Crystallography relevant to Mars and Galilean icy moons: crystal behavior of kieserite-type monohydrate sulfates at extraterrestrial conditions down to 15 K

Monohydrate sulfate kieserites (M 2+SO4·H2O) and their solid solutions are essential constituents on the surface of Mars and most likely also on Galilean icy moons in our solar system. Phase stabilities of end-member representatives (M 2+ = Mg, Fe, Co, Ni) have been examined crystallographically using single-crystal X-ray diffraction at 1 bar and temperatures down to 15 K, by means of applying open He cryojet techniques at in-house laboratory instrumentation. All four representative phases show a comparable, highly anisotropic thermal expansion behavior with a remarkable negative thermal expansion along the monoclinic b axis and a pronounced anisotropic expansion perpendicular to it. The lattice changes down to 15 K correspond to an `inverse thermal pressure' of approximately 0.7 GPa, which is far below the critical pressures of transition under hydrostatic compression (Pc ≥ 2.40 GPa). Consequently, no equivalent structural phase transition was observed for any compound, and neither dehydration nor rearrangements of the hydrogen bonding schemes have been observed. The M 2+SO4·H2O (M 2+ = Mg, Fe, Co, Ni) end-member phases preserve the kieserite-type C2/c symmetry; hydrogen bonds and other structural details were found to vary smoothly down to the lowest experimental temperature. These findings serve as an important basis for the assignment of sulfate-related signals in remote-sensing data obtained from orbiters at celestial bodies, as well as for thermodynamic considerations and modeling of properties of kieserite-type sulfate monohydrates relevant to extraterrestrial sulfate associations at very low temperatures.

Genome-wide identification and expression profiling of the COBRA-like genes reveal likely roles in stem strength in rapeseed (Brassica napus L.)

The COBRA-like (COBL) genes play key roles in cell anisotropic expansion and the orientation of microfibrils. Mutations in these genes cause the brittle stem and induce pathogen responsive phenotypes in Arabidopsis and several crop plants. In this study, an in silico genome-wide analysis was performed to identify the COBL family members in Brassica. We identified 44, 20 and 23 COBL genes in B. napus and its diploid progenitor species B. rapa and B. oleracea, respectively. All the predicted COBL genes were phylogenetically clustered into two groups: the AtCOB group and the AtCOBL7 group. The conserved chromosome locations of COBLs in Arabidopsis and Brassica, together with clustering, indicated that the expansion of the COBL gene family in B. napus was primarily attributable to whole-genome triplication. Among the BnaCOBLs, 22 contained all the conserved motifs and derived from 9 of 12 subgroups. RNA-seq analysis was used to determine the tissue preferential expression patterns of various subgroups. BnaCOBL9, BnaCOBL35 and BnaCOBL41 were highly expressed in stem with high-breaking resistance, which implies these AtCOB subgroup members may be involved in stem development and stem breaking resistance of rapeseed. Our results of this study may help to elucidate the molecular properties of the COBRA gene family and provide informative clues for high stem-breaking resistance studies.

Anisotropic expansion of hepatocyte lumina enforced by apical bulkheads

Lumen morphogenesis results from the interplay between molecular pathways and mechanical forces. In several organs, epithelial cells share their apical surfaces to form a tubular lumen. In the liver, however, hepatocytes share the apical surface only between adjacent cells and form narrow lumina that grow anisotropically, generating a 3D network of bile canaliculi (BC). Here, by studying lumenogenesis in differentiating mouse hepatoblasts in vitro, we discovered that adjacent hepatocytes assemble a pattern of specific extensions of the apical membrane traversing the lumen and ensuring its anisotropic expansion. These previously unrecognized structures form a pattern, reminiscent of the bulkheads of boats, also present in the developing and adult liver. Silencing of Rab35 resulted in loss of apical bulkheads and lumen anisotropy, leading to cyst formation. Strikingly, we could reengineer hepatocyte polarity in embryonic liver tissue, converting BC into epithelial tubes. Our results suggest that apical bulkheads are cell-intrinsic anisotropic mechanical elements that determine the elongation of BC during liver tissue morphogenesis.

