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Structural Investigation of Six Quinary Sulfides Synthesized via the Flux-Assisted Boron-Chalcogen Mixture (BCM) Method: Eu 2+ Containing Members of the RE 3 MTQ 7 (M and T = Transition or Main Group Metals, Q = Chalcogens) Family
For this work, a series of six quinary rare-earth sulfides Ce 4+ 1.85 Eu 2+ 1.15 Na 0.30 SiS 7 , Ce 4+ 1.91 Eu 2+ 1.09 K 0.18 SiS 7 , Ce 4+ 1.96 Eu 2+ 1.04 Rb 0.08 SiS 7 , Ce 4+ 1.98 Eu 2+ 1.02 Cs 0.05 SiS 7 , Ce 4+ 1.97 Eu 2+ 1.03 Ag 0.06 SiS 7 , and Ce 4+ 1.50 Eu 2+ 1.50 CuSiS 7 were obtained in an alkali iodide flux using the boron-chalcogen mixture (BCM) method. Single crystal X-ray diffraction was used to determine the structures of the high quality single crystals that were grown; their elemental compositions were confirmed by energy-dispersive spectroscopy (EDS). The compounds crystallize in the hexagonal crystal system in the noncentrosymmetric space group P63. The crystal structure consists of a three-dimensional network composed of mixed cerium and europium bicapped trigonal prisms, isolated SiS4 tetrahedra, and monovalent metals (Na, K, Rb, Cs, Ag, and Cu) located in cavities created by linked Ce/EuS 8 polyhedra. The structures are charge-balanced when Ce and Eu are in their +4 and +2 oxidation states, respectively. The effective magnetic moment of Ce 1.50 4+ Eu 1.50 2+ CuSiS 7 determined from the temperature dependence of the magnetic susceptibility data is consistent with the presence of Ce 4+ and Eu 2+ . Clear correlations between the alkali ion site occupancy, the ionic radius of the alkali cations, and the average bond length of Ce 4+ /Eu 2+ –S, were established. UV–vis diffuse reflectance data were collected for Ce 1.50 4+ Eu 1.50 2+ CuSiS 7 and a band gap of 1.9(1) eV was established.
Improving the In Vivo Stability of [ 52 Mn]Mn(II) Complexes with 18-Membered Macrocyclic Chelators for PET Imaging
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Uncovering Hidden Members and Functions of the Soil Microbiome Using De Novo Metaproteomics
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Robust evaluation of ENSO in climate models: How many ensemble members are needed?
Large ensembles of model simulations require considerable resources, and thus defining an appropriate ensemble size for a particular application is an important experimental design criterion. We estimate the ensemble size (N) needed to assess a model's ability to capture observed El Niño-Southern Oscillation (ENSO) behavior by utilizing the recently developed International CLIVAR ENSO Metrics Package (Planton et al., 2021). Using the larger ensembles available from CMIP6 and the US CLIVAR Large Ensemble Working Group, we find that larger ensembles are needed to robustly capture baseline ENSO characteristics (N > 50) and physical processes (N > 50) than the background climatology (N ≥ 12) and remote ENSO teleconnections (N ≥ 6). While these results vary somewhat across metrics and models, our study quantifies how larger ensembles are required to robustly evaluate simulated ENSO behavior, thereby providing some guidance for the design of model ensembles.
Cryo-EM reveals a composite flavobicluster electron bifurcation site in the Bfu family member NfnABC
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18-membered macrocycle appended on resin for selective rare earth element extraction and separation
The rare earth elements are critically important for a wide range of modern technologies. However, obtaining them selectively and efficiently from natural sources and recycled materials is challenging and often requires harsh or wasteful conditions. Here we show that a macrocyclic chelator appended to a solid resin can overcome this challenge by acting as a robust platform for both the extraction and separation of these elements. This resin preferably captures the large rare earth elements in mixtures of these ions, giving rise to higher extraction efficiencies for them over the smaller ions. We further demonstrate that this resin can be used to separate rare earth elements. As a proof-of-principle validation, this resin was demonstrated to selectively extract rare earth elements in the presence of many different types of competing metal ions in a bioleachate solution obtained from autoslag waste, leading to their enrichment.
