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At least 253 records · Page 14

Precision Mass Measurements of Neutron-Rich Neodymium and Samarium Isotopes and Their Role in Understanding Rare-Earth Peak Formation

The Canadian Penning Trap mass spectrometer at the Californium Rare Isotope Breeder Upgrade (CARIBU) facility was used to measure the masses of eight neutron-rich isotopes of Nd and Sm. These measurements are the first to push into the region of nuclear masses relevant to the formation of the rare-earth abundance peak at A similar to 165 by the rapid neutron-capture process. We compare our results with theoretical predictions obtained from "reverse engineering" the mass surface that best reproduces the observed solar abundances in this region through a Markov chain Monte Carlo technique. Our measured masses are consistent with the reverse-engineering predictions for a neutron star merger wind scenario.

Orford, R.↗

Formation of nickel germanides from Ni layers with thickness below 10 nm

The authors have studied the reaction between a Ge (100) substrate and thin layers of Ni ranging from 2 to 10 nm in thickness. The formation of metal-rich Ni5Ge3Ni5Ge3 was found to precede that of the monogermanide NiGe by means of real-time in situ x-ray diffraction during ramp-annealing and ex situ x-ray pole figure analyses for phase identification. The observed sequential growth of Ni5Ge3Ni5Ge3 and NiGe with such thin Ni layers is different from the previously reported simultaneous growth with thicker Ni layers. The phase transformation from Ni5Ge3Ni5Ge3 to NiGe was found to be nucleation-controlled for Ni thicknesses <5 nm<5 nm, which is well supported by thermodynamic considerations. Specifically, the temperature for the NiGe formation increased with decreasing Ni (rather Ni5Ge3Ni5Ge3) thickness below 5 nm. In combination with sheet resistance measurement and microscopic surface inspection of samples annealed with a standard rapid thermal processing, the temperature range for achieving morphologically stable NiGe layers was identified for this standard annealing process. As expected, it was found to be strongly dependent on the initial Ni thickness

36 MATERIALS SCIENCE↗

Pyrophosphate-Dependent ATP Formation from Acetyl Coenzyme A in Syntrophus aciditrophicus, a New Twist on ATP Formation

ABSTRACT Syntrophus aciditrophicus is a model syntrophic bacterium that degrades key intermediates in anaerobic decomposition, such as benzoate, cyclohexane-1-carboxylate, and certain fatty acids, to acetate when grown with hydrogen-/formate-consuming microorganisms. ATP formation coupled to acetate production is the main source for energy conservation by S. aciditrophicus . However, the absence of homologs for phosphate acetyltransferase and acetate kinase in the genome of S. aciditrophicus leaves it unclear as to how ATP is formed, as most fermentative bacteria rely on these two enzymes to synthesize ATP from acetyl coenzyme A (CoA) and phosphate. Here, we combine transcriptomic, proteomic, metabolite, and enzymatic approaches to show that S. aciditrophicus uses AMP-forming, acetyl-CoA synthetase (Acs1) for ATP synthesis from acetyl-CoA. acs1 mRNA and Acs1 were abundant in transcriptomes and proteomes, respectively, of S. aciditrophicus grown in pure culture and coculture. Cell extracts of S. aciditrophicus had low or undetectable acetate kinase and phosphate acetyltransferase activities but had high acetyl-CoA synthetase activity under all growth conditions tested. Both Acs1 purified from S. aciditrophicus and recombinantly produced Acs1 catalyzed ATP and acetate formation from acetyl-CoA, AMP, and pyrophosphate. High pyrophosphate levels and a high AMP-to-ATP ratio (5.9 ± 1.4) in S. aciditrophicus cells support the operation of Acs1 in the acetate-forming direction. Thus, S. aciditrophicus has a unique approach to conserve energy involving pyrophosphate, AMP, acetyl-CoA, and an AMP-forming, acetyl-CoA synthetase. IMPORTANCE Bacteria use two enzymes, phosphate acetyltransferase and acetate kinase, to make ATP from acetyl-CoA, while acetate-forming archaea use a single enzyme, an ADP-forming, acetyl-CoA synthetase, to synthesize ATP and acetate from acetyl-CoA. Syntrophus aciditrophicus apparently relies on a different approach to conserve energy during acetyl-CoA metabolism, as its genome does not have homologs to the genes for phosphate acetyltransferase and acetate kinase. Here, we show that S. aciditrophicus uses an alternative approach, an AMP-forming, acetyl-CoA synthetase, to make ATP from acetyl-CoA. AMP-forming, acetyl-CoA synthetases were previously thought to function only in the activation of acetate to acetyl-CoA.

