Digitally reconstructing Van Gogh's Field with Irises near Arles part 3: Determining the original colors

In earlier articles, we determined the spatial distributions and concentrations of all pigments used by Van Gogh in his painting Field with Irises near Arles. The colors of some pigments are expected to have changed over time, especially those of chrome yellow, cochineal, and eosin lake. For all pigments in this painting, we made physical paint reconstructions by following historical sources on raw materials and production processes, and we determined their optical properties. We combined this with pigment concentration maps to reconstruct the original colors of the painting digitally. When substituting the reconstruction paints into the calculations, we found that technical‐scientific data was not sufficient to resolve several issues. In those cases, discussions within the broad interdisciplinary team allowed us to make informed decisions. These issues refer to the representation of the sky area, and the original contributions of the red lake pigments to local colors. The digitally reconstructed colors of the painting show that due to discoloring of red lake pigments, the irises in the field have changed from a warm purple to purplish blue, and many pink spots in the field have turned to white. The range of yellows in the field has decreased and partly turned to dark brown. The digital reconstruction gives a better understanding of the color scheme used by Van Gogh when compared to remarks the artist made in letters when describing this painting. Also, the original color composition is seen to be aligned with color theories on which Van Gogh based his work.     

Elaboration and Characterization of Advanced Biobased Polyurethane Foams Presenting Anisotropic Behavior

Biobased and open cell polyurethane (PU) foams are produced from a synthesized sorbitol‐based polyester polyol. Different formulations are developed with various blowing agent systems (chemical vs physical blowing). Synthetized foams are fully characterized and compared. The cell morphology is carefully investigated by tomography and scanning electron microscopy. The chemical nature of the primary compounds, foaming kinetics, density, thermal behavior, and conductivity are fully studied, with also the main transition materials temperatures. It is shown that blowing agents especially impact the foaming kinetics. In the case of chemically blowing foams, higher foaming rate and temperatures are obtained. The mechanical behavior is particularly analyzed using quasi‐static compression tests, according two main axes compared to the rise direction. A direct relationship is observed between the formulation, foam structure, foam morphology, and corresponding mechanical properties. Results clearly highlight unexpected properties of biobased PU foams with unveil anisotropic mechanical properties.     

Effect of Zn addition on the structure and electrochemical properties of co-doped BaCe0.6Zr0.2Ln0.2O3-δ (Ln=Y,Gd, Yb) proton conductors

In this work, BaCe_0.6Zr_0.2Y_0.2-xYb_xO_3-δ and BaCe_0.6Zr_0.2Gd_0.2-xYb_xO_3-δ (x?=?0–0.20), proton conducting materials are prepared by the freeze-drying precursor method. The sintering conditions were optimized by adding Zn(NO₃)₂·6H₂O as sintering additive. The materials are thoroughly characterized by different structural and microstructural techniques, including X-ray diffraction, scanning and transmission electron microscopy, and thermogravimetric-differential thermal analysis. The addition of Zn favours the phase formation and densification at lower sintering temperatures; however, it leads to the segregation of a Zn-rich secondary phase, with general formula BaLn₂ZnO₅ (Ln?Y, Gd and Yb), which is identified and quantified for the first time. All samples with Zn as sintering aid exhibit cubic structure; however, the samples without Zn crystallize with orthorhombic or cubic structure, depending on the composition and thermal treatment. The electrical properties are studied by impedance spectroscopy. A deep analysis of the bulk and grain boundary contributions to the conductivity has revealed that the bulk conductivity remains almost unchanged along both series over Yb-doping; however, the grain boundary resistance decreases. The highest conductivity values are found for the intermediate members of both series, BaCe_0.6Zr_0.2Y_0.1Yb_0.1O_3-δ and BaCe_0.6Zr_0.2Gd_0.1Yb₁O_3-δ, with 33 and 28?mS?cm^?1 at 750?°C, respectively.     

Semianalytical models to predict the crystallization kinetics of thermoplastic fibrous composites

The growing interest for continuous fiber‐reinforced polymer composites leads to the development of new processes such as resin transfer molding for thermoplastics (RTM‐TP) or tape placement. In the aim of optimization, their simulations are required and have to include all involved physical phenomena and the associated couplings. During the consolidation step, the crystallization of the semicrystalline matrix occurs between the fibers of the multiscale reinforcement. A tricky task is to provide a realistic model able to describe the crystallization kinetics, which includes the effect of fibers on the polymer phase change and avoiding large computation time. In 2004, Haudin and Chenot proposed a generalization of the Avrami model, written in a differential form to compute the evolution of the crystallization of a neat thermoplastic in an infinite volume. In the present article, new extensions are proposed to predict the crystallization in long‐fiber thermoplastic composites, without or in the presence of transcrystallinity on fiber surfaces. In both cases, they are compared to three‐dimensional numerical simulations using a previously validated numerical method. All the numerical and analytical results are consistent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44508.     

