Reaction: Earth-Abundant Metal Catalysts for Energy Conversions
Earth-abundant metal catalysts offer many advantages over traditionally used precious metal catalysts for energy conversions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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Distinct assembly mechanisms underlie similar biogeographical patterns of rare and abundant bacteria in Tibetan Plateau grassland soils
Rare biosphere represents the majority of Earth's biodiversity and performs vital ecological functions, yet little is known about its biogeographical patterns and community assembly processes in terrestrial ecosystems. Herein, we investigated the community composition and phylogeny of rare (relative abundance <0.1%) and abundant (>1%) bacteria in dryland grassland soils on the Tibetan Plateau. Results revealed similar biogeographical patterns of rare and abundant bacteria at both compositional and phylogenetic levels, but rare subcommunity was more heavily influenced by stochasticity (72%) than the abundant (57%). The compositional variation of rare bacteria was less explained by environmental factors (41%) than that of the abundant (80%), while the phylogeny of rare bacteria (36%) was more explained than that of the abundant (29%). The phylogeny of rare bacteria was equally explained by local factors (soil and vegetation) and geospatial distance (11.5% and 11.9% respectively), while that of the abundant was more explained by geospatial distance (22.1%) than local factors (11.3%). Furthermore, a substantially tighter connection between the community phylogeny and composition was observed in rare (R(2) = 0.65) than in abundant bacteria (R(2) = 0.08). Our study provides novel insights into the assembly processes and biographical patterns of rare and abundant bacteria in dryland soils.
Ji, Mukan↗
Multiple marker abundance profiling: combining selected reaction monitoring and data-dependent acquisition for rapid estimation of organelle abundance in subcellular samples
Measuring changes in protein or organelle abundance in the cell is an essential, but challenging aspect of cell biology. Frequently-used methods for determining organelle abundance typically rely on detection of a very few marker proteins, so are unsatisfactory. In silico estimates of protein abundances from publicly available protein spectra can provide useful standard abundance values but contain only data from tissue proteomes, and are not coupled to organelle localization data. A new protein abundance score, the normalized protein abundance scale (NPAS), expands on the number of scored proteins and the scoring accuracy of lower-abundance proteins in Arabidopsis. NPAS was combined with subcellular protein localization data, facilitating quantitative estimations of organelle abundance during routine experimental procedures. A suite of targeted proteomics markers for subcellular compartment markers was developed, enabling independent verification of in silico estimates for relative organelle abundance. Estimation of relative organelle abundance was found to be reproducible and consistent over a range of tissues and growth conditions. In silico abundance estimations and localization data have been combined into an online tool, multiple marker abundance profiling, available in the SUBA4 toolbox (http://suba.live).
59 BASIC BIOLOGICAL SCIENCES↗
Determining the Reliability of Measuring Mercury Cycling Gene Abundance with Correlations with Mercury and Methylmercury Concentrations
Methylmercury (MeHg) is a bioaccumulative toxic contaminant in many ecosystems but factors governing its production are poorly understood. Recent work has shown that the anaerobic microbial conversion of mercury (Hg) to MeHg requires the Hg-methylation genes hgcAB and that these genes can be used as biomarkers in PCR-based estimators of Hg-methylator abundance. In an effort to determine reliable methods for assessing hgcA abundance and diversity and linking it to MeHg concentrations, multiple approaches were compared including metagenomic shotgun sequencing, 16S rRNA gene pyrosequencing and cloning/sequencing hgcAB gene products. Hg-methylator abundance was also determined by quantitative hgcA qPCR amplification and metaproteomics for comparison to the above measurements. Samples from eight Hg-contaminated sites were examined over a range of total Hg (HgT; 0.03–14 mg kg-1 wet wt. soil) and MeHg (0.05–27 µg kg-1 wet wt. soil) concentrations. In the metagenome and amplicon sequencing of hgcAB diversity, the Deltaproteobacteria were the dominant Hg-methylators, while Firmicutes and methanogenic Archaea were typically ~50% less abundant. This was consistent with metaproteomics estimates where the Deltaproteobacteria were consistently higher. The 16S rRNA gene pyrosequencing did not have sufficient resolution to identify hgcAB+ species. Metagenomic and hgcAB results were similar for Hg-methylator diversity and showed a tractable relationship between Hg-methylating bacteria and soil Hg concentrations among similar environmental samples. However, clade-specific qPCR-based approaches for hgcA are only appropriate when comparing the abundance of a particular clade across various samples.
