Iridium complexes incorporating coumarin moiety as catalyst photoinitiators: Towards household green LED bulb and halogen lamp irradiation

Household LED bulbs and halogen lamps are used to promote the ring-opening photopolymerization of epoxides in the presence of a new series of iridium(III) complexes (IrCs) exhibiting enhanced visible light absorption properties through the introduction of a coumarin moiety. These latter complexes are used as catalyst photoinitiators in an oxidative cycle in combination with a silane and an iodonium salt. Remarkably, even under the selected very soft irradiations (e.g. light intensity lower than 2 mW/cm²), excellent polymerization profiles are obtained (conversions > 80%). The mechanisms are investigated by ESR and luminescence experiments.     

The synthesis of tetrahedral bipyridyl metallo-octupoles with large second- and third-order nonlinear optical properties

Two new 4,4′-bis(donor)-6,6′-diphenyl- 2,2′-bipyridine ligands and their corresponding D_2d (Cu^I, Ag^I, Zn^II) octupolar metal complexes were synthesized, and their linear and nonlinear optical properties were investigated. A single crystal X-ray structure was also determined for the bis[4,4′-bis(diethylaminostyryl)-6,6′-diphenyl-bipyridine]copper(I) complex, which revealed a distorded pseudo-tetrahedral geometry. Molecular second-order nonlinear optical properties were determined for the complexes using the Harmonic Light Scatterring technique at 1.91 μm. These metallo-chromophores display large first hyperpolarizabilities β_1.91 in the range of 211-340 × 10⁻³⁰ esu, which increase with the Lewis acidity of the metal ion. The two-photon absorption properties of the bipyridyl ligands and related complexes were determined using either the two-photon emission method for fluorescent compounds or the open aperture Z-scan technique for non emissive ones. The complexes display red-shifted two-photon absorption bands compared to their metal-ion free chromophores, as well as a large increase of the maximum two-photon absorption cross-sections.     

Water Penetration—Its Effect on the Strength and Toughness of Silica Glass

When a crack forms in silica glass, the surrounding environment flows into the crack opening, and water from the environment reacts with the glass to promote crack growth. A chemical reaction between water and the strained crack-tip bonds is commonly regarded as the cause of subcritical crack growth in glass. In silica glass, water can also have a secondary effect on crack growth. By penetrating into the glass, water generates a zone of swelling and, hence, creates a compression zone around the crack tip and on the newly formed fracture surfaces. This zone of compression acts as a fracture mechanics shield to the stresses at the crack tip, modifying both the strength and subcritical crack growth resistance of the glass. Water penetration is especially apparent in silica glass because of its low density and the fact that it contains no modifier ions. Using diffusion data from the literature, we show that the diffusion of water into silica glass can explain several significant experimental observations that have been reported on silica glass, including (1) the strengthening of silica glass by soaking the glass in water at elevated temperatures, (2) the observation of permanent crack face displacements near the crack tip of a silica specimen that had been soaked in water under load, and (3) the observation of high concentrations of water close to the fracture surfaces that had been formed in water. These effects are consistent with a model suggesting that crack growth in silica glass is modified by a physical swelling of the glass around the crack tip. An implication of water-induced swelling during fracture is that silica glass is more resistant to crack growth than it would be if swelling did not occur.     

Anaerobic methane oxidation and aerobic methane production in an east African great lake (Lake Kivu)

We investigated CH₄ oxidation in the water column of Lake Kivu, a deep meromictic tropical lake with CH₄-rich anoxic deep waters. Depth profiles of dissolved gases (CH₄ and N₂O) and a diversity of potential electron acceptors for anaerobic CH₄ oxidation (NO₃^?, SO₄^2?, Fe and Mn oxides) were determined during six field campaigns between June 2011 and August 2014. Denitrification measurements based on stable isotope labelling experiments were performed twice. In addition, we quantified aerobic and anaerobic CH₄ oxidation, NO₃^? and SO₄^2? consumption rates, with and without the presence of an inhibitor of SO₄^2?-reducing bacteria activity. Aerobic CH₄ production was also measured in parallel incubations with the addition of an inhibitor of aerobic CH₄ oxidation. The maximum aerobic and anaerobic CH₄ oxidation rates were estimated to be 27?±?2 and 16?±?8?μmol/L/d, respectively. We observed a difference in the relative importance of aerobic and anaerobic CH₄ oxidation during the rainy and the dry season, with a greater role for aerobic oxidation during the dry season. Lower anaerobic CH₄ oxidation rates were measured in presence of molybdate in half of the measurements, suggesting the occurrence of linkage between SO₄^2? reduction and anaerobic CH₄ oxidation. NO₃^? consumption and dissolved Mn production rates were never high enough to sustain the measured anaerobic CH₄ oxidation, reinforcing the idea of a coupling between SO₄^2? reduction and CH₄ oxidation in the anoxic waters of Lake Kivu. Finally, significant rates (up to 0.37?μmol/L/d) of pelagic CH₄ production were also measured in oxygenated waters.     

