Compressibility and structural stability of ultra-incompressible bimetallic interstitial carbides and nitrides

We have investigated by means of high-pressure x-ray diffraction the structural stability of Pd2Mo3N, Ni2Mo3C0.52N0.48, Co3Mo3C0.62N0.38, and Fe3Mo3C. We have found that they remain stable in their ambient-pressure cubic phase at least up to 48 GPa. All of them have a bulk modulus larger than 330 GPa, being the least compressible material Fe3Mo3C, B0 = 374(3) GPa. In addition, apparently a reduction of compressibility is detected as the carbon content increased. The equation of state for each material is determined. A comparison with other refractory materials indicates that interstitial nitrides and carbides behave as ultra-incompressible materials.Comment: 14 pages, 3 figures, 1 tabl

Characterization of the response to zinc deficiency in the cyanobacterium Anabaena sp. strain PCC 7120

Zur regulators control zinc homeostasis by repressing target genes under zinc-sufficient conditions in a wide variety of bacteria. This paper describes how part of a survey of duplicated genes led to the identification of the open reading frame all2473 as the gene encoding the Zur regulator of the cyanobacterium Anabaena sp. strain PCC 7120. All2473 binds to DNA in a zinc-dependent manner, and its DNA-binding sequence was characterized, which allowed us to determine the relative contribution of particular nucleotides to Zur binding. A zur mutant was found to be impaired in the regulation of zinc homeostasis, showing sensitivity to elevated concentrations of zinc but not other metals. In an effort to characterize the Zur regulon in Anabaena, 23 genes containing upstream putative Zur-binding sequences were identified and found to be regulated by Zur. These genes are organized in six single transcriptional units and six operons, some of them containing multiple Zur-regulated promoters. The identities of genes of the Zur regulon indicate that Anabaena adapts to conditions of zinc deficiency by replacing zinc metalloproteins with paralogues that fulfill the same function but presumably with a lower zinc demand, and with inducing putative metallochaperones and membrane transport systems likely being involved in the scavenging of extracellular zinc, including plasma membrane ABC transport systems and outer membrane TonB-dependent receptors. Among the Zur-regulated genes, the ones showing the highest induction level encode proteins of the outer membrane, suggesting a primary role for components of this cell compartment in the capture of zinc cations from the extracellular medium.Ministerio de Ciencia e Innovación y Fondo Social Europeo BFU2007-66589/BMC BFU2010-19544Junta de Andalucía y FEDER P07-CVI-0316

Cosmology of an Axion-Like Majoron

We propose a singlet majoron model that defines an inverse seesaw mechanism in the v sector. The majoron phi has a mass m(phi) approximate to 0.5 eV and a coupling to the tau lepton similar to the one to neutrinos. In the early universe it is initially in thermal equilibrium, then it decouples at T approximate to 500 GeV and contributes with just Delta N-eff = 0.026 during BBN. At T = 26 keV (final stages of BBN) a primordial magnetic field induces resonant gamma phi oscillations that transfer 6% of the photon energy into majorons, implying Delta N-eff = 0.55 and a 4.7% increase in the baryon to photon ratio. At T approximate to m(phi) the majoron enters in thermal contact with the heaviest neutrino and it finally decays into v (v) over bar pairs near recombination, setting Delta N-eff = 0.85. The boost in the expansion rate at later times may relax the Hubble tension (we obtain H-0 = (71.4 +/- 0.5) km/s/Mpc), while the processes v (v) over bar phi suppress the free streaming of these particles and make the model consistent with large scale structure observations. Its lifetime and the fact that it decays into neutrinos instead of photons lets this axion-like majoron avoid the strong bounds that affect other axion-like particles of similar mass and coupling to photons.We would like to thank Mar Bastero, Adrián Carmona, Mikael R. Chala, Miguel Escudero, Javier Olmedo, José Santiago and Samuel Witte for discussions. This work was partially supported by the Spanish Ministry of Science, Innovation and Universities (PID2019-107844GB-C21/AEI/10.13039/501100011033) and by the Junta de Andalucía (FQM 101, SOMM17/6104/UGR, P18-FR-1962, P18-FR-5057)

Short communication: Application of site‐level assessment of governance and equity (sage) methodology to a candidate oecm: AndakÍ municipal natural park, caquetÁ, colombia.