59 BASIC BIOLOGICAL SCIENCES↗
Using nature’s blueprint to expand catalysis with Earth-abundant metals
Original title changed for publication from; " Using Nature's Blueprint to Enable Catalysis with Earth-Abundant Metals" A diverse array of redox transformations that are essential to life are catalyzed by metalloenzymes that feature an earth-abundant metal. In contrast, platinum-group metals have been the cornerstone of many industrial catalytic reactions for decades, providing high activity, thermal stability and tolerance to chemical poisons. We assert that Nature’s blueprint provides the fundamental principles for vastly expanding the use of abundant metals in catalysis. We highlight the key physical properties of abundant metals that distinguish them from precious metals, and we look to Nature to understand how the inherent attributes of abundant metals can be embraced, leading to unique, highly efficient catalysts, emphasizing reactions crucial to the sustainable production and transformation of fuels and chemicals.
Bullock, Ronald M.↗
The Southern Stellar Stream Spectroscopic Survey (S{sup 5}): Chemical Abundances of Seven Stellar Streams
We present high-resolution Magellan/MIKE spectroscopy of 42 red giant stars in seven stellar streams confirmed by the Southern Stellar Stream Spectroscopic Survey (S {sup 5}): ATLAS, Aliqa Uma, Chenab, Elqui, Indus, Jhelum, and Phoenix. Abundances of 30 elements have been derived from over 10,000 individual line measurements or upper limits using photometric stellar parameters and a standard LTE analysis. This is currently the most extensive set of element abundances for stars in stellar streams. Three streams (ATLAS, Aliqa Uma, and Phoenix) are disrupted metal-poor globular clusters, although only weak evidence is seen for the light-element anticorrelations commonly observed in globular clusters. Four streams (Chenab, Elqui, Indus, and Jhelum) are disrupted dwarf galaxies, and their stars display abundance signatures that suggest progenitors with stellar masses ranging from 10{sup 6} to 10{sup 7} M {sub ⊙}. Extensive description is provided for the analysis methods, including the derivation of a new method for including the effect of stellar parameter correlations on each star’s abundance and uncertainty. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile.
79 ASTRONOMY AND ASTROPHYSICS↗
Sensitivity to Thermonuclear Reaction Rates in Modeling the Abundance Anomalies of NGC 2419
Abundance anomalies in globular clusters provide strong evidence for multiple stellar populations within each cluster. These populations are usually interpreted as distinct generations, with the currently observed second-generation stars having formed in part from the ejecta of massive, first-generation “polluter” stars, giving rise to the anomalous abundance patterns. The precise nature of the polluters and their enrichment mechanism are still unclear. Even so, the chemical abundances measured in second-generation stars within the globular cluster NGC 2419 provide insight into this puzzling process. Previous work used Monte Carlo nuclear reaction network calculations to constrain the temperature–density conditions that could reproduce the observed abundances, thereby placing robust limits on the origins of the polluter material. The effect of individual reaction rates on these conditions has not been studied, however. Thus, we perform an exhaustive sensitivity study on the nuclear physics input to determine which reactions have the greatest impact on these predictions. We find that the {sup 30}Si(p,γ){sup 31}P, {sup 37}Ar(p,γ){sup 38}K, {sup 38}Ar(p,γ){sup 39}K, and {sup 39}K(p,γ){sup 40}Ca reactions are all critical in determining the temperature–density conditions, and ultimately, the origins of the polluter material. We conclude with recommendations for future experiments.
