solar cells based on P3HT:PCBM blend

We have investigated the short-circuit current density of organic solar cells based on poly (3-hexylthiophene)(P3HT)/6,6-phenyl C61-butyric acid methyl ester (PCBM) blend. In order to model charge collection efficiencies with respect to short circuit density in such blends, a full optical modeling of the cell is performed. From the distribution of the electromagnetic field, we compute the rate of exciton generation. This exciton generation rate is used as input in the transport equations of holes and electrons. Charge densities at steady state are obtained as solutions are used for computing short-circuit current densities generated in the cell. The dependence of short-circuit current densities versus the thickness of the blend is analyzed and compared with our experimental data and with data extracted from the literature.     

Lipolysis-Stimulated Lipoprotein Receptor Acts as Sensor to Regulate ApoE Release in Astrocytes

Astroglia play an important role, providing de novo synthesized cholesterol to neurons in the form of ApoE-lipidated particles; disruption of this process can increase the risk of Alzheimer’s disease. We recently reported that glia-specific suppression of the lipolysis-stimulated lipoprotein receptor (LSR) gene leads to Alzheimer’s disease-like memory deficits. Since LSR is an Apo-E lipoprotein receptor, our objective of this study was to determine the effect of LSR expression modulation on cholesterol and ApoE output in mouse astrocytes expressing human ApoE3. qPCR analysis showed that siRNA-mediated lsr knockdown significantly increased expression of the genes involved in cholesterol synthesis, secretion, and metabolism. Analysis of media and lipoprotein fractions showed increased cholesterol and lipidated ApoE output in HDL-like particles. Further, lsr expression could be upregulated when astrocytes were incubated 5 days in media containing high levels (two-fold) of lipoprotein, or after 8 h treatment with 1 µM LXR agonist T0901317 in lipoprotein-deficient media. In both conditions of increased lsr expression, the ApoE output was repressed or unchanged despite increased abca1 mRNA levels and cholesterol production. We conclude that LSR acts as a sensor of lipoprotein content in the medium and repressor of ApoE release, while ABCA1 drives cholesterol efflux, thereby potentially affecting cholesterol load, ApoE lipidation, and limiting cholesterol trafficking towards the neuron.