High diversity and morphological convergence among melanised fungi from rock formations in the Central Mountain System of Spain

Melanised fungi were isolated from rock surfaces in the Central Mountain System of Spain. Two hundred sixty six isolates were recovered from four geologically and topographically distinct sites. Microsatellite-primed PCR techniques were used to group isolates into genotypes assumed to represent species. One hundred and sixty three genotypes were characterised from the four sites. Only five genotypes were common to two or more sites. Morphological and molecular data were used to characterise and identify representative strains, but morphology rarely provided a definitive identification due to the scarce differentiation of the fungal structures or the apparent novelty of the isolates. Vegetative states of fungi prevailed in culture and in many cases could not be reliably distinguished without sequence data. Morphological characters that were widespread among the isolates included scarce micronematous conidial states, endoconidia, mycelia with dark olive-green or black hyphae, and mycelia with torulose, isodiametric or moniliform hyphae whose cells develop one or more transverse and/or oblique septa. In many of the strains, mature hyphae disarticulated, suggesting asexual reproduction by a thallic micronematous conidiogenesis or by simple fragmentation. Sequencing of the internal transcribed spacers (ITS1, ITS2) and 5.8S rDNA gene were employed to investigate the phylogenetic affinities of the isolates. According to ITS sequence alignments, the majority of the isolates could be grouped among four main orders of Pezizomycotina: Pleosporales, Dothideales, Capnodiales, and Chaetothyriales. Ubiquitous known soil and epiphytic fungi species were generally absent from the rock surfaces. In part, the mycota of the rock surfaces shared similar elements with melanised fungi from plant surfaces and fungi described from rock formations in Europe and Antarctica. The possibility that some of the fungi were lichen mycobionts or lichen parasites could not be ruled out

Bifunctional Paramagnetic and Luminescent Clays Obtained by Incorporation of Gd3+and Eu3+Ions in the Saponite Framework

A novel bifunctional saponite clay incorporating gadolinium (Gd3+) and europium (Eu3+) in the inorganic framework was prepared by one-pot hydrothermal synthesis. The material exhibited interesting luminescent and paramagnetic features derived from the co-presence of the lanthanide ions in equivalent structural positions. Relaxometry and photoluminescence spectroscopy shed light on the chemical environment surrounding the metal sites, the emission properties of Eu3+, and the dynamics of interactions between Gd3+ and the inner-sphere water placed in the saponite gallery. The optical and paramagnetic properties of this solid make it an attractive nanoplatform for bimodal diagnostic applications

Surprising Complexity of the [Gd(AAZTA)(H2O)2]- Chelate Revealed by NMR in the Frequency and Time Domains

Typically, Ln(III) complexes are isostructural along the series, which enables studying one particular metal chelate to derive the structural features of the others. This is not the case for [Ln(AAZTA)(H2O)x]- (x = 1, 2) systems, where structural variations along the series cause changes in the hydration number of the different metal complexes, and in particular the loss of one of the two metal-coordinated water molecules between Ho and Er. Herein, we present a 1H field-cycling relaxometry and 17O NMR study that enables accessing the different exchange dynamics processes involving the two water molecules bound to the metal center in the [Gd(AAZTA)(H2O)2]- complex. The resulting picture shows one Gd-bound water molecule with an exchange rate ∼6 times faster than that of the other, due to a longer metal-water distance, in accordance with density functional theory (DFT) calculations. The substitution of the more labile water molecule with a fluoride anion in a diamagnetic-isostructural analogue of the Gd-complex, [Y(AAZTA)(H2O)2]-, allows us to follow the chemical exchange process by high-resolution NMR and to describe its thermodynamic behavior. Taken together, the variety of tools offered by NMR (including high-resolution 1H, 19F NMR as a function of temperature, 1H longitudinal relaxation rates vs B0, and 17O transverse relaxation rates vs T) provides a complete description of the structure and exchange dynamics of these Ln-complexes along the series

The chemical consequences of the gradual decrease of the ionic radius along the Ln-series

