High-Pressure Synthesis of a Pentazolate Salt

The pentazolates, the last all-nitrogen members of the azole series, have been notoriously elusive for the last hundred years despite enormous efforts to make these compounds in either gas or condensed phases. Here we report a successful synthesis of a solid state compound consisting of isolated pentazolate anions N5-, which is achieved by compressing and laser heating cesium azide (CsN3) mixed with N2 cryogenic liquid in a diamond anvil cell. The experiment was guided by theory, which predicted the transformation of the mixture at high pressures to a new compound, cesium pentazolate salt (CsN5). Electron transfer from Cs atoms to N5 rings enables both aromaticity in the pentazolates as well as ionic bonding in the CsN5 crystal. This work provides a critical insight into the role of extreme conditions in exploring unusual bonding routes that ultimately lead to the formation of novel high nitrogen content species

Importance of correlation effects in hcp iron revealed by a pressure-induced electronic topological transition

We discover that hcp phases of Fe and Fe0.9Ni0.1 undergo an electronic topological transition at pressures of about 40 GPa. This topological change of the Fermi surface manifests itself through anomalous behavior of the Debye sound velocity, c/a lattice parameter ratio and M\"ossbauer center shift observed in our experiments. First-principles simulations within the dynamic mean field approach demonstrate that the transition is induced by many-electron effects. It is absent in one-electron calculations and represents a clear signature of correlation effects in hcp Fe

Local Extinction and Unintentional Rewilding of Bighorn Sheep (Ovis canadensis) on a Desert Island

Bighorn sheep ( Ovis canadensis) were not known to live on Tiburón Island, the largest island in the Gulf of California and Mexico, prior to the surprisingly successful introduction of 20 individuals as a conservation measure in 1975. Today, a stable island population of ∼500 sheep supports limited big game hunting and restocking of depleted areas on the Mexican mainland. We discovered fossil dung morphologically similar to that of bighorn sheep in a dung mat deposit from Mojet Cave, in the mountains of Tiburón Island. To determine the origin of this cave deposit we compared pellet shape to fecal pellets of other large mammals, and extracted DNA to sequence mitochondrial DNA fragments at the 12S ribosomal RNA and control regions. The fossil dung was 14C-dated to 1476-1632 calendar years before present and was confirmed as bighorn sheep by morphological and ancient DNA (aDNA) analysis. 12S sequences closely or exactly matched known bighorn sheep sequences; control region sequences exactly matched a haplotype described in desert bighorn sheep populations in southwest Arizona and southern California and showed subtle differentiation from the extant Tiburón population. Native desert bighorn sheep previously colonized this land-bridge island, most likely during the Pleistocene, when lower sea levels connected Tiburón to the mainland. They were extirpated sometime in the last ∼1500 years, probably due to inherent dynamics of isolated populations, prolonged drought, and (or) human overkill. The reintroduced population is vulnerable to similar extinction risks. The discovery presented here refutes conventional wisdom that bighorn sheep are not native to Tiburón Island, and establishes its recent introduction as an example of unintentional rewilding, defined here as the introduction of a species without knowledge that it was once native and has since gone locally extinct

Southwest Pacific deep-water carbonate chemistry during the Mid-Pleistocene Transition

After more than 40 years of research, there is still wide disagreement in defining when the Mid-Pleistocene Transition (MPT) occurred, with climate reconstructions ranging from an abrupt versus gradual transition that began as early as 1500 ka and ended as late as 600 ka. Our recent work in the Southwest Pacific (Ocean Drilling Program Site 1123) has provided some evidence for a rapid transition, suggesting that the MPT was initiated by an abrupt increase in global ice volume 900 thousand years ago [1]. This study uses shallow-infaunal benthic foraminifera Uvigerina spp. to disentangle the contributions of deep-water temperature (using Mg/Ca ratios) and ice volume to the oxygen isotopic composition of foraminiferal calcite over the last 1.5 Ma. The resulting sea-level reconstruction across the MPT shows that the critical step in ice-volume variation was associated with the suppression of melting in Marine Isotope Stage (MIS) 23, followed by renewed ice growth in MIS 22 to yield a very large ice sheet with 120 m of sea level lowering. Here, we built on this work with the aim to investigate further the abrupt event centered on MIS 24 to 22 (the ‘900-ka event’) and try to shed some light on the processes and mechanisms that caused the MPT. Different hypotheses account for the origin of the MPT as a response to long-term ocean cooling, perhaps because of lowering CO2. To better quantify the role of the carbon system during the MPT, we reconstruct past changes in bottom water inorganic carbon chemistry from the trace element (B/Ca) and stable isotopic composition of calcite shells of the infaunal benthic foraminifera Uvigerina spp. from 1100 ka to 350 ka at ODP Site 1123. This site was retrieved from Chatham Rise, east of New Zealand in the Southwest Pacific Ocean (41º47.2’S, 171º 29.9’ W, 3290 m water depth) and lies under the Deep Western Boundary Current (DWBC) that flows into the Pacific Ocean, and is responsible for most of the deep water in that ocean; DWBC strength is directly related to processes occurring around Antarctica. The ratio of boron to calcium (B/Ca) in benthic foraminifer shells has proven to be a reliable indicator of the calcite saturation state of ocean bottom waters. The comparison between benthic foraminifera δ18O and δ13C shows a similar trend at ODP Site 1123, implying a close relationship between these climate and carbon cycle signals, and we use our B/Ca record reconstructed from the same samples to explore the potential processes behind this tight coupling. These results permit preliminary discussion on the deep-water carbonate saturation state during glacial/interglacial cycles. Deep-water temperatures estimates using Mg/Ca and oxygen isotopic composition of seawater (δ18Osw) are available from Site 1123 for the last 1.5 million years [1] and the phase relationship between the different signals is tentatively assessed for the early/middle Pleistocene, when different patterns of climate variability have been inferred from marine and ice cores records. [1] Elderfield et al. (2012). Evolution of ocean temperature and ice volume through the Mid Pleistocene Climate Transition. Science, vol. 337, 6095, 704-70