Five vs. six membered-ring PAH products from reaction of o -methylphenyl radical and two C 3 H 4 isomers
Gas-phase o -methylphenyl reactions with propyne and allene form PAHs: with preferences for either six–six or five–six bicyclic products.
A comparison of hydrogen release kinetics from 5- and 6-membered 1,2-BN-cycloalkanes
The reaction order and Arrhenius activation parameters for spontaneous hydrogen release from cyclic amine boranes, i.e. , BN-cycloalkanes, were determined for 1,2-BN-cyclohexane (1) and 3-methyl-1,2-BN-cyclopentane (2) in tetraglyme.
Tetravalent biepitopic targeting enables intrinsic antibody agonism of tumor necrosis factor receptor superfamily members
Abstract not provided
Phyllosphere exudates select for distinct microbiome members in sorghum epicuticular wax and aerial root mucilage
Phyllosphere exudates create specialized microhabitats that shape microbial community diversity. We explored the microbiome associated with two sorghum phyllosphere exudates, the epicuticular wax and aerial root mucilage. We assessed the microbiome associated with the wax from sorghum plants over two growth stages, and the root mucilage additionally from nitrogen-fertilized and non-fertilized plants. In parallel, we isolated and characterized hundreds of bacteria from wax and mucilage, and integrated data from cultivation-independent and cultivation-dependent approaches to gain insights into exudate diversity and bacterial phenotypes. We found that Sphingomonadaceae and Rhizobiaceae families were the major taxa in the wax regardless of water availability and plant developmental stage to plants. The cultivation-independent mucilage-associated bacterial microbiome contained Erwiniaceae, Flavobacteriaceae, Rhizobiaceae, Pseudomonadaceae, Sphingomonadaceae, and its structure was strongly influenced by sorghum development but only modestly influenced by fertilization. In contrast, the fungal community structure of mucilage was strongly affected by the year of sampling but not by fertilization or plant developmental stage, suggesting a decoupling of fungal-bacterial dynamics in the mucilage. Our bacterial isolate collection from wax and mucilage had several isolates that matched 100% to detected amplicon sequence variants, and were enriched on media that selected for phenotypes including phosphate solubilization, putative diazotrophy, resistance to desiccation, capability to grow on methanol as a carbon source, and ability to grow in the presence of linalool and β-caryophyllene (terpenes in sorghum wax). This work expands our understanding of the microbiome of phyllosphere exudates and supports our long-term goal to translate microbiome research to support sorghum cultivation.
Patulin Inhibition of Specific Apple Microbiome Members Uncovers Hanseniaspora uvarum as a Potential Biocontrol Agent
Penicillium expansum is a major postharvest pathogen of apples, causing loss in fruits through tissue damage, as well as in apple products due to contamination with the mycotoxin patulin. During infections, patulin is a cultivar-dependent virulence factor that facilitates apple lesion development. Patulin also has characterized antimicrobial activity and is important for inhibiting other competitive phytopathogens, but the role of this inhibitory activity has not been investigated in the context of the apple microbiome. Here, in our current study, we isolated 68 apple microbiota and characterized their susceptibility to P. expansum extracts. We found gram-negative bacteria and basidiomycete yeast to demonstrate largely patulin-specific growth inhibition compared with gram-positive and ascomycete isolates. From co-cultures, we identified a Hanseniaspora and Gluconobacter pairing that reduced P. expansum biomass and found that H. uvarum alone is sufficient to reduce apple disease progression in vivo. We investigated possible mechanisms of H. uvarum biocontrol activity and found modest inhibition on apple puree plates, as well as a trend toward lower patulin levels at the wound site. Active biocontrol activity required live yeast, which was also effective in controlling Botrytis cinerea apple infections. Lastly, we explored the breadth of H. uvarum biocontrol activity with over 30 H. uvarum isolates and found consistent inhibition of P. expansum apple disease.