[Abstract] In the periodical system, the lanthanides (the 15 elements in the periodic table between barium and hafnium) are unique in the sense that their trivalent cations have their valence electrons hidden behind the 5s and 5p electrons. They show a gradual decrease in ionic radius with increasing atomic number (also known as the lanthanide contraction). The resulting steric effects determine to a large extent the geometries of complexes of these ions. Here, we discuss these effects, particularly upon the properties of the complexes in aqueous solution, for selected families of Ln3+-complexes of oxycarboxylate and aminocarboxylate ligands. The physical properties of the cations are very different, which is very useful for the elucidation of the configuration, conformation and the dynamics of the complexes by X-ray techniques, NMR spectroscopy, and optical techniques. Often the structural analysis is assisted by computational methods

Magnetic and relaxation properties of vanadium(iv) complexes: an integrated H-1 relaxometric, EPR and computational study

We report a detailed study of the magnetic and relaxation properties of a series of oxovanadium(IV) complexes comprising the aqua ion [VO(H2O)5]2+ and [VO(ox)2]2- (ox = oxalate), [VO(nta)]- (nta = nitrilotriacetate), [VO(dtpa)] 3- (dtpa = diethylenetriaminepentaacetate) and [VO(acac)2] (acac = acetylacetonato) in solution. The complexes were characterized using continuous wave (X-band) and pulsed (Q-band) EPR measurements and 1H nuclear magnetic relaxation dispersion (NMRD) studies in the 0.01-120 MHz 1H Larmor frequency range. The 51V A-tensor parameters obtained from the analysis of EPR spectra are in good agreement with those obtained using theoretical calculations at the DFT and coupled-cluster levels (DLPNO-CCSD), while g-tensors were obtained with CASSCF/NEVPT2 calculations. EPR measurements reveal significant differences in the electronic Te1 and Te m relaxation times, with [VO(acac)2] showing a markedly different behaviour due to the trans coordination geometry. The NMRD profiles measured at different temperatures have contributions from both the outer- and inner-sphere mechanisms, with the latter showing contributions from the dipolar and scalar mechanisms. The rotational correlation times ( tR) obtained from the fitting of NMRD and EPR data are in good mutual agreement. The scalar mechanism depends on the hyperfine coupling constants of the coordinated water molecule Haiso, which were obtained from the fitting of the NMRD profiles and DFT calculations. Finally, the analysis of the data provided information on the exchange rate of coordinated water molecules, which display mean residence times of similar to 7-17 mu s at 298 K

Phase stability and dense polymorph of the BaCa(CO3)2 barytocalcite carbonate

The double carbonate BaCa(CO3)2 holds potential as host compound for carbon in the Earth?s crust and mantle. Here, we report the crystal structure determination of a high-pressure BaCa(CO3)2 phase characterized by single-crystal X-ray diffraction. This phase, named post-barytocalcite, was obtained at 5.7 GPa and can be described by a monoclinic Pm space group. The barytocalcite to post-baritocalcite phase transition involves a significant discontinuous 1.4% decrease of the unit-cell volume, and the increase of the coordination number of 1/4 and 1/2 of the Ba and Ca atoms, respectively. High-pressure powder X-ray diffraction measurements at room- and high-temperatures using synchrotron radiation and DFT calculations yield the thermal expansion of barytocalcite and, together with single-crystal data, the compressibility and anisotropy of both the low- and high-pressure phases. The calculated enthalpy differences between different BaCa(CO3)2 polymorphs confirm that barytocalcite is the thermodynamically stable phase at ambient conditions and that it undergoes the phase transition to the experimentally observed post-barytocalcite phase. The double carbonate is significantly less stable than a mixture of the CaCO3 and BaCO3 end-members above 10 GPa. The experimental observation of the high-pressure phase up to 15 GPa and 300 ºC suggests that the decomposition into its single carbonate components is kinetically hindered.Authors thank the fnancial support from the Spanish Ministerio de Ciencia e Innovación (MICINN) and the Agencia Estatal de Investigación under projects MALTA Consolider Ingenio 2010 network (RED2018-102612-T), PID2019-106383GB-C44, FIS2017-83295-P and PGC2018-097520-A-I00 (cofnanced by EU FEDER funds), and from the Generalitat Valenciana under project PROMETEO/2018/123. A.O.R. acknowledges the fnancial support of the Spanish MINECO RyC-2016-20301 Ramon y Cajal Grant. Authors also thank Dr. Nicolescu and the Mineralogy and Meteoritic Department of the Yale Peabody Museum of Natural History for providing the mineral samples, the MALTA Consolider supercomputing centre and Compute Canada for computational resources, the General Services of Research Support (SEGAI) at La Laguna University and ALBA-CELLS synchrotron for providing beamtime under experiments 2020084419 and 2021024988. Tese experiments were performed at the MSPD beamline with the collaboration of ALBA staf

