Calcium carbonate and ammonium polyphosphate flame retardant additives formulated to protect ethylene vinyl acetate copolymer against fire: Hydrated or carbonated calcium?

In this study, the effect of the chemical nature of different calcium (Ca)-based minerals as flame retardant additives in combination with ammonium polyphosphate (APP), in 1:1 proportions, on the flame retardancy behavior and performance of ethylene vinyl acetate copolymer was discussed. Combining APP with partly and completely hydrated calcium oxide led to superior flame-retardant function detected in mass loss calorimeter measurements with respect to the corresponding system containing carbonated calcium. This privileged character was attributed to the higher reactivity of hydrated Ca-based fillers toward APP in comparison with Ca carbonate, which induced the formation of an intumescent residue. The difference between reactivity potential of hydrated and dry Ca was demonstrated by the newly formed thermally stable species, and further evidenced by thermogravimetric analysis performed on APP/fillers blends. Moreover, the presence of more crystalline domains in the Ca/phosphorus-based compounds was evidenced by XRD analysis of the mass loss calorimeter test residues. The results of this work highlight the role of blend additive systems on the performance of flame retardancy of polymer materials.     

Mechanical Behavior of Nanostructured and Microstructured Explosives

Nanostructured hexolites (40/60), (60/40), (80/20) and microstructured hexolite (60/40) powders are pressed by uniaxial compression to obtain explosive charges. This kind of composition is often used for the synthesis of detonation nanodiamonds. The morphology, density and cohesion of the resulting pellets are analyzed in the light of the different used compression parameters. This study allows optimizing the compression parameters to obtain well suited explosive charges from nanostructured explosive components. A good cohesion of the nanostructured explosive pellets could be obtained with increasing the temperature used for the compression. Another very important point is that the nanostructuring of the composites is maintained for every compression.     

A new genetic algorithm in proteomics: Feature selection for SELDI-TOF data

Mass spectrometry from clinical specimens is used in order to identify biomarkers in a diagnosis. Thus, a reliable method for both feature selection and classification is required. A novel method is proposed to find biomarkers in SELDI-TOF in order to perform robust classification.The feature selection is based on a new genetic algorithm. Concerning the classification, a method which takes into account the great variability on intensity by using decision stumps has been developed. Moreover, as the samples are often small, it is more appropriate to use the decision stumps simultaneously than building a complete tree. The thresholds of the decision stumps are determined in the same genetic algorithm. Finally, the method was generalized to more than two groups based on pairwise coupling. The obtained algorithm was applied on two data sets: a publicly available one containing two groups allowing a comparison with other methods from the literature and a new one containing three groups.     

Copper(I/II), α/β‐Synuclein and Amyloid‐β: Menage à Trois?

Copper binding to α‐synuclein (aS) and to amyloid‐β (Ab) has been connected to Parkinson's and Alzheimer's disease (AD), respectively, because Cu ions can modulate the peptide aggregation, and these Cu ? peptide complexes can catalyse the production of reactive oxygen species (ROS). In a significant proportion of AD brains, aggregation of aS and Ab has been detected, and it was proposed that Ab and aS interact with each other. Thus, we investigated the potential interactions of Ab and aS through their binding of copper(I) and copper(II). Additionally, β‐synuclein (bS) was investigated, due to its additional methionine residue, a potential Cu^I ligand. We found that: 1) the peptides containing the Cu‐binding domains Ab1–16, aS1–15 and bS1–15 have similar affinities towards Cu^II and towards Cu^I, with Ab1–16 being slightly stronger, 2) in the case of Cu^I, the additional Met residue in bS1–15 increased the affinity slightly, 3) the exchange of Cu^I/II between the two peptides is rapid (≤ms), 4) a/bS1–15 and Ab1–16 form a heterodimeric complex with Cu^II, 5) Cu^I probably promotes a transient ternary complex, 6) the different Cu^I/II coordination of Ab1–16, aS1–15 and bS1–15 impacts the capacity to produce ROS and to oxidise catechol, and 7) when Ab1–16, aS1–15 and Cu are present, the ROS production more closely resembles that by Ab1–16. The work gives insights into the coordination chemistry of these related peptides, and the relevance of coordination differences, the ternary complex and ROS production are discussed.     