59 BASIC BIOLOGICAL SCIENCES↗

Film breakdown and nano-porous Mg(OH) 2 formation from corrosion of magnesium alloys in salt solutions

In this paper, small angle neutron scattering (SANS) and scanning transmission electron microscopy (STEM) were used to study film formation by magnesium alloys AZ31B (Mg-3Al-1Zn base) and ZE10A (Elektron 717, E717: Mg-1Zn + Nd, Zr) in H 2 O and D 2 O with and without 1 or 5 wt% NaCl. No SANS scattering changes were observed after 24 h D 2 O or H 2 O exposures compared with as-received (unreacted) alloy, consistent with relatively dense MgO-base film formation. However, exposure to 5 wt% NaCl resulted in accelerated corrosion, with resultant SANS scattering changes detected. The SANS data indicated both particle and rough surface (internal and external) scattering, but with no preferential size features. The films formed in 5 wt% NaCl consisted of a thin, inner MgO-base layer, and a nano-porous and filamentous Mg(OH) 2 outer region tens of microns thick. Chlorine was detected extending to the inner MgO-base film region, with segregation of select alloying elements also observed in the inner MgO, but not the outer Mg(OH) 2 . Modeling of the SANS data suggested that the outer Mg(OH) 2 films had very high surface areas, consistent with loss of film protectiveness. Finally, implications for the NaCl corrosion mechanism, and the potential utility of SANS for Mg corrosion, are discussed.

36 MATERIALS SCIENCE↗

Connecting CO intensity mapping to molecular gas and star formation in the epoch of galaxy assembly

Intensity mapping, which images a single spectral line from unresolved galaxies across cosmological volumes, is a promising technique for probing the early universe. Here we present predictions for the intensity map and power spectrum of the CO(1–0) line from galaxies at z∼2.4–2.8, based on a parameterized model for the galaxy–halo connection, and demonstrate the extent to which properties of high-redshift galaxies can be directly inferred from such observations. We find that our fiducial prediction should be detectable by a realistic experiment. Motivated by significant modeling uncertainties, we demonstrate the effect on the power spectrum of varying each parameter in our model. Using simulated observations, we infer constraints on our model parameter space with an MCMC procedure, and show corresponding constraints on the L{sub IR}–L{sub CO} relation and the CO luminosity function. These constraints would be complementary to current high-redshift galaxy observations, which can detect the brightest galaxies but not complete samples from the faint end of the luminosity function. By probing these populations in aggregate, CO intensity mapping could be a valuable tool for probing molecular gas and its relation to star formation in high-redshift galaxies.

79 ASTRONOMY AND ASTROPHYSICS↗

THE LINK BETWEEN RARE-EARTH PEAK FORMATION AND THE ASTROPHYSICAL SITE OF THE R PROCESS

The primary astrophysical source of the rare-earth elements is the rapid neutron capture process ( r process). The rare-earth peak that is seen in the solar r -process residuals has been proposed to originate as a pile-up of nuclei during the end of the r process. We introduce a new method utilizing Monte Carlo studies of nuclear masses in the rare-earth region, that includes self-consistently adjusting β -decay rates and neutron capture rates, to find the mass surfaces necessary for the formation of the rare-earth peak. We demonstrate our method with two types of astrophysical scenario, one corresponding to conditions typical of hot winds from core-collapse supernovae and stellar-mass accretion disks, and one corresponding to conditions typical of the ejection of the material from the tidal tails of neutron star mergers. In each type of astrophysical condition, this method successfully locates a region of enhanced stability in the mass surface that is responsible for the rare-earth peak. For each scenario, we find that the change in the mass surface has qualitatively different features, thus future measurements can shed light on the type of environment in which the r process occurred.

79 ASTRONOMY AND ASTROPHYSICS↗

How the First Stars Regulated Star Formation. II. Enrichment by Nearby Supernovae

Metals from Population III (Pop III) supernovae led to the formation of less massive Pop II stars in the early universe, altering the course of evolution of primeval galaxies and cosmological reionization. There are a variety of scenarios in which heavy elements from the first supernovae were taken up into second-generation stars, but cosmological simulations only model them on the largest scales. We present small-scale, high-resolution simulations of the chemical enrichment of a primordial halo by a nearby supernova after partial evaporation by the progenitor star. We find that ejecta from the explosion crash into and mix violently with ablative flows driven off the halo by the star, creating dense, enriched clumps capable of collapsing into Pop II stars. Metals may mix less efficiently with the partially exposed core of the halo, so it might form either Pop III or Pop II stars. Both Pop II and III stars may thus form after the collision if the ejecta do not strip all the gas from the halo. The partial evaporation of the halo prior to the explosion is crucial to its later enrichment by the supernova.