Tractography of the Spider Monkey (\u3cem\u3eAteles geoffroyi\u3c/em\u3e) Corpus Callosum Using Diffusion Tensor Magnetic Resonance Imaging

The objective of this research was to describe the organization, connectivity and microstructure of the corpus callosum of the spider monkey (Ateles geoffroyi). Non-invasive magnetic resonance imaging and diffusion-tensor imaging were obtained from three subjects using a 3T Philips scanner. We hypothesized that the arrangement of fibers in spider monkeys would be similar to that observed in other non-human primates. A repeated measure (n = 3) of fractional anisotropy values was obtained of each subject and for each callosal subdivision. Measurements of the diffusion properties of corpus callosum fibers exhibited a similar pattern to those reported in the literature for humans and chimpanzees. No statistical difference was reached when comparing this parameter between the different CC regions (p = 0.066). The highest fractional anisotropy values corresponded to regions projecting from the corpus callosum to the posterior cortical association areas, premotor and supplementary motor cortices. The lowest fractional anisotropy corresponded to projections to motor and sensory cortical areas. Analyses indicated that approximately 57% of the fibers projects to the frontal cortex and 43% to the post-central cortex. While this study had a small sample size, the results provided important information concerning the organization of the corpus callosum in spider monkeys

Peptide metal-organic frameworks under pressure: flexible linkers for cooperative compression

We investigate the structural response of a dense peptide metal-organic framework using in situ powder and single-crystal X-ray diffraction under high-pressures. Crystals of Zn(GlyTyr)2 show a reversible compression by 13% in volume at 4 GPa that is facilitated by the ability of the peptidic linker to act as a flexible string for a cooperative response of the structure to strain. This structural transformation is controlled by changes to the conformation of the peptide, which enables a bond rearrangement in the coordination sphere of the metal and changes to the strength and directionality of the supramolecular interactions specific to the side chain groups in the dipeptide sequence. Compared to other structural transformations in Zn(II) peptide MOFs, this behaviour is not affected by host/guest interactions and relies exclusively on the conformational flexibility of the peptide and its side chain chemistry

Genome-wide parent-of-origin DNA methylation analysis reveals the intricacies of human imprinting and suggests a germline methylation-independent mechanism of establishment

Differential methylation between the two alleles of a gene has been observed in imprinted regions, where the methylation of one allele occurs on a parent-of-origin basis, the inactive X-chromosome in females, and at those loci whose methylation is driven by genetic variants. We have extensively characterized imprinted methylation in a substantial range of normal human tissues, reciprocal genome-wide uniparental disomies, and hydatidiform moles, using a combination of whole-genome bisulfite sequencing and high-density methylation microarrays. This approach allowed us to define methylation profiles at known imprinted domains at base-pair resolution, as well as to identify 21 novel loci harboring parent-of-origin methylation, 15 of which are restricted to the placenta. We observe that the extent of imprinted differentially methylated regions (DMRs) is extremely similar between tissues, with the exception of the placenta. This extra-embryonic tissue often adopts a different methylation profile compared to somatic tissues. Further, we profiled all imprinted DMRs in sperm and embryonic stem cells derived from parthenogenetically activated oocytes, individual blastomeres, and blastocysts, in order to identify primary DMRs and reveal the extent of reprogramming during preimplantation development. Intriguingly, we find that in contrast to ubiquitous imprints, the majority of placenta-specific imprinted DMRs are unmethylated in sperm and all human embryonic stem cells. Therefore, placental-specific imprinting provides evidence for an inheritable epigenetic state that is independent of DNA methylation and the existence of a novel imprinting mechanism at these loci