Benzophenone vs. Copper/Benzophenone in Light‐Promoted Atom Transfer Radical Additions (ATRAs): Highly Effective Iodoperfluoroalkylation of Alkenes/Alkynes and Mechanistic Studies

Iodoperfluooralkylation of terminal alkenes and alkynes is effectively photo‐promoted by benzophenone 2 (BP) or the photoreducible copper(II) complex 1 . In particular, BP at 1 mol% in methanol upon 365 nm irradiation with a low‐pressure mercury lamp (type TLC=thin layer chromatography, 6 W) results in a fast reaction with excellent reaction yields. Complex 1 and BP 2 exhibited very similar reactivity, suggesting that the reactions involving 1 are likely to be governed by the benzophenone photoactivation processes, rather than copper(I)/(II) redox processes. Mechanistic investigations using transient absorption spectroscopy revealed that a deactivation pathway of the benzophenone triplet (³BP*) is via its reaction with the methanol solvent. We propose that the generated radicals, in particular ^.CH₂OH, play a key role in the initiation step forming R_f^. by reacting with R_fI, R_f^. then entering a radical chain cycle. ¹H NMR studies provided evidence that a substantial amount (∼7% NMR yield) of the hemiacetal CH₃OCH₂OH is formed, i.e., the possible by‐product of the reaction between ^.CH₂OH and R_fI. Finally, DFT calculations indicate that a triplet‐triplet energy transfer (TTET) process from ³BP* to perfluorooctyl iodide (C₈F₁₇I) is unlikely or should be rather slow under the reaction conditions, consistent with the transient absorption studies.

     

Estimation of chlorination by-products presence in drinking water in epidemiological studies on adverse reproductive outcomes: A review

Chlorination of drinking water is essential to prevent waterborne disease. However, chlorine reacts with organic matter present in surface waters to form various by-products. In the last decade, several epidemiological studies have been conducted to determine the connection between exposure to these chlorination by-products (CBPs) and human health defects, such as adverse reproductive outcomes. However, the methodology used to assess exposure of pregnant women in these studies had serious limitations, particularly in relation to determining CBP presence in the subject's tap water. The purpose of this paper is to critically review of methods used to evaluate the CBP presence in a subject's tap water for exposure assessment purposes in epidemiological studies focused on adverse reproductive outcomes and CBPs in drinking water. Interest is directed more precisely at space-time features related to CBPs for an optimal estimation of their presence in a subject's tap water.     

Salt influence upon the structure of aqueous solutions of branched PEO-PPO-PEO copolymers

Triblock copolymers composed of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), present an amphiphilic character in aqueous solution. Since PPO is less hydrophilic than PEO and since their solubilities decrease when the temperature increases, the copolymers self-assemble spontaneously, forming micelles at moderate temperature. For higher temperature or concentration, these solutions can form lyotropic liquid crystalline phases. In order to improve their properties for particular applications, these solutions are often used in the presence of salts. The influence of the salts nature is qualitatively well described for linear copolymer solutions of PEO-PPO-PEO type. The presence of a ‘salting out’ electrolyte shifts the cloud point and the critical micelle temperature to lower temperature while ‘salting in’ electrolyte induces opposite effects. In this article, we study the influence of the presence of sodium chloride (NaCl) on the structure of aqueous solutions of a four-branched copolymer. First, we show by viscosimetric studies that NaCl has a ‘salting out’ effect with these star copolymers as with theirs linear counterparts. Secondly, small angle neutron scattering studies make it possible to determine quantitatively the influence of the NaCl amount on the equilibrium unimers-micelles. These experiments allow obtaining the radius of micelles, their volume fraction and their aggregation number. These informations are compared with the data obtained with salt-free solutions. SANS results are also used to demonstrate that the micelles form bcc polycrystals in a significant zone of the phase diagram. The cell parameter of these crystals is determined according to the salinity of the solution. At last, we observe that the solution presents at high temperature a phase separation. Our results show clearly that this phenomenon is due to the dehydration of the PEO external layer of the micelles.     