79 ASTRONOMY AND ASTROPHYSICS↗
Dark Energy Survey Year 1 Results: Cosmological Constraints from Cluster Abundances, Weak Lensing, and Galaxy Correlations
We present the first joint analysis of cluster abundances and auto or cross-correlations of three cosmic tracer fields: galaxy density, weak gravitational lensing shear, and cluster density split by optical richness. From a joint analysis (4×2pt+N) of cluster abundances, three cluster cross-correlations, and the auto correlations of the galaxy density measured from the first year data of the Dark Energy Survey, we obtain Ωm=0.305-0.038+0.055 and σ8=0.783-0.054+0.064. This result is consistent with constraints from the DES-Y1 galaxy clustering and weak lensing two-point correlation functions for the flat νΛCDM model. Consequently, we combine cluster abundances and all two-point correlations from across all three cosmic tracer fields (6×2pt+N) and find improved constraints on cosmological parameters as well as on the cluster observable-mass scaling relation. This analysis is an important advance in both optical cluster cosmology and multiprobe analyses of upcoming wide imaging surveys.
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Chemical abundances in Seyfert galaxies – X. Sulphur abundance estimates
For the first time, the sulphur abundance relative to hydrogen (S/H) in the narrow-line regions of a sample of Seyfert 2 nuclei (Sy 2s) has been derived via direct estimation of the electron temperature. Narrow emission-line intensities from the Sloan Digital Sky Survey (SDSS) Data Release 17 (DR17) [in the wavelength range 3000 < λ(Å) < 9100] and from the literature for a sample of 45 nearby (z < 0.08) Sy 2s were considered. Our direct estimates indicate that Sy 2s have similar temperatures in the gas region where most of the $\rm S\rm ^{+}$ ions are located in comparison with that of star-forming regions (SFs). However, Sy 2s present higher temperature values (${\sim} 10\, 000$ K) in the region where most of the $\rm S\rm ^{2+}$ ions are located relative to that of SFs. We derive the total sulphur abundance in the range of $6.2 \: \lesssim 12+\log (\rm S/H) \: \lesssim \: 7.5$, corresponding to 0.1–1.8 times the solar value. These sulphur abundance values are lower by ∼0.4 dex than those derived in SFs with similar metallicity, indicating a distinct chemical enrichment of the interstellar medium (ISM) for these object classes. The sulphur abundance relative to oxygen (S/O) values for our Sy 2 sample present an abrupt (∼0.5 dex) decrease with increasing oxygen abundance relative to hydrogen (O/H) for the high-metallicity regime [$\rm 12+\log (O/H) \: \gtrsim 8.7)$], what is not seen for the SFs. However, when our Sy 2 estimates are combined with those from a large sample of SFs, we did not find any dependence between S/O and O/H.
79 ASTRONOMY AND ASTROPHYSICS↗
Chemical abundances in Seyfert galaxies – Ⅸ. Helium abundance estimates
For the first time, the helium abundance relative to hydrogen (He/H), which relied on direct measurements of the electron temperature, has been derived in the narrow line regions (NLRs) from a local sample of Seyfert 2 nuclei. In view of this, optical emission line intensities [3000 < λ(Å) < 7000] of 65 local Seyfert 2 nuclei (z < 0.2), taken from Sloan Digital Sky Survey Data Release 15 and additional compilation from the literature, were considered. Here we used photoionization model grid to derive an Ionization Correction Factor (ICF) for the neutral helium. The application of this ICF indicates that the NLRs of Seyfert 2 present a neutral helium fraction of ~50 percent in relation to the total helium abundance. We find that Seyfert 2 nuclei present helium abundance ranging from 0.60 to 2.50 times the solar value, while ~85 percent of the sample present oversolar abundance values. The derived (He/H)–(O/H) abundance relation from the Seyfert 2 is stepper than that of star-forming regions (SFs) and this difference could be due to excess of helium injected into the interstellar medium by the winds of Wolf–Rayet stars. From a regression to zero metallicity, by using Seyfert 2 estimates combined with SFs estimates, we obtained a primordial helium mass fraction Y p = 0.2441 ± 0.0037, a value in good agreement with the one inferred from the temperature fluctuations of the cosmic microwave background by the Planck Collaboration, i.e. $Y_{p}^{Planck}$ =0.2471 ± 0.0003.
