Direct Synthesis of N-Heterocyclic Carbene-Stabilized Copper Nanoparticles from an N-Heterocyclic Carbene–Borane

N-Heterocyclic carbene (NHC)-stabilized copper nanoparticles (NPs) were synthesized from an NHC–borane adduct and mesitylcopper(I) under thermal conditions (refluxing toluene for 2.5 h). NPs with a size distribution of 11.6±1.8 nm were obtained. The interaction between Cu NPs and NHC ligands was probed by X-ray photoelectron spectroscopy, which showed covalent binding of the NHC to the surface of the NPs. Mechanistic studies suggested that NHC–borane plays two roles: contributing to the reduction of [CuMes]₂ to release Cu⁰ species and providing NHC ligands to stabilize the copper NPs.     

Frontal free‐radical photopolymerization of thick samples: Applications to LED‐induced fiber‐reinforced polymers

Free‐radical photopolymerization is scarcely used for the manufacturing of fiber‐reinforced polymers. The main issue relies on the penetration depth of light which affects the conversion degree when photopolymerizing thick samples. Consequently, this could lead to inhomogeneous polymer properties. The ability of acylphosphine oxides to photobleach under near UV irradiation makes them of great interest for the curing of thick samples. Therefore, the influence of (2,4,6‐trimethylbenzoyl) phosphine oxide on the curing of composites under LED is investigated. Although that a frontal photopolymerization process can be evidenced, it was found that full photobleaching is hardly obtained at high concentration of photoinitiator. Six layers laminates made of unidirectional fiber glass and unsaturated polyester resin were prepared. The existence of an optimal range of concentration for which the conversion of the resin is the most homogeneous throughout its thickness was pointed out, a fact that is confirmed by dynamic mechanical analysis. Interestingly, this effect is reflected in the shrinkage of the resin as shown by direct measurements or deflection experiments. Mechanical analysis was undertaken whose results correlate well with the aforementioned study, demonstrating the occurrence of a balance between the concentration of photoinitiator and the mechanical properties of the samples. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 898–906     

Effect of Titanium Dioxide Film Thickness on Photocatalytic and Bactericidal Activities Against Listeria monocytogenes

Structural, microstructural and bactericidal surface properties of TiO₂‐coated glass substrates elaborated by reactive Radiofrequency sputtering are investigated. As pathogenic bacteria in biofilms are a major concern in food industries due to their growing resistance to cleaning and sanitizing procedures, the development of photoactive surfaces exhibiting bactericidal properties is acknowledged as an effective approach to tackle bacterial contaminations. Our principal aim concerns the study of the photoactive top‐layer thickness impact (from 80 nm to ~500 nm) on Listeria monocytogenes. Structural characterization of the TiO₂ layers demonstrates that anatase and rutile phases are both present, depending on the film thickness. Photocatalytic activity of the samples has been evaluated through the degradation of aqueous methylene blue (MB) solutions under UVA light illumination for various time periods. The results show an efficiency rating increase according to TiO₂ film thickness up to a threshold value close to 400 nm. Moreover, a significant decrease of the adherent bacteria number is observed after 20 min of UVA illumination. The quantitative study of the bactericidal activity associated with scanning electron microscopy observations of the postprocess bacteria damaged cells demonstrates the efficiency of the 240‐nm‐thick TiO₂ coating sample. The results are correlated with the production of hydroxyl radicals during the process of photocatalysis.     

