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.

     

Engineering of an MBR supernatant fouling layer by fine particles addition: a possible way to control cake compressibility

For membrane bioreactors (MBR) applied to wastewater treatment membrane fouling is still the prevalent issue. The main limiting phenomena related to fouling is a sudden jump of the transmembrane pressure (TMP) often attributed to the collapse of the fouling layer. Among existing techniques to avoid or to delay this collapse, the addition of active particles membrane fouling reducers (polymer, resins, powdered activated carbon (PAC), zeolithe…) showed promising results.Thus the main objective of this work is to determine if fouling can be reduced by inclusion of inert particles (500 nm and inert compared to other fouling reducers) and which is the impact on filtration performances of the structuring of the fouling. Those particles were chosen for their different surface properties and their capability to form well structured layer.Results, obtained at constant pressure in dead end mode, show that the presence of particles changes foulant deposition and induces non-compressible fouling (in the range of 0.5-1 bar) and higher rejection values compared to filtration done on supernatant alone. Indeed dead end filtration tests show that whatever interactions between biofluid and particles, the addition of particles leads to better filtration performances (in terms of rejection, and fouling layer compressibility). Moreover results confirm the important role played by macromolecular compounds, during supernatant filtration, creating highly compressible and reversible fouling.In conclusion, this study done at lab-scale suggests the potential benefit to engineer fouling structure to control or to delay the collapse of the fouling layer. Finally this study offers the opportunities to enlarge the choice of membrane fouling reducers by taking into consideration their ability to form more consistent fouling (i.e. rigid, structured fouling).     

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.     

Mice Lacking Gpr179 with Complete Congenital Stationary Night Blindness Are a Good Model for Myopia

Mutations in GPR179 are one of the most common causes of autosomal recessive complete congenital stationary night blindness (cCSNB). This retinal disease is characterized in patients by impaired dim and night vision, associated with other ocular symptoms, including high myopia. cCSNB is caused by a complete loss of signal transmission from photoreceptors to ON-bipolar cells. In this study, we hypothesized that the lack of Gpr179 and the subsequent impaired ON-pathway could lead to myopic features in a mouse model of cCSNB. Using ultra performance liquid chromatography, we show that adult Gpr179^−/− mice have a significant decrease in both retinal dopamine and 3,4-dihydroxyphenylacetic acid, compared to Gpr179^+/+ mice. This alteration of the dopaminergic system is thought to be correlated with an increased susceptibility to lens-induced myopia but does not affect the natural refractive development. Altogether, our data added a novel myopia model, which could be used to identify therapeutic interventions.     

Power Trench MOSFETs with very low specific on-resistance for 25V applications

In this paper, an investigation of the benefits of deep ultra violet lithography for the manufacturing of Trench MOSFETs and its impact on device performance is presented. We discuss experimental results for devices with a pitch size down to 0.6 μm fabricated with an unconventional implant topology and a simplified manufacturing scheme. The fabricated Trench MOSFETs are benchmarked against previously published TrenchMOS technologies by de-embedding the parasitic substrate resistance, revealing a record-low specific on-resistance of 5.3 mΩ mm² at a breakdown voltage of 30 V (V_gs = 10 V).     

Multifunctional hybrid coating on titanium towards hydroxyapatite growth: Electrodeposition of tantalum and its molecular functionalization with organophosphonic acids films

Titanium and its alloys are base materials used in the dental and orthopaedic fields owing to suitable intrinsic properties: good biocompatibility, high corrosion resistance and excellent mechanical properties. However, the bonding between titanium and bone tissue is not always strong enough and can become a critical problem. In this context, the two main objectives of this paper are the increase of the corrosion resistance and the improvement of the hydroxyapatite (HAp) growth. The surface modification considered here is achieved in three main steps and consists in the elaboration of different inorganic and organic coatings. The first step is the elaboration of electrodeposition of tantalum on the titanium oxide film of a titanium substrate. The second step is the modification of the tantalum oxide coating with organophosphonic acids. The last step is the nucleation and growth of HAP on the outermost layer of the system by immersion in a simulated body fluid. The hybrid coating tantalum oxide/organophosphonic acids/molecular layer is shown to be promising for orthopaedic implants.     

Lipid domains in the milk fat globule membrane: Specific role of sphingomyelin

Lipids are secreted in milk in the form of unique colloidal assemblies, the milk fat globules, which are surrounded by a biological membrane, the milk fat globule membrane (MFGM). Recent confocal laser scanning microscopy experiments showed heterogeneities in the composition and structure of the MFGM. For the first time, we revealed the phase separation of polar lipids in the plane of the MFGM with the lateral segregation of sphingomyelin and cholesterol in rigid liquid‐ordered (L_o) domains surrounded by the fluid matrix of glycerophospholipids in the liquid‐disordered (L_d) phase. The MFGM is a unique and highly dynamic biophysical system, the functional and nutritional properties of which need to be further studied for health benefits.     

Mechanical,Thermal, and Morphological Behavior of Silicone Rubber during Accelerated Aging

An accelerated aging study on silicone rubber exploring the effects of exposure to a functional oil (polyalkylene glycol) at elevated temperature (195°C) is reported in this paper. Variations in mechanical (tensile, tear, hardness) and thermal (conductivity, specific heat capacity) properties were monitored versus aging time while permanent deformation of the rubber was evaluated through creep and recovery measurements. Morphology and surface chemistry of the aged rubber were also investigated through scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy, respectively. Aging had a significant impact on the mechanical properties with the ultimate tensile strength and elongation at break decreasing from 7.4?MPa and 2250% in unaged samples to 1.5?MPa and 760% in 6-week aged samples, respectively. The tear strength and hardness exhibited an initial increase during the early stages of aging, followed by a decreasing trend. In contrast, the thermal properties did not change significantly and FTIR did not detect any changes in the surface chemistry of the rubber with aging. SEM however, provided evidence of an increase in brittle behavior from the morphology of the fractured surfaces.     

Gallium phosphide nanowires as a substrate for cultured neurons

Dissociated sensory neurons were cultured on epitaxial gallium phosphide (GaP) nanowires grown vertically from a gallium phosphide surface. Substrates covered by 2.5 microm long, 50 nm wide nanowires supported cell adhesion and axonal outgrowth. Cell survival was better on nanowire substrates than on planar control substrates. The cells interacted closely with the nanostructures, and cells penetrated by hundreds of wires were observed as well as wire bending due to forces exerted by the cells.