Hydrolytic kinetic model predicting embrittlement in thermoplastic elastomers

A hydrolytic kinetic model predicting chains scissions of a polyurethane elastomer (TPU) containing an anti-hydrolysis agent (stabilization via carbodiimide) was developed. This model is based on four components: uncatalysed hydrolysis, acid-catalysed hydrolysis, carboxylic acid dissociation and competitive carbodiimide-based deactivation of acid. Protons were considered as the key catalyst responsible for the hydrolysis. Model parameters were determined by fitting experimental data measured on unstabilized and stabilized TPUs, aged in immersion from 40 to 90 °C. Scission kinetics were predicted for immersion and 50% relative humidity conditions, from 10 to 100 °C. Structure-failure property relationships were also investigated, between molar mass and elongation at break. A master curve was established for elongation at break with molar mass, including both TPUs at four ageing temperatures. By combining predictions for scission kinetics with the molar mass-elongation at break master curve and an embrittlement molar mass as the end-of-life criterion, non-Arrhenian lifetime predictions are proposed for all exposure conditions considered

Carbon Nanotube and Porphyrins:Materials for Optics and Energy Applications

International audienceThe fabrication of functional hybrid materials that preserves and combines the properties of their building blocks is a central issue of nanosciences. Among the different classes of nanomaterials, carbon nanotubes are promising for electronics, opto-electronics, catalysis and composite applications. In this context the combination of nanotubes with porphyrins has been widely explored for catalytic or electron transfer purposes. Here I present two results obtained recently on the nanotube/porphyrincomposites, the first deals with the supramolecular organization in micelles of porphyrins around the nanotubes. In this work we were able to explain the Davidoff splitting observed on the absorption bands of the porphyrins by their organization around the nanotubes. The second deals with the synergic effect on catalytic activity of carbon nanotubes and strapped iron porphyrin hybrids for Oxygen Reduction Reaction (ORR). In particular, we demonstrated that the combination of both components - MWNTs and porphyrin - leads to a better catalytic activity than those of the nanotubes or the porphyrins taken separately.This study highlights the importance of the carbon support for the catalysis. The nanotubes ensure the availability of electrons to the porphyrin catalysts and allow the ORR to occur via the 4-electron pathway, avoiding the production of hydrogen peroxide

Unprecedented incorporation of α-emitter radioisotope 213Bi into porphyrin chelates with reference to a daughter isotope mediated assistance mechanism.

International audienceFor the first time, α-emitter radioisotope (213)Bi has been incorporated into porphyrin chelates, with rates matching with the short period of the radionuclide. An in situ transmetalation mechanism involving the daughter isotope (209)Pb is expected to boost the (213)Bi radiolabeling process

A novel hypomorphic splice variant in EIF2B5 gene is associated with mild ovarioleukodystrophy

Objective: To identify the genetic cause in an adult ovarioleukodystrophy patient resistant to diagnosis. Methods: We applied whole-exome sequencing (WES) to a vanishing white matter disease patient associated with premature ovarian failure at 26 years of age. We functionally tested an intronic variant by RT-PCR on patient's peripheral blood mononuclear cells (PBMC) and by minigene splicing assay. Results: WES analysis identified two novel variants in the EIF2B5 gene: c.725A > G (p.Tyr242Cys) and an intronic noncanonical mutation (c.1156 + 13G>A). This intronic mutation resulted into generation of various isoforms both in patient's PBMC and in the minigene splicing assay, showing that ~20% residual wild-type isoform is still expressed by the intronic-mutated allele alone, concordant with an hypomorphic effect of this variant. Conclusion: We report two novel variants in EIF2B5, one of them a noncanonical intronic splice variant, located at a +13 intronic position. This position is mutated only in 0.05% of ClinVar intronic mutations described so far. Furthermore, we illustrate how minigene splicing assay may be advantageous when validating splice-altering variants, in this case highlighting the coexistence of wild-type and mutated forms, probably explaining this patient's milder, late-onset phenotype