79 ASTRONOMY AND ASTROPHYSICS↗

Spiral structure and star formation. I - Formation mechanisms and mean free paths

The wide variety of optical appearances observed in spiral galaxies has encouraged the growth of two theoretical approaches to explain the spiral patterns exhibited by such young objects as OB associations, giant H II regions, and dark dust lanes. These approaches are related to the density wave theory of spiral structure and 'stochastic, self-propagating star formation'. Levinson and Roberts (1981) tried to reconcile these two theoretical approaches, and considered a disk filled with discrete gas clouds. The present investigation is concerned with refinements and extensions of the model of Levinson and Roberts. Attention is given to gravitational forces and dynamical propagation, cloud-cloud collisions, supernova interactions, computational models, a theory concerning the interactions of the gas cloud and stellar association systems, the time evolution of the gas cloud-stellar association systems, and aspects of collisionally triggered star formation.

Roberts, W. W., Jr.↗

Core formation by giant impacts: Conditions for intact melt region formation

Among the many effects of high-speed, giant impacts is widescale melting that can potentially trigger catastrophic core formation. If the projectile is sufficiently large, the melt pools to form an intact melt region. The dense phase then segregates from the melt, forming a density anomoly at the melt region's base. If the anomoly produces a differential stress larger than a certain minimum, it overcomes the mantle's long-term elastic strength and rapidly forms a core. It was previously shown that giant impacts effectively trigger core formation in silicate bodies by the time they grow to the mass of Mercury and in icy bodies by the time they grow larger than Triton. In order for this process to be viable, an intact melt region must be formed. Conditions under which this occurs is examined in more detail than previously published.

Tonks, W. B.↗

Montmorillonite catalysis of RNA oligomer formation in aqueous solution. A model for the prebiotic formation of RNA

Oligomers of adenylic acid of up to the 11-mer in length are formed by the reaction of the phosphorimidazolide of adenosine (ImpA) in pH 8 aqueous solution at room temperature in the presence of Na(+)-montmorillonite. These oligomers are joined by phosphodiester bonds in which the 3',5'-linkage predominates over the 2',5'-linkage by a 2:1 ratio. Reaction of a 9:1 mixture of ImpA, A5'ppA results in the formation of oligomers with a 3:1 ratio of 3',5'- to 2',5'-linked phosphodiester bonds. A high proportion of these oligomers contain the A5'ppA grouping. A5'ppA reacts much more rapidly with ImpA than does 5'-ADP (ppA) or 5'-ATP (pppA). The exchangeable cation associated with the montmorillonite effects the observed catalysis with Li+, Na+, NH4+, and Ca2+ being the more effective while Mg2+ and Al3+ are almost ineffective catalysts. 2',5'-Linked oligomers, up to the tetramer in length, are formed using UO2(2+)-montmorillonite. The structure analysis of individual oligomer fractions was performed by selective enzymatic and KOH hydrolytic studies followed by HPLC analysis of the reaction products. It is concluded from the composition of the oligomers that the rate of addition ImpA to a 3'-terminus containing a 2',5'-linkage is slower than the addition to a nucleoside joined by a 3',5'-linked phosphodiester bond. The potential importance of mineral catalysis of the formation of RNA and other oligomers on primitive Earth is discussed.

Non-NASA Center↗

Effect of phosphate activating group on oligonucleotide formation on montmorillonite: the regioselective formation of 3',5'-linked oligoadenylates

The effects of amine structure on the montmorillonite-catalyzed oligomerization of the 5'-phosphoramidates of adenosine are investigated. 4-Aminopyridine derivatives yielded oligoadenylates as long as dodecamers with a regioselectivity for 3',5'-phosphodiester bond formation averaging 88%. Linear and cyclic oligomers are obtained and no A5'ppA-containing products are detected. Oligomers as long as the hexanucleotide are obtained using 2-aminobenzimidazole as the activating group. A predominance of pA2'pA is detected in the dimer fraction along with cyclic 3',5'-trimer; no A5'ppA-containing oligomers were detected. Little or no oligomer formation was observed when morpholine, piperidine, pyrazole, 1,2,4-triazole, and 2-pyridone are used as phosphate-activating groups. The effects of the structure of the phosphate activating group on the oligomer structure and chain lengths are discussed.