Governance is a fundamental aspect and precondition for conservation strategies, such as protected areas or OECMs. A methodology for Site-level Assessment of Governance and Equity (SAGE) has been proposed by IUCN to explore different aspects of governance, based on ten principles. This article describes the application of SAGE to a candidate OECM for what we believe is the first time: the Andakí Municipal Natural Park in the Amazon region of Colombia. The application of SAGE generated useful insights into different aspects of governance, including the importance of good communication and recognising and respecting the rights and responsibilities of different actors. Based on this experience, we believe that the SAGE methodology could be a useful tool not only to identify priorities for improving governance, but also to assess governance and equity in order to evaluate if an area meets the criteria for an OECM that it is governed and managed to achieve sustained and effective contributions to in situ conservation of biodiversity, associated ecosystem functions and services, and cultural, spiritual, socio-economic and other locally relevant values. © 2021, IUCN - International Union for the Conservation of Nature. All rights reserved.This process was made possible with the support of: a) the Local Protected Areas Regional Project implemented by Deutsche Gesellschaft f?r Internationale Zusammenarbeit (GIZ) GmbH, ICLEI ? Local Governments for Sustainability and the International Union for Conservation of Nature (IUCN); Environment ministries in Brazil, Colombia, Ecuador and Peru; commissioned by the German Federal Ministry for the Environment, Nature Protection and Nuclear Safety; b) the project adaptation of the OECM criteria to the Colombian context supported by PPD-GEF-PNUD, and implemented by Resnatur, Instituto Humboldt, Fundaci?n Natura and the Local Protected Areas Project; and c) the EUROCLIMA+ programme supported by Expertise France, GIZ and the International Institute for the Environment and Development (IIED); and d) Thora Amend, Vice Chair, IUCN World Commission on Protected Areas (thematic area: Governance)

Trans-oligomerization of duplicated aminoacyl-tRNA synthetases maintains genetic code fidelity under stress

Aminoacyl-tRNA synthetases (aaRSs) play a key role in deciphering the genetic message by producing charged tRNAs and are equipped with proofreading mechanisms to ensure correct pairing of tRNAs with their cognate amino acid. Duplicated aaRSs are very frequent in Nature, with 25,913 cases observed in 26,837 genomes. The oligomeric nature of many aaRSs raises the question of how the functioning and oligomerization of duplicated enzymes is organized. We characterized this issue in a model prokaryotic organism that expresses two different threonyl-tRNA synthetases, responsible for Thr-tRNAThr synthesis: one accurate and constitutively expressed (T1) and another (T2) with impaired proofreading activity that also generates mischarged Ser-tRNAThr. Low zinc promotes dissociation of dimeric T1 into monomers deprived of aminoacylation activity and simultaneous induction of T2, which is active for aminoacylation under low zinc. T2 either forms homodimers or heterodimerizes with T1 subunits that provide essential proofreading activity in trans. These findings evidence that in organisms with duplicated genes, cells can orchestrate the assemblage of aaRSs oligomers that meet the necessities of the cell in each situation. We propose that controlled oligomerization of duplicated aaRSs is an adaptive mechanism that can potentially be expanded to the plethora of organisms with duplicated oligomeric aaRSs.Ministerio de Economía y Competitividad BFU2010–19544, BFU2013–44686-

Covalent Cross-Linking of 2H-MoS2 Nanosheets

The combination of 2D materials opens a wide range of possibilities to create new-generation structures with multiple applications. Covalently cross-linked approaches are a ground-breaking strategy for the formation of homo or heterostructures made by design. However, the covalent assembly of transition metal dichalcogenides flakes is relatively underexplored. Here, a simple covalent cross-linking method to build 2H-MoS2–MoS2 homostructures is described, using commercially available bismaleimides. These assemblies are mainly connected vertically, basal plane to basal plane, creating specific molecular sized spaces between MoS2 sheets. Therefore, this straightforward approach gives access to the controlled connection of sulfide-based 2D materials

A Bridging bis-Allyl Titanium Complex: Mechanistic Insights into the Electronic Structure and Reactivity

Treatment of the dinuclear compound [{Ti(η5-C5Me5)Cl2}2(μ-O)] with allylmagnesium chloride provides the formation of the allyltitanium(III) derivative [{Ti(η5-C5Me5)(μ-C3H5)}2(μ-O)] (1), structurally identified by single-crystal X-ray analysis. Density functional theory (DFT) calculations confirm that the electronic structure of 1 is a singlet state, and the molecular orbital analysis, along with the short Ti −Ti distance, reveal the presence of a metal −metal single bond between the two Ti(III) centers. Complex 1 reacts rapidly with organic azides, RN3 (R = Ph, SiMe3), to yield the allyl μ-imido derivatives [{Ti(η5-C5Me5)(CH2CH=CH2)}2(μ-NR)(μ-O)] [R = Ph(2), SiMe3(3)] along with molecular nitrogen release. Reaction of 2 and 3 with H2 leads to the μ-imido propyl species [{Ti(η5-C5Me5)(CH2CH2CH3)}2(μ-NR)(μ-O)] [R = Ph(4), SiMe3(5)]. Theoretical calculations were used to gain insight into the hydrogenation mechanism of complex 3 and rationalize the lower reactivity of 2. Initially, the μ-imido bridging group in these complexes activates the H2 molecule via addition to the Ti −N bonds. Subsequently, the titanium hydride intermediates induce a change in hapticity of the allyl ligands, and the nucleophilic attack of the hydride to the allyl groups leads to metallacyclopropane intermediates. Finally, the proton transfer from the amido group to the metallacyclopropane moieties affords the propyl complexes 4 and 5.Ministerio de Ciencia, Innovación y Universidades Universidad de Alcalá Generalitat de Cataluny