Altimetry for the future: building on 25 years of progress

In 2018 we celebrated 25 years of development of radar altimetry, and the progress achieved by this methodology in the fields of global and coastal oceanography, hydrology, geodesy and cryospheric sciences. Many symbolic major events have celebrated these developments, e.g., in Venice, Italy, the 15th (2006) and 20th (2012) years of progress and more recently, in 2018, in Ponta Delgada, Portugal, 25 Years of Progress in Radar Altimetry. On this latter occasion it was decided to collect contributions of scientists, engineers and managers involved in the worldwide altimetry community to depict the state of altimetry and propose recommendations for the altimetry of the future. This paper summarizes contributions and recommendations that were collected and provides guidance for future mission design, research activities, and sustainable operational radar altimetry data exploitation. Recommendations provided are fundamental for optimizing further scientific and operational advances of oceanographic observations by altimetry, including requirements for spatial and temporal resolution of altimetric measurements, their accuracy and continuity. There are also new challenges and new openings mentioned in the paper that are particularly crucial for observations at higher latitudes, for coastal oceanography, for cryospheric studies and for hydrology. The paper starts with a general introduction followed by a section on Earth System Science including Ocean Dynamics, Sea Level, the Coastal Ocean, Hydrology, the Cryosphere and Polar Oceans and the “Green” Ocean, extending the frontier from biogeochemistry to marine ecology. Applications are described in a subsequent section, which covers Operational Oceanography, Weather, Hurricane Wave and Wind Forecasting, Climate projection. Instruments’ development and satellite missions’ evolutions are described in a fourth section. A fifth section covers the key observations that altimeters provide and their potential complements, from other Earth observation measurements to in situ data. Section 6 identifies the data and methods and provides some accuracy and resolution requirements for the wet tropospheric correction, the orbit and other geodetic requirements, the Mean Sea Surface, Geoid and Mean Dynamic Topography, Calibration and Validation, data accuracy, data access and handling (including the DUACS system). Section 7 brings a transversal view on scales, integration, artificial intelligence, and capacity building (education and training). Section 8 reviews the programmatic issues followed by a conclusion

COVID-19 symptoms at hospital admission vary with age and sex: results from the ISARIC prospective multinational observational study

Background: The ISARIC prospective multinational observational study is the largest cohort of hospitalized patients with COVID-19. We present relationships of age, sex, and nationality to presenting symptoms. Methods: International, prospective observational study of 60 109 hospitalized symptomatic patients with laboratory-confirmed COVID-19 recruited from 43 countries between 30 January and 3 August 2020. Logistic regression was performed to evaluate relationships of age and sex to published COVID-19 case definitions and the most commonly reported symptoms. Results: ‘Typical’ symptoms of fever (69%), cough (68%) and shortness of breath (66%) were the most commonly reported. 92% of patients experienced at least one of these. Prevalence of typical symptoms was greatest in 30- to 60-year-olds (respectively 80, 79, 69%; at least one 95%). They were reported less frequently in children (≤ 18 years: 69, 48, 23; 85%), older adults (≥ 70 years: 61, 62, 65; 90%), and women (66, 66, 64; 90%; vs. men 71, 70, 67; 93%, each P < 0.001). The most common atypical presentations under 60 years of age were nausea and vomiting and abdominal pain, and over 60 years was confusion. Regression models showed significant differences in symptoms with sex, age and country. Interpretation: This international collaboration has allowed us to report reliable symptom data from the largest cohort of patients admitted to hospital with COVID-19. Adults over 60 and children admitted to hospital with COVID-19 are less likely to present with typical symptoms. Nausea and vomiting are common atypical presentations under 30 years. Confusion is a frequent atypical presentation of COVID-19 in adults over 60 years. Women are less likely to experience typical symptoms than men

Match-mismatch effects in two-fold transfer of chirality within a Mobius metallo-receptor

International audienceTwo-fold transfer of chirality has been investigated in a Mobius Zn(ii) hexaphyrin metallo-receptor able to bind simultaneously two different chiral molecules. Match/mismatch effects influence the dynamic stereoselective twisting of the pi-system, and allow tuning of the induced chiroptical activity. Such allosteric control is attractive for building chirality sensing systems

The overhanging carboxylic acid strategy: an alternative route to the porphyrin core expansion/modification for the coordination of large metal ions

International audienceThis account summarizes how the binding properties of a regular porphyrin macrocycle for large cations can be significantly modified and even tuned when the surrounding skeleton delivers at least one carboxylic acid group close to the N-core. While kinetics of metal insertion are drastically improved, unique dinuclear species can be obtained with a possible control of the nuclearity. The first incorporation of an α-core emitter radioisotope of particular interest for cancer therapy was recently demonstrated. All in all, this overhanging carboxylic acid strategy can be regarded as an alternative to either expanded porphyrins for the coordination of large cations from groups 14-15 (PbII, BiIII) or contracted and isomeric porphyrins for the coordination of smaller cations from group 12 (HgII