Simple N‐Heterocyclic Carbenes as Ligands in Ullmann‐Type Ether and Thioether Formations

A simple N‐heterocyclic carbene (NHC) derived from 1‐methyl‐3‐ethylimidazolium tetrafluoroborate was found to be an efficient ligand for a range of copper‐catalyzed cross‐coupling reactions, leading to the formation of aromatic ethers and thioethers.

     

Water�CGas Shift and CO Methanation Reactions over Ni�CCeO2(111) Catalysts

X-ray and ultraviolet photoelectron spectroscopies were used to study the interaction of Ni atoms with CeO₂(111) surfaces. Upon adsorption on CeO₂(111) at 300 K, nickel remains in a metallic state. Heating to elevated temperatures (500?C800 K) leads to partial reduction of the ceria substrate with the formation of Ni²⁺ species that exists as NiO and/or Ce_1?xNi_xO_2?y. Interactions of nickel with the oxide substrate significantly reduce the density of occupied Ni 3d states near the Fermi level. The results of core-level photoemission and near-edge X-ray absorption fine structure point to weakly bound CO species on CeO₂(111) which are clearly distinguishable from the formation of chemisorbed carbonates. In the presence of Ni, a stronger interaction is observed with chemisorption of CO on the admetal. When the Ni is in contact with Ce⁺³ cations, CO dissociates on the surface at 300 K forming NiC_x compounds that may be involved in the formation of CH₄ at higher temperatures. At medium and large Ni coverages (>0.3 ML), the Ni/CeO₂(111) surfaces are able to catalyze the production of methane from CO and H₂, with an activity slightly higher than that of Ni(100) or Ni(111). On the other hand, at small coverages of Ni (<0.3 ML), the Ni/CeO₂(111) surfaces exhibit a very low activity for CO methanation but are very good catalysts for the water?Cgas shift reaction.     

Unraveling the Dynamic Nanoscale Reducibility (Ce4+ → Ce3+) of CeOx–Ru in Hydrogen Activation

The interaction of molecular hydrogen with ceria is of important relevance for heterogeneous catalysis related to green chemistry and renewable energy. Here, the complex structural transformations of a well‐defined cerium oxide model catalyst are followed in situ and in real time when exposed to a reactive H₂ environment. By using electron spectromicroscopy and diffraction with chemical and structural sensitivities, it is demonstrated that the transition from CeO₂ to crystalline Ce₂O₃ occurs through a mixture of transient, coexisting phases on the nanoscale. The findings establish a clear relationship between structure and functionality for hydrogen dissociation over ceria(111), bearing profound implications on the nature of the reduction (Ce⁴⁺ → Ce³⁺) and mechanism for H₂ scission.     

The reactions of formaldehyde over the surfaces of uranium oxides. A comparative study between polycrystalline and single crystal materials

The reaction of formaldehyde has been studied on the surfaces of UO₂(1 1 1) single crystal and polycrystalline UO₂. Most of adsorbed formaldehyde on the single crystal at room temperature reacted to give ethylene during TPD. On the polycrystalline surface, IR analyses showed that the main species present in the 88–200 K temperature domain are poly- and dioxymethylene. These species are mainly converted to stable formates that decompose at high temperature (above 550 K). The apparent activation energy for the reaction of the oxymethylenic species to formates in the 250–450 K region (calculated from the intensity of the ν_a COO IR band of formates, at 1575 cm⁻¹) is found equal to 12 kJ/mol. Overall, both surfaces (single crystal and polycrystalline) give qualitatively the same products, with the exception of formation of traces of methyl formate in the case of powder. However, the single crystal is far more active for the reductive coupling of formaldehyde to ethylene than the polycrystalline material. The difference in reaction selectivity between the single crystal and powder work is attributed to the method of preparation of the polycrystalline UO₂ material (made by H₂-reduction of -U₃O₈) rather than to an intrinsic difference between both materials.     