Evolution of nontrivial Fermi surface features in the band structures of the homologous members Pb 5 Bi 6 Se 14 and Pb 5 Bi 12 Se 23
High-quality single crystals of (PbSe) 5 (Bi 2 Se 3 ) 3m were grown and analyzed by nuclear magnetic resonance (NMR) spectroscopy. We report on 77 Se and 207 Pb NMR shifts and nuclear spin-lattice relaxation measurements in the naturally formed heterostructure homology (PbSe) 5 (Bi 2 Se 3 ) 3m with m = 1 (Pb 5 Bi 6 Se 14 ) and m = 2 (Pb 5 Bi 12 Se 23 ). A distinct site-specific contribution has been detected for both nuclei as a function of temperature, which reveals an electronic changeover from a semiconducting (Pb 5 Bi 6 Se 14 ) to a semimetalliclike (Pb 5 Bi 12 Se 23 ) system with nontrivial band structure features near the Fermi level. The temperature dependences of the relaxation rates are dominated by significant changes in the topology of energy dispersions accompanied with band edges and crossings in the region of the Fermi surface. These results, which interrogate nuclear spin interactions from selected atomic sites, clearly expose the effects of the added Bi 2 Se 3 layer on the crystal and electronic structure of (Pb 5 Bi 12 Se 23 ). These findings provide direct microscopic insight into the unconventional and dual nature of the electronic structure of these homologous thermoelectric and topologically nontrivial compounds.
Al 2 MnCu : A magnetically ordered member of the Heusler alloy family despite having a valence electron count of 24
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Complete genome sequence of Luteolibacter sp. strain Populi, a member of phylum Verrucomicrobiota isolated from the Populus trichocarpa rhizosphere
Luteolibacter sp. strain Populi is a bacterium from the phylum Verrucomicrobiota, isolated from the rhizosphere of a black cottonwood tree, Populus trichocarpa, from the Cascade mountains in Washington. Its 6.6-Mb chromosome was completely sequenced using Oxford Nanopore long-read sequencing and is predicted to encode 5,301 proteins and 60 RNAs.
Bobfinchite, Na[(UO2)8O3(OH)11]·10H2O, a new Na-bearing member of the schoepite family
Abstract The new mineral bobfinchite (IMA2020-082), Na[(UO2)8O3(OH)11]·10H2O, was found in the Burro mine, Slick Rock district, San Miguel County, Colorado, U.S.A., where it occurs as an oxidation product of uraninite on asphaltite matrix in intimate association with gypsum, natrozippeite, metaschoepite, and uranopilite. Bobfinchite crystals are transparent to translucent, yellow, lozenge-shaped disks up to 0.3 mm wide. Crystals are flattened on [100] and exhibit the forms {100}, {011}, {021}, {021}, and {011}. Bobfinchite has a pale-yellow streak and emits very dim yellow fluorescence under 365 nm ultraviolet illumination. The crystals are brittle with very good {100} cleavage and irregular, stepped fracture. The Mohs hardness is ca. 2 based on scratch tests. The calculated density is 5.044 g/cm3 based on the empirical formula and 5.036 g/cm3 for the ideal formula. Bobfinchite is optically biaxial (–), with α = 1.690(5), β = 1.7205(5), and γ = 1.730(5) (white light). The measured 2V, estimated from the interference figure, is 55(5)° and the calculated value is 59.1°. Dispersion is moderate, r > v; orientation: X = a, Y = b, Z = c; pleochroism: X nearly colorless, Y yellow, Z yellow; X < Y ≈Z. Electron microprobe analysis provided the empirical formula (Na0.99Pb0.02)[(UO2)7.99O3(OH)11]·10H2O. The five strongest X-ray powder diffraction lines are [dobs in Å(I)(hkl)]: 7.34(100)(200), 3.59(50)(024), 3.23(60)(224), 3.18(36)(240), and 2.01(23)(624,551,208,640,346). Bobfinchite is orthorhombic, Pbcn, a = 14.6249(9), b = 14.0389(10), c = 16.6923(10) Å, V = 3427.2(4) Å3, and Z = 4. The structure of bobfinchite (R1 = 0.0330 for 3770 I > 4σI) is built from uranyl oxide-hydroxide sheets that adopt the fourmarierite topology, with interlayer Na+ and H2O groups. Both the sheet and interlayer topology mimic those observed in natural and synthetic Na-metaschoepites studied previously, and as seen in other uranyl oxide hydrate minerals, charge balance is achieved at specific sites in the sheet through the substitution O2– ↔ (OH)–.