Base Catalysis of Sodium Salts of [Ta6−xNbxO19]8− Mixed-Oxide Clusters

The solid base catalysis of sodium salts of Lindqvist-type metal oxide clusters was investigated using a Knoevenagel condensation reaction. We successfully synthesized the sodium salts of Ta and Nb mixed-oxide clusters Na8−nHn[(Ta6−xNbx)O19]·15H2O (Na-Ta6−xNbx, n = 0, 1, x = 0–6) and found them to exhibit activity for proton abstraction from nitrile substrates with a pKa value of 23.8, which is comparable to that of the conventional solid base MgO. The Ta-rich Na-Ta6 and Na-Ta4Nb2 exhibited high activity among Ta and Nb mixed-oxide clusters. Synchrotron X-ray diffraction (SXRD) measurements, Fourier-transform infrared (FT-IR) spectroscopy, and X-ray absorption spectroscopy (XAS) revealed the structure of Na-Ta6−xNbx: (1) The crystal structure changed from Na7H[M6O19]·15H2O to Na8[M6O19]·15H2O (M = Ta or Nb) by the anisotropic expansion of the unit cell with an increase in Ta content; (2) Highly symmetrical Lindqvist [Ta6−xNbxO19]8− was generated in Na-Ta4Nb2 and Na-Ta6 because of the symmetrical association of Na+ ions with [Ta6−xNbxO19]8− in the structure. DFT calculation revealed that the Lindqvist structures with high symmetry have large NBO charges on surface oxygen species, which are strongly related to base catalytic activity, whereas the composition hardly affects the NBO charges. The above results showed that the Brønsted base catalysis was sensitive to the symmetry of the Lindqvist [Ta6−xNbxO19]8− structure. These findings contribute to the design of solid base catalysts composed of anionic metal oxide clusters with alkaline-metal cations.

How Smooth Muscle Contractions Shape the Developing Enteric Nervous System

Neurons and glia of the enteric nervous system (ENS) are constantly subject to mechanical stress stemming from contractions of the gut wall or pressure of the bolus, both in adulthood and during embryonic development. Because it is known that mechanical forces can have long reaching effects on neural growth, we investigate here how contractions of the circular smooth muscle of the gut impact morphogenesis of the developing fetal ENS, in chicken and mouse embryos. We find that the number of enteric ganglia is fixed early in development and that subsequent ENS morphogenesis consists in the anisotropic expansion of a hexagonal honeycomb (chicken) or a square (mouse) lattice, without de-novo ganglion formation. We image the deformations of the ENS during spontaneous myogenic motility and show that circular smooth muscle contractile waves induce longitudinal strain on the ENS network; we rationalize this behavior by mechanical finite element modeling of the incompressible gut wall. We find that the longitudinal anisotropy of the ENS vanishes when contractile waves are suppressed in organ culture, showing that these contractile forces play a key role in sculpting the developing ENS. We conclude by summarizing different key events in the fetal development of the ENS and the role played by mechanics in the morphogenesis of this unique nerve network.

Synthesis, crystal structure, and X-ray diffraction data of lithium m-phenylenediamine sulfate Li2(C6H10N2)(SO4)2

A new organic–inorganic hybrid lithium m-phenylenediamine sulfate (LPS), Li2(C6H10N2)(SO4)2, was synthesized under aqueous solution conditions. The X-ray powder diffraction study determined that the title compound crystallized in a monoclinic system at 300 K, with unit-cell parameters a = 7.8689(6) Å, b = 6.6353(5) Å, c = 11.8322(10) Å, β = 109.385(3) °, V = 582.77(8) Å3. Indexing of the diffraction patterns collected from 100 to 600 K reveals that LPS has no structural phase transition within the measured temperature range, and the volume expansion coefficient is approximately 2.79 × 10−5 K−1. The crystal structure was solved based on the single-crystal diffraction data with space group P21/m. Lithium and SO42− are found to form quasi-two-dimensional anti-fluorite [LiSO4] layers stacking along the c-axis, with m-phenylenediamine molecules inserted in the anti-fluorite layers and forming hydrogen bonds to the SO42−. This explains a moderate anisotropic expansion in LPS.