Reductive Hydrogenation of Sulfido-Bridged Tantalum Alkyl Complexes: A Mechanistic Insight

Hydrogenolysis of a series of alkyl sulfido-bridged tantalum(IV) dinuclear complexes [Ta(?5-C5Me5)R(?-S)]2 [R = Me, nBu (1), Et, CH2SiMe3, C3H5, Ph, CH2Ph (2), p-MeC6H4CH2 (3)] has led quantitatively to the Ta(III) tetrametallic sulfide cluster [Ta(?5-C5Me5)(?3-S)]4 (4) along with the corresponding alkane. Mechanistic information for the formation of the unique low-valent tetrametallic compound 4 was gathered by hydrogenation of the phenyl-substituted precursor [Ta(?5-C5Me5)Ph(?- S)]2, which proceeds through a stepwise hydrogenation process, disclosing the formation of the intermediate tetranuclear hydride sulfide [Ta2(?5-C5Me5)2(H)Ph(?-S)(?3-S)]2 (5). Extending our studies toward tantalum alkyl precursors containing functional groups susceptible to hydrogenation, such as the allyl-and benzylsubstituted compounds [Ta(?5-C5Me5)(?3-C3H5)(?-S)]2 and [Ta(?5-C5Me5)(CH2Ph)(?-S)]2 (2), enables alternative reaction pathways en route to the formation of 4. In the former case, the dimetallic system undergoes selective hydrogenation of the unsaturated allyl moiety, forming the asymmetric complex [{Ta(?5-C5Me5)(?3-C3H5)}(?-S)2{Ta(?5-C5Me5)(C3H7)}] (6) with only one propyl fragment. Species 2, in addition to the hydrogenation of one benzyl fragment and concomitant toluene release, also undergoes partial hydrogenation and dearomatization of the phenyl ring on the vicinal benzyl unity to give a ?5-cyclohexadienyl complex [Ta2(?5-C5Me5)2(?-CH2C6H6)(?-S)2] (7). The mechanistic implications of the latter hydrogenation process are discussed by means of DFT calculationsComunidad de MadridUniversidad de AlcaláPrograma Estímulo a la Investigación de Jóvenes Investigadore

Unveiling the stellar origin of the Wolf-Rayet nebula NGC6888 through infrared observations

We present a comprehensive infrared (IR) study of the iconic Wolf-Rayet (WR) wind-blown bubble NGC6888 around WR136. We use Wide-field Infrared Survey Explorer (WISE), Spitzer IRAC and MIPS and Herschel PACS IR images to produce a sharp view of the distribution of dust around WR136. We complement these IR photometric observations with Spitzer IRS spectra in the 5-38 $\mu$m wavelength range. The unprecedented high-resolution IR images allowed us to produce a clean spectral energy distribution, free of contamination from material along the line of sight, to model the properties of the dust in NGC6888. We use the spectral synthesis code Cloudy to produce a model for NGC6888 that consistently reproduces its optical and IR properties. Our best model requires a double distribution with the inner shell composed only of gas, whilst the outer shell requires a mix of gas and dust. The dust consists of two populations of grain sizes, one with small sized grains $a_\mathrm{small}$=[0.002-0.008] $\mu$m and another one with large sized grains $a_\mathrm{big}$=[0.05-0.5] $\mu$m. The population of big grains is similar to that reported for other red supergiants stars and dominates the total dust mass, which leads us to suggest that the current mass of NGC6888 is purely due to material ejected from WR136, with a negligible contribution of swept up interstellar medium. The total mass of this model is 25.5$^{+4.7}_{-2.8}$ M$_{\odot}$, a dust mass of $M_\mathrm{dust}=$0.14$^{+0.03}_{-0.01}$ M$_{\odot}$, for a dust-to-gas ratio of $5.6\times10^{-3}$. Accordingly, we suggest that the initial stellar mass of WR136 was $\lesssim$50 M$_{\odot}$, consistent with current single stellar evolution models.Comment: 13 pages, 11 figures, 6 tables; Accepted to MNRA