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The Open Cluster Chemical Abundances and Mapping Survey. IV. Abundances for 128 Open Clusters Using SDSS/APOGEE DR16
The Open Cluster Chemical Abundances and Mapping (OCCAM) survey aims to constrain key Galactic dynamical and chemical evolution parameters by the construction of a large, comprehensive, uniform, infrared-based spectroscopic data set of hundreds of open clusters. This fourth contribution from the OCCAM survey presents analysis using Sloan Digital Sky Survey/APOGEE DR16 of a sample of 128 open clusters, 71 of which we designate to be “high quality” based on the appearance of their color–magnitude diagram. We find the APOGEE DR16 derived [Fe/H] abundances to be in good agreement with previous high-resolution spectroscopic open cluster abundance studies. Using the high-quality sample, we measure Galactic abundance gradients in 16 elements, and find evolution of some of the [X/Fe] gradients as a function of age. We find an overall Galactic [Fe/H] versus R {sub GC} gradient of −0.068 ± 0.001 dex kpc{sup −1} over the range of 6 < R {sub GC} < 13.9 kpc; however, we note that this result is sensitive to the distance catalog used, varying as much as 15%. We formally derive the location of a break in the [Fe/H] abundance gradient as a free parameter in the gradient fit for the first time. We also measure significant Galactic gradients in O, Mg, S, Ca, Mn, Cr, Cu, Na, Al, and K, some of which are measured for the first time. Our large sample allows us to examine four well-populated age bins in order to explore the time evolution of gradients for a large number of elements and comment on possible implications for Galactic chemical evolution and radial migration.
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Alterations in the relative abundance of Faecalibacterium prausnitzii correlate with changes in fecal calprotectin in patients with ileal Crohn’s disease: a longitudinal study [Increasing abundance of Faecalibacterium prausnitzii associated with a reduced degree of intestinal inflammation in Crohn’s disease: A longitudinal study]
Objectives: Crohn’s disease is characterized by a gut dysbiosis with decreased abundance of butyrate producers such as Faecalibacterium prausnitzii . Although F. prausnitzii secretes anti-inflammatory molecules, few studies have addressed the importance of F. prausnitzii in a longitudinal setting. We aimed to examine the relationship between temporal profiles of F. prausnitzii , the C. leptum group, overall butyrate production, and inflammatory activity. Material and methods: Fecal samples ( n = 59) were collected every third month from nine patients with ileal Crohn’s disease. The abundance of F. prausnitzii and C. leptum was quantified relative to the total amount of bacteria using quantitative-PCR. To assess butyrate production of gut microbiota, gene copy numbers of the butyryl-CoA:acetate-CoA transferase (BCoAT) gene were quantified by qPCR. The inflammatory activity was defined by fecal (f)-calprotectin. Results: No correlation between the relative abundance of F. prausnitzii , the C. leptum group, or copy numbers of the BCoAT gene, and f-calprotectin was observed in the total sample set. By analyzing alterations between consecutive samples, a negative correlation between changes in the relative abundance of F. prausnitzii and f-calprotectin was observed ( R = 0.39; p = .009). Changes in C. leptum ( R = 0.18, p = .23) and number of copies of the BCoAT gene ( R = 0.12; p = .42) did not correlate with f-calprotectin. Conclusions: There was an inverse correlation between temporal changes in the relative abundance of F. prausnitzii , but not overall butyrate producing capacity, and changes in inflammatory activity in ileal Crohn’s disease. These findings indicate that F. prausnitzii may play a role in gut homeostasis, even though causality is still to be demonstrated.
60 APPLIED LIFE SCIENCES↗
Statistical detection of differentially abundant ions in mass spectrometry-based imaging experiments with complex designs
Mass Spectrometry Imaging (MSI) characterizes changes in chemical composition between regions of biological samples such as tissues. This translates into a statistical goal of class comparison, i.e. determining analytes that change in abundance between conditions more systematically than as expected by random variation. To reach accurate and reproducible conclusions, statistical analysis must appropriately reflect the initial research question, the design of the MSI experiment, and all the associated sources of variation. This manuscript highlights the importance of following these general statistical principles. Using the example of two case studies with complex experimental designs, and with dierent strategies of data acquisition, we demonstrate the extent to which choices made at key points of this workflow impact the results, and provide suggestions for appropriate design and analysis of MSI experiments that aim at detecting dierentially abundant analytes.