Comparison of an effect-model-law-based method versus traditional clinical practice guidelines for optimal treatment decision-making: application to statin treatment in the French population

Healthcare authorities make difficult decisions about how to spend limited budgets for interventions that guarantee the best cost-efficacy ratio. We propose a novel approach for treatment decision-making, OMES—in French: Objectif thérapeutique Modèle Effet Seuil (in English: Therapeutic Objective–Threshold–Effect Model; TOTEM). This approach takes into consideration results from clinical trials, adjusted for the patients'' characteristics in treatment decision-making. We compared OMES with the French clinical practice guidelines (CPGs) for the management of dyslipidemia with statin in a computer-generated realistic virtual population, representing the adult French population, in terms of the number of all-cause deaths avoided (number of avoided events: NAEs) under treatment and the individual absolute benefit. The total budget was fixed at the annual amount reimbursed by the French social security for statins. With the CPGs, the NAEs was 292 for an annual cost of 122.54 M€ compared with 443 with OMES. For a fixed NAEs, OMES reduced costs by 50% (60.53 M€ yr⁻¹). The results demonstrate that OMES is at least as good as, and even better than, the standard CPGs when applied to the same population. Hence the OMES approach is a practical, useful alternative which will help to overcome the limitations of treatment decision-making based uniquely on CPGs.     

Influence of flour blend composition on fermentation kinetics and phytate hydrolysis of sourdough used to make injera

The influence of cereal blends, teff–white sorghum (TwS), barley–wheat (BW) and wheat–red sorghum (WrS), on fermentation kinetics during traditional fermentation of dough to prepare injera, an Ethiopian traditional fermented pancake, was investigated in samples collected in households. Barley malt was used with BW and WrS flours. WrS- and BW-injera sourdough fermentations were characterised by a transient accumulation of glucose and maltose and a two-step fermentation process: lactic acid fermentation and alcoholic fermentation with ethanol as the main end product. Only transient accumulation of glucose was observed in TwS-injera, and equimolar concentrations of lactic acid and ethanol were produced simultaneously. Final α-galactoside concentrations were low in all sourdoughs. Phytic acid (IP6) was completely hydrolyzed in WrS and BW-injeras probably due to the combined action of endogenous malt and microbial phytases. Only 28% IP6 hydrolysis was observed in TwS injera. Ways to improve IP6 hydrolysis in TwS-injera need to be investigated.     

Selective Laser Melting process optimization of Ti–Mo–TiC metal matrix composites

Selective Laser Melting (SLM) was used to process a powder mixture of CP Ti, 6.5 wt% Mo and 3.5 wt% Mo₂C. The process parameters were optimized to obtain full-density, crack free parts. After the in situ decomposition of Mo₂C in favor of the formation of TiC, the material consisted of a homogeneous dispersion of submicrometer sized TiC platelets in a β-(Ti,Mo) matrix exhibiting a high hardness up to 550 HV and compressive yield stress of 1164 ± 37 MPa. The microstructure and mechanical properties could be tailored by variation of the process parameters within the high-density processing window, as well as through post-process heat treatments.     

Tribological behavior of composites fabricated by reactive SPS sintering in Ti-Si-C system

In this study, wear and friction behavior of two based-composites from the Ti-Si-C system, (40 wt% TiC; 28 wt% Ti₅Si₃; 17 wt% Ti₃SiC₂) and (18 wt% TiC; 26 wt% Ti₅Si₃; 41 wt% Ti₃SiC₂) reinforced by 15 wt% of large size SiC (100-150 µm) particles were investigated. The four-phase composites exhibited approximatively the same friction coefficient (µ ~ 0.9) under high loads (10 N and 7 N). The composite with high Ti₃SiC₂ showed higher wear rate values by one order of magnitude. However, under 1 N, the composite with high TiC content showed a higher running-in period and a lower steady state µ value (0.37 after 1000 m sliding distance). Scanning electron microscopy, Energy Dispersive X-Ray and Raman spectroscopy analysis of the worn surfaces of the two composites revealed that oxidation was the dominant wear mechanism. The oxidation process and the removal kinetics of the oxides during sliding controlled the tribological behavior of the composites. The influence of processing variables on microstructures development and wear mechanisms of the composites is discussed.     

Engineered Neutral Phosphorous Dendrimers Protect Mouse Cortical Neurons and Brain Organoids from Excitotoxic Death

Nanoparticles are playing an increasing role in biomedical applications. Excitotoxicity plays a significant role in the pathophysiology of neurodegenerative diseases, such as Alzheimer’s or Parkinson’s disease. Glutamate ionotropic receptors, mainly those activated by N-methyl-D-aspartate (NMDA), play a key role in excitotoxic death by increasing intraneuronal calcium levels; triggering mitochondrial potential collapse; increasing free radicals; activating caspases 3, 9, and 12; and inducing endoplasmic reticulum stress. Neutral phosphorous dendrimers, acting intracellularly, have neuroprotective actions by interfering with NMDA-mediated excitotoxic mechanisms in rat cortical neurons. In addition, phosphorous dendrimers can access neurons inside human brain organoids, complex tridimensional structures that replicate a significant number of properties of the human brain, to interfere with NMDA-induced mechanisms of neuronal death. Phosphorous dendrimers are one of the few nanoparticles able to gain access to the inside of neurons, both in primary cultures and in brain organoids, and to exert pharmacological actions by themselves.