Solid-state NMR study of N labelled polyaniline upon reaction with DPPH

The quantitative investigation of the radical scavenging properties of polyaniline (PANI) upon reaction with excess of the stable DPPH radical (a 4:1 ratio of DPPH to aniline units in the polymer) was carried out using ¹⁵N and ¹³C solid state NMR spectroscopy. During the process the polyaniline was oxidised so that the imine content increased from 45 to 65%. The extent of oxidation measured by NMR was confirmed by N1s XPS analysis. However, within a 30 min reaction time, about 85% of the DPPH radicals were scavenged as monitored by the decay in its EPR signal. This is about 20 times greater than the fraction of DPPH required to oxidize PANI from an imine content of 45-65%. An identification of further redox processes is required to explain the high degree of radical scavenging. At the same time, there was no evidence of significant chemical binding or trapping of DPPH in the PANI structure.     

Oxidative stability of structured lipids produced from borage (<Emphasis Type="Italic">Borago officinalis</Emphasis> L.) and evening primrose (<Emphasis Type="Italic">Oenothera biennis</Emphasis> L.) oils with docosahexaenoic acid

This study utilized γ-linolenic acid (18∶3n−6; GLA)-rich borage oil (BO) and evening primrose oil (EPO) for the synthesis of structured lipids (SL) and compared the oxidative stability of the products with those of unmodified BO and EPO as controls. Immobilized Novozym 435 lipase from Candida antarctica was used as the biocatalyst for SL production. BO or EPO eas enzymatically modified with docosahexaenoic acid (22∶6n−3; DHA), as the acyl donor, to produce SI. The SI were characterized and their oxidative stabilities evaluated. Among the oils examined, SL gave rise to higher quantities (P≤0.05) of conjugated dienes, TBARS, and headspace volatiles as compared to their unmodified counterparts. Results indicated that modified oils were less stable than their unmodified counterparts. The double bond index (DBI) and methylene bridge index (MBI) of oils decreased (P<0.05) during oxidation in the more unsaturated oils. An attempt was made to correlate various parameters of oxidation with DBI and MBI of oils; correlation coefficients (−r) were within the range of 0.574–0.973. This suggests that indicators such as DBI and MBI can reflect oxidative stability of oils.     

Positional distribution of FA in TAG of enzymatically modified borage and evening primrose oils

Stereospecific analysis was carried out to establish positional distribution of FA in the TAG of DHA, EPA, and (EPA+DHA)-enriched oils. In this study, TAG of enzymatically modified oils were purified using a silicic acid column. The TAG were then subjected to positional distribution analysis using a modified procedure involving reductive cleavage with Grignard reagent. The results showed that in DHA-enriched borage oil (BO), DHA was randomly distributed over the three positions of TAG, whereas γ-linolenic acid (GLA) was mainly esterified at the sn-2 and-3 positions. In DHA-enriched evening primrose oil (EPO), however, DHA and GLA were concentrated in the sn-2 position. In EPA-enriched BO, EPA was randomly distributed over the three positions of TAG, similar to that observed for DHA. In EPA-enriched EPO, however, this FA was mainly located at the primary positions (sn-1 and sn-3) of TAG. In both oils, GLA was preferentially esterified at the sn-2 position. In (EPA+DHA)-enriched BO, EPA and DHA were mainly esterified at the sn-1 and -3 positions of TAG, whereas GLA was mainly located at the sn-2 position. In (EPA+DHA)-enriched EPO, GLA was mainly located at the sn-2 and-3 positions; EPA was preferentially esterified at the sn-1 and-3 positions, and DHA was found mainly at the sn-3 position.     

A comparative study of the dependency of colour measurement on surface temperature

In this paper, we evaluated in depth how the spectrophotometric colour measurement of an object will respond to surface temperature change. The colorimetric variations of eight coloured ceramic tiles against temperature changes were studied. Colorimetric data measured at specific temperature were compared with data measured at about 20 °C. For each coloured ceramic tile, reflectance curves and colorimetric differences resulting from temperature differences were examined to demonstrate the exact dependency of colorimetric properties across the temperature range studied. Experimental data showed that peaks and slopes on a reflectance curve are the major impact resulting from temperature variation. Colours with lower lightness and lower chroma showed smaller colorimetric changes with change in temperature, while colour with higher lightness and chroma exhibited a distinct thermochromism and linearity changes across the temperature range. A conspicuous correlation potential between surface temperature and CIE colorimetric coordinates was observed.