Non-NASA Center↗

Isotopic Constraints on the Nature of Primary Precipitates in Archean–Early Paleoproterozoic Iron Formations from Determinations of the Iron Phonon Density of States of Greenalite and 2L- and 6L-Ferrihydrite

Iron formations (IFs) are chemical sedimentary rocks that were widely deposited before the Great Oxidation Event (GOE) around 2.4- 2.2 Ga. It is generally thought that IFs precipitated as hydrated Fe 3+ oxides (HFOs) such as ferrihydrite following surface oxidation of Fe 2+ -rich, anoxic deep waters. This model often implicates biological oxidation and underpins reconstructions of marine nutrient concentrations. However, nanoscale petrography indicates that an Fe 2+ silicate, greenalite, is a common primary mineral in well-preserved IFs, motivating an alternative depositional model of anoxic ferrous silicate precipitation. It is unclear, however, if Fe 2+ -rich silicates can produce the Fe isotopic variations in IFs that are well explained by Fe 2+ oxidation. To address this question, we constrain the equilibrium Fe isotopic ( 56 Fe/ 54 Fe) fractionation of greenalite and ferrihydrite by determining the iron phonon densities of states for those minerals. Here, we use ab initio density functional theory (DFT + U) calculations and nuclear resonant inelastic X-ray scattering spectroscopy to show that ferrous greenalite should be isotopically lighter than ferrihydrite by similar to 1-1.2 parts per thousand at equilibrium, and fractionation should scale linearly with increasing Fe 3+ content in greenalite. By anchoring ferrihydrite-greenalite mineral pair fractionations to published experimental Fe isotopic fractionations between HFOs and aqueous Fe 2+ , we show that ferrous greenalite may produce all but the heaviest pre-GOE Fe isotopic compositions and mixed valence greenalites can produce the entire record. Our results suggest that heavy Fe isotope enrichments alone are not diagnostic of primary IF mineralogies, and ferrihydrite and partially oxidized or even purely ferrous greenalite are all viable primary IF mineralogies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Conversion of CO 2 to Methyl Formate in a Flow Electrolyzer with Mixed Propylene Carbonate/Methanol Catholyte

Despite the promise of electrochemical carbon dioxide reduction as a technology for the production of clean fuels and decarbonization of the chemical industry, research has mostly focused on aqueous systems with a relatively limited set of products that have been achieved via electrosynthesis. Increasingly, CO 2 electroreduction in nonaqueous solvents is being pursued to develop new avenues for expanding the suite of products that can be made with high selectivity. CO 2 reduction in alcohols coupled with in situ esterification to produce esters is one such route that utilizes nonaqueous electrolyte. To be practical, such electrochemical syntheses need to be translated to a high-performance reactor such as a flow electrolyzer. However, many organic solvents, such as alcohols, wet and flood porous electrodes, thus impeding reactor performance. In this work, methanol was mixed with propylene carbonate as a catholyte for a gas-fed CO 2 flow electrolyzer that avoided cathode flooding. Simultaneously, a dual aqueous anolyte was used for water oxidation as a scalable and sustainable anodic half-reaction. The performance effect of methanol concentration, catholyte acidity, CO 2 flow rate, and dilute water in the catholyte were investigated. With 10 vol % methanol in 90 vol % propylene carbonate, 63% faradaic efficiency for methyl formate ester product was sustained without cathode flooding. However, improvements are still needed to lower the cell resistance and further increase the operating current density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formation of S0s in extreme environments Ⅲ: the role of environment in the formation pathways

It is well established that there are at least two main channels to form lenticular (or S0) galaxies. The first, which we name ‘faded spiral’ scenario, includes quenching events that led to consumption or removal of gas from a spiral progenitor. The second, which we call ‘merger’ scenario, includes merger-like events and interactions between galaxies. Each scenario leaves characteristic signatures in the newly formed lenticular galaxy. However, the conditions that trigger one mechanism over another are still unknown. This paper is the third of a series aimed at understanding the role of the environment in the formation of lenticular galaxies. In this study, we combine the kinematics, morphology, and properties of the stellar populations of 329 S0s from the SAMI and MaNGA surveys in order to highlight the role of the environment in the process. We divide the S0s into two classes (A and B) according to their global properties, that we can associate to the products of a faded spiral scenario (class A) or a merger scenario (class B). Here we then study how the various classes are distributed within different environments. Our study reveals that the ‘faded spiral’ pathway is the most efficient channel to produce S0s, and it becomes more efficient as the mass of the group or cluster or local density of galaxies increase. The merger pathway is also a viable channel, and its efficiency becomes higher with decreasing local density or environment mass.

79 ASTRONOMY AND ASTROPHYSICS↗