Potential maternal kinship among humans from the Northern Caucasus “post-dolmen” burials

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The charge-assisted hydrogen-bonded organic framework (CAHOF) self-assembled from the conjugated acid of tetrakis(4-aminophenyl)methane and 2,6-naphthalenedisulfonate as a new class of recyclable Brønsted acid catalysts

The acid–base neutralization reaction of commercially available disodium 2,6-naphthalenedisulfonate (NDS, 2 equivalents) and the tetrahydrochloride salt of tetrakis(4-aminophenyl)methane (TAPM, 1 equivalent) in water gave a novel three-dimensional charge-assisted hydrogen-bonded framework (CAHOF, F-1). The framework F-1 was characterized by X-ray diffraction, TGA, elemental analysis, and 1H NMR spectroscopy. The framework was supported by hydrogen bonds between the sulfonate anions and the ammonium cations of NDS and protonated TAPM moieties, respectively. The CAHOF material functioned as a new type of catalytically active Brønsted acid in a series of reactions, including the ring opening of epoxides by water and alcohols. A Diels–Alder reaction between cyclopentadiene and methyl vinyl ketone was also catalyzed by F-1 in heptane. Depending on the polarity of the solvent mixture, the CAHOF F-1 could function as a purely heterogeneous catalyst or partly dissociate, providing some dissolved F-1 as the real catalyst. In all cases, the catalyst could easily be recovered and recycled

Inhibition by Water during Heterogeneous Brønsted Acid Catalysis by Three-Dimensional Crystalline Organic Salts

A new self-assembled and self-healing class of metal free, recyclable, heterogeneous Brønsted acid catalysts has been developed by the protonation of aniline derivatives (tetrakis(4-aminophenyl)methane, leuco-crystal violet, benzidine, and p-phenylenediamine) with aromatic sulfonic acids (tetrakis(phenyl-4-sulfonic acid)methane, and 2,6-naphthalenedisulfonic acid). As a result, five three-dimensional crystalline organic salts (F-1a, F-1b, F-1c, F-2, and F-3) were obtained, linked by hydrogen bonds and additionally stabilized by the opposite charges of the components. Frameworks F-2 and F-3 were prepared for the first time and characterized by elemental analysis, X-ray structural analysis (for F-2), thermogravimetry, SEM, and FTIR spectroscopy. The catalytic activities of crystalline organic salts F-1-3 have been explored in industrially important epoxide ring-opening and acetal formation reactions. The presence of encapsulated water inside frameworks F-1a and F-2 had an inhibitory effect on the performance of the catalysts. X-ray diffraction analysis of hydrated and dehydrated samples of F-1a and F-2 indicated that water of crystallization served as a cross-linking agent, diminishing the substrate induced "breathing"affinities of the frameworks

Carbonate record of temporal change in oxygen fugacity and gaseous species in asteroid Ryugu

The Hayabusa2 spacecraft explored asteroid Ryugu and brought its surface materials to Earth. Ryugu samples resemble Ivuna-type (CI) chondrites-the most chemically primitive meteorites-and contain secondary phyllosilicates and carbonates, which are indicative of aqueous alteration. Understanding the conditions (such as temperature, redox state and fluid composition) during aqueous alteration is crucial to elucidating how Ryugu evolved to its present state, but little is known about the temporal changes in these conditions. Here we show that calcium carbonate (calcite) grains in Ryugu and Ivuna samples have variable O-18/O-16 and C-13/C-12 ratios that are, respectively, 24-46 & PTSTHOUSND; and 65-108 & PTSTHOUSND; greater than terrestrial standard values, whereas those of calcium-magnesium carbonate (dolomite) grains are much more homogeneous, ranging within 31-36 & PTSTHOUSND; for oxygen and 67-75 & PTSTHOUSND; for carbon. We infer that the calcite precipitated first over a wide range of temperatures and oxygen partial pressures, and that the proportion of gaseous CO2/CO/CH4 molecules changed temporally. By contrast, the dolomite formed later in a more oxygen-rich and thus CO2-dominated environment when the system was approaching equilibrium. The characteristic isotopic compositions of secondary carbonates in Ryugu and Ivuna are not observed for other hydrous meteorites, suggesting a unique evolutionary pathway for their parent asteroid(s). The asteroid Ryugu experienced aqueous alteration under changing temperature and redox conditions, according to an isotopic analysis of secondary calcite and dolomite grains in samples from Ryugu obtained by the Hayabusa2 spacecraft

The Magnesium Isotope Composition of Samples Returned from Asteroid Ryugu

International audienceThe nucleosynthetic isotope composition of planetary materials provides a record of the heterogeneous distribution of stardust within the early solar system. In 2020 December, the Japan Aerospace Exploration Agency Hayabusa2 spacecraft returned to Earth the first samples of a primitive asteroid, namely, the Cb-type asteroid Ryugu. This provides a unique opportunity to explore the kinship between primitive asteroids and carbonaceous chondrites. We report high-precision μ 26Mg* and μ 25Mg values of Ryugu samples together with those of CI, CM, CV, and ungrouped carbonaceous chondrites. The stable Mg isotope composition of Ryugu aliquots defines μ 25Mg values ranging from -160 ± 20 ppm to -272 ± 30 ppm, which extends to lighter compositions relative to Ivuna-type (CI) and other carbonaceous chondrite groups. We interpret the μ 25Mg variability as reflecting heterogeneous sampling of a carbonate phase hosting isotopically light Mg (μ 25Mg ~ -1400 ppm) formed by low temperature equilibrium processes. After correcting for this effect, Ryugu samples return homogeneous μ 26Mg* values corresponding to a weighted mean of 7.1 ± 0.8 ppm. Thus, Ryugu defines a μ 26Mg* excess relative to the CI and CR chondrite reservoirs corresponding to 3.8 ± 1.1 and 11.9 ± 0.8 ppm, respectively. These variations cannot be accounted for by in situ decay of 26Al given their respective 27Al/24Mg ratios. Instead, it requires that Ryugu and the CI and CR parent bodies formed from material with a different initial 26Al/27Al ratio or that they are sourced from material with distinct Mg isotope compositions. Thus, our new Mg isotope data challenge the notion that Ryugu and CI chondrites share a common nucleosynthetic heritage