Specific transgenerational imprinting effects of the endocrine disruptor methoxychlor on male gametes

Endocrine-disrupting chemicals (EDCs), among which methoxychlor (MXC), have been reported to affect the male reproductive system. This study evaluates the possible deleterious effects of MXC on imprinted genes. After administration of the chemical in adult male mice or in pregnant mice we analyzed by pyrosequencing possible methylation defects in two paternally imprinted (H19 and Meg3 (Gtl2)) and three maternally imprinted (Mest (Peg1), Snrpn, and Peg3) genes in the sperm and in the tail, liver, and skeletal muscle DNAs of the adult male mice and of the male offspring. MXC treatment of adult mice decreased the percentages of methylated CpGs of Meg3 and increased those of Mest, Snrpn, and Peg3 in the sperm DNA. MXC treatment of pregnant mice decreased the mean sperm concentrations by 30% and altered the methylation pattern of all the imprinted genes tested in the F1 offspring. In the latter case, MXC effects were transgenerational but disappeared gradually from F1 to F3. MXC did not affect imprinting in the somatic cells, suggesting that it exerts its damaging effects via the process of reprogramming that is unique to gamete development. A systematic analysis at the CpG level showed a heterogeneity in the CpG sensitivity to MXC. This observation suggests that not only DNA methylation but also other epigenetic modifications can explain the transgenerational effects of MXC. The reported effects of EDCs on human male spermatogenesis might be mediated by complex imprinting alterations analogous to those described in this study.     

Expression and effect of resistin on bovine and rat granulosa cell steroidogenesis and proliferation

Resistin, initially identified in adipose tissue and macrophages, was implicated in insulin resistance. Recently, its mRNA was found in hypothalamo-pituitary axis and rat testis, leading us to hypothesize that resistin may be expressed in ovary. In this study, we determined in rats and cows 1) the characterization of resistin in ovary by RT-PCR, immunoblotting, and immunohistochemistry and 2) the effects of recombinant resistin (10, 100, 333, and 667 ng/ml) ± IGF1 (76 ng/ml) on steroidogenesis, proliferation, and signaling pathways of granulosa cells (GC) measured by enzyme immunoassay, [(3)H]thymidine incorporation, and immunoblotting respectively. We observed that resistin mRNA and protein were present in several bovine and rat ovarian cells. Nevertheless, only bovine GC abundantly expressed resistin mRNA and protein. Resistin treatment decreased basal but not IGF1-induced progesterone (P<0.05; whatever the dose) and estradiol (P<0.005; for 10 and 333 ng/ml) production by bovine GC. In rats, resistin (10 ng/ml) increased basal and IGF1-induced progesterone secretion (P<0.0001), without effect on estradiol release. We found no effect of resistin on rat GC proliferation. Conversely, in cows, resistin increased basal proliferation (P<0.0001; for 100-667 ng/ml) and decreased IGF1-induced proliferation of GC (P<0.0001; for 10-333 ng/ml) associated with a decrease in cyclin D2 protein level (P<0.0001). Finally, resistin stimulated AKT and p38-MAPK phosphorylation in both species, ERK1/2-MAPK phosphorylation in rats and had the opposite effect on the AMPK pathway (P<0.05). In conclusion, our results show that resistin is expressed in rat and bovine ovaries. Furthermore, it can modulate GC functions in basal state or in response to IGF1 in vitro.     

Assessment of fly ash-aided phytostabilisation of highly contaminated soils after an 8-year field trial Part 2. Influence on plants

Aided phytostabilisation is a cost-efficient technique to manage metal-contaminated areas, particularly in the presence of extensive pollution. Plant establishment and survival in highly metal-contaminated soils are crucial for phytostabilisation success, as metal toxicity for plants is widely reported. A relevant phytostabilisation solution must limit metal transfer through the food chain. Therefore, this study aimed at evaluating the long-term efficiency of aided phytostabilisation on former agricultural soils highly contaminated by cadmium, lead, and zinc. The influence of afforestation and fly ash amendments on reducing metal phytoavailability was investigated as were their effects on plant development. Before being planted with a tree mix, the site was divided into three plots: a reference plot with no amendment, a plot amended with silico-aluminous fly ash and one with sulfo-calcic fly ash. Unlike Salix alba and Quercus robur, Alnus glutinosa, Acer pseudoplatanus and Robinia pseudoacacia grew well on the site and accumulated, overall, quite low concentrations of metals in their leaves and young twigs. This suggests that these three species have an excluder phenotype for Cd, Zn and Pb. After 8 years, metal availability to A. glutinosa, A. pseudoplatanus and R. pseudoacacia, and translocation to their above-ground parts, strongly decreased in fly ash-amended soils. Such decreases fit well together with the depletion of CaCl₂-extractable metals in amended soils. Although both fly ashes were effective to decrease Cd, Pb and Zn concentrations in above-ground parts of trees, the sulfo-calcic ash was more efficient.