Reactions of late transition metal complexes with molecular oxygen

Limited natural resources, high energy consumption, economic considerations, and environmental concerns demand that we develop new technologies for the sustainable production of chemicals and fuels. New methods that combine the selective activation of C-H bonds of hydrocarbons with oxidation by a green oxidant such as molecular oxygen would represent huge advances toward this goal. The spectacular selectivity of transition metals in cleaving C-H bonds offers the potential for the direct use of hydrocarbons in the production of value-added organics such as alcohols. However, the use of oxygen, which is abundant, environmentally benign, and inexpensive (particularly from air), has proven challenging, and more expensive and less green oxidants are often employed in transition-metal-catalyzed reactions. Advances in the use of oxygen as an oxidant in transition-metal-catalyzed transformations of hydrocarbons will require a better understanding of how oxygen reacts with transition metal alkyl and hydride complexes. For alkane oxidations, researchers will need to comprehend and predict how metals that have shown particularly high activity and selectivity in C-H bond activation (e.g. Pt, Pd, Rh, Ir) will react with oxygen. In this Account, we present our studies of reactions of late metal alkyls and hydrides with molecular oxygen, emphasizing the mechanistic insights that have emerged from this work. Our studies have unraveled some of the general mechanistic features of how molecular oxygen inserts into late metal hydride and alkyl bonds along with a nascent understanding of the scope and limitations of these reactions. We present examples of the formation of metal hydroperoxide species M-OOH by insertion of dioxygen into Pt(IV)-H and Pd(II)-H bonds and show evidence that these reactions proceed by radical chain and hydrogen abstraction pathways, respectively. Comparisons with recent reports of insertion of oxygen into other Pd(II)-H complexes, and also into Ir(III)-H and Rh(III)-H complexes, point to potentially general mechanisms for this type of reaction. Additionally, we observed oxygen-promoted C-H and H-H reductive elimination reactions from five-coordinate Ir(III) alkyl hydride and dihydride complexes, respectively. Further, when Pd(II)Me(2) and Pt(II)Me(2) complexes were exposed to oxygen, insertion processes generated M-OOMe complexes. Mechanistic studies for these reactions are consistent with radical chain homolytic substitution pathways involving five-coordinate M(III) intermediates. Due to the remarkable ability of Pt(II) and Pd(II) to activate the C-H bonds of hydrocarbons (RH) and form M-R species, this reactivity is especially exciting for the development of partial alkane-oxidation processes that utilize molecular oxygen. Our understanding of how late transition metal alkyls and hydrides react with molecular oxygen is growing rapidly and will soon approach our knowledge of how other small molecules such as olefins and carbon monoxide react with these species. Just as advances in understanding olefin and CO insertion reactions have shaped important industrial processes, key insight into oxygen insertion should lead to significant gains in sustainable commercial selective oxidation catalysis.     

High Resolution Crystal Structures of the Cerebratulus lacteus Mini-Hb in the Unligated and Carbomonoxy States

The nerve tissue mini-hemoglobin from Cerebratulus lacteus (CerHb) displays an essential globin fold hosting a protein matrix tunnel held to allow traffic of small ligands to and from the heme. CerHb heme pocket hosts the distal TyrB10/GlnE7 pair, normally linked to low rates of O(2) dissociation and ultra-high O(2) affinity. However, CerHb affinity for O(2) is similar to that of mammalian myoglobins, due to a dynamic equilibrium between high and low affinity states driven by the ability of ThrE11 to orient the TyrB10 OH group relative to the heme ligand. We present here the high resolution crystal structures of CerHb in the unligated and carbomonoxy states. Although CO binds to the heme with an orientation different from the O(2) ligand, the overall binding schemes for CO and O(2) are essentially the same, both ligands being stabilized through a network of hydrogen bonds based on TyrB10, GlnE7, and ThrE11. No dramatic protein structural changes are needed to support binding of the ligands, which can freely reach the heme distal site through the apolar tunnel. A lack of main conformational changes between the heme-unligated and -ligated states grants stability to the folded mini-Hb and is a prerequisite for fast ligand diffusion to/from the heme.     

Development of novel soy-protein-based superabsorbent matrixes through the addition of salts

The addition of salts, like sodium bicarbonate (SB) or carbonate (SC), into the formulation of bioplastic materials may alter their hydrophilic character to a significant extent. Soy protein isolate (SPI) is a byproduct of the soybean oil industry, which, when properly blended with glycerol (GL), can be further processed through a lab-scale injection molding device. A maximum in the water uptake around 2250 or 2500% is obtained for bioplastics obtained when either SB or SC content is around 1 wt %, respectively. Thus, they exceed the limit to be considered superabsorbent materials (SAMs). Regarding their mechanical properties, a higher presence of SB within the SPI/GL matrix provides materials with a higher extensibility and lower Young's modulus. A higher water uptake is observed after replacing SB for SC in the formulation, probably related to a higher alkalinization of the material as well as to the high hydrophilicity of the carbonate. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47012.     

DOPO‐Based Phosphorus‐Containing Methacrylic (Co)Polymers: Glass Transition Temperature Investigation

A two‐step synthetic procedure is designed for preparing new flame‐retardant methacrylic monomers containing 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) as a substituent side group. DOPO and methacrylate moieties are linked by linear aliphatic hydrocarbon spacers (3 to 11 carbon atoms). Copolymerization with methyl methacrylate is carried out leading to copolymers containing between 2 and 10 wt% phosphorus. All homo‐ and copolymers exhibit a unique glass transition temperature (T_g ). A new group contribution for DOPO‐based substituent is extracted that leads to reasonable estimations of T_g s of other published polymers. The Fox equation provides a good estimation of T_g s for most copolymers and for physical blends of poly(methyl methacrylate) (PMMA) and DOPO. When using monomers having three and four carbon atoms in the hydrocarbon spacer, the T_g of copolymers remains close to that of PMMA over a wide range of composition.