Mixtures of foam and paste: suspensions of bubbles in yield stress fluids

We study the rheological behavior of mixtures of foams and pastes, which can be described as suspensions of bubbles in yield stress fluids. Model systems are designed by mixing monodisperse aqueous foams and concentrated emulsions. The elastic modulus of the bubble suspensions is found to depend on the elastic capillary number $\textit{Ca}_{_G}$ , defined as the ratio of the paste elastic modulus to the bubble capillary pressure. For values of $\textit{Ca}_{_G}$ larger than $\simeq 0.5$ , the dimensionless elastic modulus of the aerated material decreases as the bubble volume fraction $\phi $ increases, suggesting that bubbles behave as soft elastic inclusions. Consistently, this decrease is all the sharper as $\textit{Ca}_{_G}$ is high, which accounts for the softening of the bubbles as compared to the paste. By contrast, we find that the yield stress of most studied materials is not modified by the presence of bubbles. This suggests that their plastic behavior is governed by the plastic capillary number $\textit{Ca}_{\tau_y}$ , defined as the ratio of the paste yield stress to the bubble capillary pressure. At low $\textit{Ca}_{\tau_y}$ values, bubbles behave as nondeformable inclusions, and we predict that the suspension dimensionless yield stress should remain close to unity, in agreement with our data up to $\textit{Ca}_{\tau_y}=0.2$ . When preparing systems with a larger target value of $\textit{Ca}_{\tau_y}$ , we observe bubble breakup during mixing, which means that they have been deformed by shear. It then seems that a critical value $\textit{Ca}_{\tau_y}\simeq 0.2$ is never exceeded in the final material. These observations might imply that, in bubble suspensions prepared by mixing a foam and a paste, the suspension yield stress is always close to that of the paste surrounding the bubbles. Finally, at the highest $\phi $ investigated, the yield stress is shown to increase abruptly with $\phi $ : this is interpreted as a “foamy yield stress fluid” regime, which takes place when the paste mesoscopic constitutive elements (here, the oil droplets) are strongly confined in the films between the bubbles.     

Coupled effects of grain size distributions and crystallographic textures on the plastic behaviour of IF steels

Micro-macro scale transition theories were developed to model the inelastic behaviour of polycrystals starting from the local behaviour of the grains. The anisotropy of the plastic behaviour of polycrystalline metals was essentially explained by taking into account the crystallographic textures. Issues like plastic heterogeneities due to grain size dispersion, involving the Hall-Petch mechanism at the grain scale, were often not taken into account, and, only the role of a mean grain size was investigated in the literature. Here, both sources of plastic heterogeneities are studied using: (i) experimental data from EBSD measurements and tensile tests, and, (ii) a self-consistent model devoted to elastic-viscoplastic heterogeneous materials. The results of the model are applied to two different industrial IF steels with similar global orientation distributions functions but different mean grain sizes and grain size distributions. The coupled role of grain size distributions and crystallographic textures on the overall tensile behaviour, local stresses and strains, stored energy and overall plastic anisotropy (Lankford coefficients) is deeply analyzed by considering different other possible correlations between crystallographic orientations and grain sizes from the measured data.     

Validation of Molecular Simulation: An Overview of Issues

Computer simulation of molecular systems enables structure–energy–function relationships of molecular processes to be described at the sub‐atomic, atomic, supra‐atomic, or supra‐molecular level. To interpret results of such simulations appropriately, the quality of the calculated properties must be evaluated. This depends on the way the simulations are performed and on the way they are validated by comparison to values Q^exp of experimentally observable quantities Q. One must consider 1) the accuracy of Q^exp, 2) the accuracy of the function Q( r ^N) used to calculate a Q‐value based on a molecular configuration r ^N of N particles, 3) the sensitivity of the function Q( r ^N) to the configuration r ^N, 4) the relative time scales of the simulation and experiment, 5) the degree to which the calculated and experimental properties are equivalent, and 6) the degree to which the system simulated matches the experimental conditions. Experimental data is limited in scope and generally corresponds to averages over both time and space. A critical analysis of the various factors influencing the apparent degree of (dis)agreement between simulations and experiment is presented and illustrated using examples from the literature. What can be done to enhance the validation of molecular simulation is also discussed.     

Facile and efficient aerobic one-pot synthesis of benzimidazoles using Ce(NO3)3·6H2O as promoter

A series of 2-substituted benzimidazoles was synthesized under aerobic conditions, by simply heating 1,2-diaminobenzene and aldehydes in DMF at 80 °C, employing Ce(NO₃)₃·6H₂O as promoter and atmospheric air as an efficient oxidant. The procedure afforded the products from good to excellent yields. Furthermore, this new economic and eco-friendly protocol avoids the use of toxic metal catalysts, as well as additional bases and oxidants.     

Electrochemical analysis of gildings in Valencia altarpieces: a cross-age study since fifteenth until twentieth century

Journal of Solid State Electrochemistry - The application of the voltammetry of microparticles methodology to the study of gildings in paintings and architectural ornaments is described....