Nuclear magnetic resonance characterization of high- and ultrahigh-performance concrete: Application to the study of water leaching

In the present study, we show that high-resolution ²⁹Si and ²⁷Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) can be a powerful tool for analyzing actual concrete mixes. The influence of the amount of silica fume and of the type of cement in high-performance concrete (HPC), as well as the influence of the type of silica fume and of the granular packing in ultrahigh-performance concrete (UHPC) were investigated. Significant effects on the amount and shape of C-S-H, on the incorporation of aluminum in the C-S-H structure, and on the distribution of aluminum-containing hydrates were observed. Nuclear magnetic relaxation of protons was also performed and it showed the fractal feature of the pore size distribution in UHPC and the higher amount of larger pores in HPC. The microstructure of the surface of these same formulations leached by mineral water for up to 1 year exhibits slight modifications.     

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.     

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.     

Densification of alumina by SPS and HP: A comparative study

In this study, the densification of alumina by spark plasma sintering (SPS) was investigated and compared to conventional hot pressing. It was shown that SPS is very effective in the sintering of alumina leading to higher densities and allows to work at lower temperatures and with shorter sintering cycles. The effect of the heating rate is dependent on the heating mode (SPS or HP). The identification of active sintering mechanisms was attempted by an isothermal and an anisothermal methods, showing that other mechanisms probably related to electrical effects enhance the densification. We suggest the higher contribution of surface diffusion mainly during the initial stage of sintering and an influence of the presence of impurities segregated at the grain boundaries. They could create conductive layers and also introduce ions with a lower valence than Al³⁺; defects are created in the surface layers and the diffusion of the species is increased.     

Nanomaterials based on phosphorus dendrimers

Dendrimers constitute an increasingly important field of research in chemistry for more than 15 years. After pioneering works concerning synthesis, the interest in dendrimers is now mainly driven by their properties and applications. This Account will emphasize the properties of a special class of dendrimers, that is, phosphorus-containing dendritic macromolecules, as tools for the elaboration of nanomaterials. Indeed, these dendrimers can be considered themselves as materials, or they can be used as an intrinsic constituent of a material or as a modifier of the surface of a material. In this latter case, a fundamental work about surfaces covalently modified by dendrimers recently opened the way to the elaboration of DNA chips.     

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.     

Mathematical Modeling of Theoretical Cryptosporidium Inactivation in Full-Scale Ozonation Reactors

Conditions for theoretical inactivation of Cryptosporidium by ozone could be achieved at full-scale facilities if their design is appropriate. To perform this task correctly the chemical engineer's approach for process design must be applied. This paper discusses the basic equations the estimation of the disinfection efficiency of different ozone reacting systems. Available kinetic data have been integrated in a global model accounting for the hydrodynamics and mass transfer performances of the ozonation reactor. Thus the proposed method allows one to predict Cryptosporidium inactivation level in a given ozonation system. However, if a specified disinfection goal is to be achieved for Cryptosporidium with the developed model it is also possible to choose and optimize the design of the ozone reactor.     

Dislocations at Prismatic Fracture Surfaces in Sapphire

Single-crystal sapphire exhibits a highly anisotropic fracture behavior. The surfaces of specimens fractured along prismatic planes are wavy, with fractographic features appearing as small areas of contrast under an optical microscope. Optical microscopy, atomic force microscopy, X-ray topography, and confocal microscopy are used to demonstrate a correlation between the areas of contrast and dislocations penetrating the sample surface. The surface features are argued to be a consequence of the stress field surrounding the dislocations, which deflect the crack approximately 10 nm normal to the surface as the crack cuts the dislocations. The lateral extent of measurable surface deflection is of the order of 5 μm. These images can be compared directly to show the equivalence of the position of the dislocations observed by X-ray topography and the surface contrast observed optically.     

Mass Spectrometry-Based Proteomics Reveal Alcohol Dehydrogenase 1B as a Blood Biomarker Candidate to Monitor Acetaminophen-Induced Liver Injury

Acute liver injury (ALI) is a severe disorder resulting from excessive hepatocyte cell death, and frequently caused by acetaminophen intoxication. Clinical management of ALI progression is hampered by the dearth of blood biomarkers available. In this study, a bioinformatics workflow was developed to screen omics databases and identify potential biomarkers for hepatocyte cell death. Then, discovery proteomics was harnessed to select from among these candidates those that were specifically detected in the blood of acetaminophen-induced ALI patients. Among these candidates, the isoenzyme alcohol dehydrogenase 1B (ADH1B) was massively leaked into the blood. To evaluate ADH1B, we developed a targeted proteomics assay and quantified ADH1B in serum samples collected at different times from 17 patients admitted for acetaminophen-induced ALI. Serum ADH1B concentrations increased markedly during the acute phase of the disease, and dropped to undetectable levels during recovery. In contrast to alanine aminotransferase activity, the rapid drop in circulating ADH1B concentrations was followed by an improvement in the international normalized ratio (INR) within 10–48 h, and was associated with favorable outcomes. In conclusion, the combination of omics data exploration and proteomics revealed ADH1B as a new blood biomarker candidate that could be useful for the monitoring of acetaminophen-induced ALI.