NanoDESI, mass spectrometry, MSIQuickView↗
Chemical abundances of Seyfert 2 AGNs – I. Comparing oxygen abundances from distinct methods using SDSS
ABSTRACT We compare the oxygen abundance (O/H) of the narrow-line regions (NLRs) of Seyfert 2 AGNs obtained through strong-line methods and from direct measurements of the electron temperature (Te-method). The aim of this study is to explore the effects of the use of distinct methods on the range of metallicity and on the mass–metallicity relation of active galactic nuclei (AGNs) at low redshifts (z ≲ 0.4). We used the Sloan Digital Sky Survey (SDSS) and NASA/IPAC Extragalactic Database (NED) to selected optical (3000 < λ(Å) < 7000) emission line intensities of 463 confirmed Seyfert 2 AGNs. The oxygen abundances of the NLRs were estimated using the theoretical Storchi-Bergmann et al. calibrations, the semi-empirical N2O2 calibration, the Bayesian H ii-Chi-mistry code and the Te-method. We found that the oxygen abundance estimations via the strong-line methods differ from each other up to ∼0.8 dex, with the largest discrepancies in the low-metallicity regime ($\rm 12+\log (O/H) \: \lesssim \: 8.5$). We confirmed that the Te-method underestimates the oxygen abundance in NLRs, producing unreal subsolar values. We did not find any correlation between the stellar mass of the host galaxies and the metallicity of their AGNs. This result is independent of the method used to estimate Z.
Dors, O. L.↗
Endogenous Dynamic Nuclear Polarization for Natural Abundance 17O and Lithium NMR in the Bulk of Inorganic Solids
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99 GENERAL AND MISCELLANEOUS↗
Median Statistics Analysis of Deuterium Abundance Measurements and Spatial Curvature Constraints
Zavarygin et al. compiled a list of 15 deuterium abundance measurements; two were discarded because the remaining 13 measurements are then consistent with Gaussianity. Here, those authors found that the weighted-mean baryon density (Ω b h 2) determined from the 13 measurements is mildly discrepant (1.6σ) with that determined from the Planck 2015 cosmic microwave background anisotropy data in a flat cosmogony. We find that a median statistic central estimate of Ω b h 2 from all 15 deuterium abundance measurements is a more accurate estimate; is very consistent with Ω b h 2 estimated from Planck 2015 data in a flat cosmogony, but is about 2σ lower than that found in a closed cosmogonical model from the Planck 2015 data.
79 ASTRONOMY AND ASTROPHYSICS↗
The Open Cluster Chemical Abundances and Mapping Survey. V. Chemical Abundances of CTIO/Hydra Clusters Using The Cannon
Open clusters are key chemical and age tracers of Milky Way evolution. While open clusters provide significant constraints on galaxy evolution, their use has been limited due to discrepancies in measuring abundances from different studies. We analyze medium-resolution ( R ~ 19,000) Cerro Tololo Inter-American Observatory/Hydra spectra of giant stars in 58 open clusters using The Cannon to determine [Fe/H], [Mg/Fe], [Si/Fe], [Al/Fe], and [O/Fe]. This work adds an additional 55 primarily southern hemisphere open clusters calibrated to the Sloan Digital Sky Survey/Apache Point Observatory Galactic Evolution Experiment DR16 metallicity system. This uniform analysis is compared to previous studies [Fe/H] measurements for 23 clusters and we present spectroscopic metallicities for the first time for 35 open clusters.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Measuring Long-Range 13 C– 13 C Correlations on a Surface under Natural Abundance Using Dynamic Nuclear Polarization-Enhanced Solid-State Nuclear Magnetic Resonance [Measuring Long Range 13 C– 13 C Correlations on Surface under Natural Abundance Using DNP-enhanced Solid-state NMR]
Here, we report that spatial (<1 nm) proximity between different molecules in solid bulk materials and, for the first time, different moieties on the surface of a catalyst, can be established without isotope enrichment by means of homonuclear CHHC solid-state nuclear magnetic resonance experiment. This 13 C– 13 C correlation measurement, which hitherto was not possible for natural-abundance solids, was enabled by the use of dynamic nuclear polarization. Importantly, it allows the study of long-range correlations in a variety of materials with high resolution.
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