The effect of anisotropic vesiculation on the porous-permeable evolution in magmatic foams

<p>Volcanoes can undergo rapid transitions between effusive and explosive eruptions that are often dependant on the melt’s ability to devolatilise and outgas. Eruptive products show widely contrasting permeability values for a given porosity owing to the fact that magma properties evolve over time and space, hence porosity and permeability vary depending on transport and deformation history, scale and orientation. The vesicularity that enables bubble coalescence and permeability development, termed the percolation threshold, is experimentally determined to be at ~30-80 %, depending on the microstructure of magma (i.e. bubble size and shape distribution, crystal content, dominant mode of rheological deformation during vesiculation and flow). During ascent of magma pressure decreases and the magma adapts to these new conditions by vesiculating and expanding against wall rocks. Friction between the vesicular magma and the conduit wall encourages shear, which modifies the architecture of the vesicular network. The geometrical constriction associated with conduits, dykes or fractures which host magma thus prevents or limits the isotropic growth of vesicles; we hypothesise that geometrical constraints instead lead to different ratios of isotropic to anisotropic expansion, which impacts vesicle coalescence and the onset and development of permeable gas flow in magma. We present experimental results detailing the impact of constricting geometry on the development of a permeable porous network, by combining various diameter basalt crucibles with different sized cylindrical cores of aphyric rhyolitic glass (0.12 wt.% H<sub>2</sub>O). We vesiculate the samples in a furnace at 1009 °C for different isothermal dwell increments, before cooling our sample assembly and determining porosity, strain and gas permeability. The vesiculated rhyolites host an impervious glass rind (due to near-surface bubble resorption via diffusion) surrounding a vesicular core; as such, we measure gas permeability of the assembly after cutting the upper and lower glassy rind, to expose the permeability of the internal porous network developed experimentally. The findings indicate that increasing anisotropy, caused by minimising the extent of isotropic vesiculation and maximising vesiculation under constricted conditions, lowers the porosity at which the percolation threshold occurs by ~30 %. We postulate that pure and simple shear, developed parallel to the constricting walls, increase bubble aspect ratios and enhance coalescence. This suggests magmatic foams form connected networks at lower porosities when they vesiculate in constricted conduits, dykes and fractures, thus impacting outgassing efficiency. This implies that the physico-chemical evolution of vesiculating magma may be more strongly linked to structural and rheological controls than previously anticipated, with important implications on ascending magma evolution and eruptive processes, such as degassing, outgassing and fragmentation.</p>

Measuring the tidal response of structure Formation: Anisotropic separate universe simulations using TreePM

We present anisotropic ‘separate universe’ simulations which modify the N-body code gadget4 in order to represent a large-scale tidal field through an anisotropic expansion factor. These simulations are used to measure the linear, quasi-linear and nonlinear response of the matter power spectrum to a spatially uniform trace-free tidal field up to wavenumber k = 7 h Mpc−1. Together with the response to a large-scale overdensity measured in previous work, this completely describes the nonlinear matter bispectrum in the squeezed limit. We find that the response amplitude does not approach zero on small scales in physical coordinates, but rather a constant value at z = 0, RK ≈ 0.5 for k ≥ 3 h Mpc−1 up to the scale where we consider our simulations reliable, k ≤ 7 h Mpc−1. This shows that even the inner regions of haloes are affected by the large-scale tidal field. We also measure directly the alignment of halo shapes with the tidal field, finding a clear signal which increases with halo mass.