Local Extinction and Unintentional Rewilding of Bighorn Sheep (Ovis canadensis) on a Desert Island

Bighorn sheep (Ovis canadensis) were not known to live on Tiburón Island, the largest island in the Gulf of California and Mexico, prior to the surprisingly successful introduction of 20 individuals as a conservation measure in 1975. Today, a stable island population of ~500 sheep supports limited big game hunting and restocking of depleted areas on the Mexican mainland. We discovered fossil dung morphologically similar to that of bighorn sheep in a dung mat deposit from Mojet Cave, in the mountains of Tiburón Island. To determine the origin of this cave deposit we compared pellet shape to fecal pellets of other large mammals, and extracted DNA to sequence mitochondrial DNA fragments at the 12S ribosomal RNA and control regions. The fossil dung was ¹⁴C-dated to 1476–1632 calendar years before present and was confirmed as bighorn sheep by morphological and ancient DNA (aDNA) analysis. 12S sequences closely or exactly matched known bighorn sheep sequences; control region sequences exactly matched a haplotype described in desert bighorn sheep populations in southwest Arizona and southern California and showed subtle differentiation from the extant Tiburón population. Native desert bighorn sheep previously colonized this land-bridge island, most likely during the Pleistocene, when lower sea levels connected Tiburón to the mainland. They were extirpated sometime in the last ~1500 years, probably due to inherent dynamics of isolated populations, prolonged drought, and (or) human overkill. The reintroduced population is vulnerable to similar extinction risks. The discovery presented here refutes conventional wisdom that bighorn sheep are not native to Tiburón Island, and establishes its recent introduction as an example of unintentional rewilding, defined here as the introduction of a species without knowledge that it was once native and has since gone locally extinct

The anaplerotic node is essential for the intracellular survival of Mycobacterium tuberculosis

Enzymes at the phosphoenolpyruvate (PEP)–pyruvate–oxaloacetate or anaplerotic (ANA) node control the metabolic flux to glycolysis, gluconeogenesis, and anaplerosis. Here we used genetic, biochemical, and 13C isotopomer analysis to characterize the role of the enzymes at the ANA node in intracellular survival of the world's most successful bacterial pathogen, Mycobacterium tuberculosis (Mtb). We show that each of the four ANA enzymes, pyruvate carboxylase (PCA), PEP carboxykinase (PCK), malic enzyme (MEZ), and pyruvate phosphate dikinase (PPDK), performs a unique and essential metabolic function during the intracellular survival of Mtb. We show that in addition to PCK, intracellular Mtb requires PPDK as an alternative gateway into gluconeogenesis. Propionate and cholesterol detoxification was also identified as an essential function of PPDK revealing an unexpected role for the ANA node in the metabolism of these physiologically important intracellular substrates and highlighting this enzyme as a tuberculosis (TB)-specific drug target. We show that anaplerotic fixation of CO2 through the ANA node is essential for intracellular survival of Mtb and that Mtb possesses three enzymes (PCA, PCK, and MEZ) capable of fulfilling this function. In addition to providing a back-up role in anaplerosis we show that MEZ also has a role in lipid biosynthesis. MEZ knockout strains have an altered cell wall and were deficient in the initial entry into macrophages. This work reveals that the ANA node is a focal point for controlling the intracellular replication of Mtb, which goes beyond canonical gluconeogenesis and represents a promising target for designing novel anti-TB drugs

Same-Sex Parents Negotiating the Law in Italy: Between Claims of Recognition and Practices of Exclusion

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