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1. Noncentrosymmetric Triangular Magnet CaMnTeO 6 : Strong Quantum Fluctuations and Role of s 0 versus s 2 Electronic States in Competing Exchange Interactions

   https://doi.org/10.1002/adma.202313763  

   Huai, Xudong ; Acheampong, Emmanuel ; Delles, Erich ; Winiarski, Michał J. ; Sorolla, II, Maurice ; Nassar, Lila ; Liang, Mingli ; Ramette, Caleb ; Ji, Huiwen ; Scheie, Allen ; et al ( March 2024 , Advanced Materials)

   Noncentrosymmetric triangular magnets offer a unique platform for realizing strong quantum fluctuations. However, designing these quantum materials remains an open challenge attributable to a knowledge gap in the tunability of competing exchange interactions at the atomic level. Here, a new noncentrosymmetric triangularS = 3/2 magnet CaMnTeO₆is created based on careful chemical and physical considerations. The model material displays competing magnetic interactions and features nonlinear optical responses with the capability of generating coherent photons. The incommensurate magnetic ground state of CaMnTeO₆with an unusually large spin rotation angle of 127°(1) indicates that the anisotropic interlayer exchange is strong and competing with the isotropic interlayer Heisenberg interaction. The moment of 1.39(1) µB, extracted from low‐temperature heat capacity and neutron diffraction measurements, is only 46% of the expected value of the static moment 3 µB. This reduction indicates the presence of strong quantum fluctuations in the half‐integer spinS = 3/2 CaMnTeO₆magnet, which is rare. By comparing the spin‐polarized band structure, chemical bonding, and physical properties of AMnTeO₆(A = Ca, Sr, Pb), how quantum‐chemical interpretation can illuminate insights into the fundamentals of magnetic exchange interactions, providing a powerful tool for modulating spin dynamics with atomically precise control is demonstrated.

    

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2. Interaction of Pb 2+ ions in water with two-dimensional molybdenum disulfide

   https://doi.org/10.1088/2515-7639/ab7ab3  

   Li, Duo O. ; Gilliam, Matthew S. ; Debnath, Abhishek ; Chu, Ximo S. ; Yousaf, Ahmed ; Green, Alexander A. ; Wang, Qing Hua ( March 2020 , Journal of Physics: Materials)

   The removal of heavy metal contaminants from water is important for public health, and recently many two-dimensional (2D) materials with high specific surface areas are being studied as promising new active components in water purification. In particular, 2D MoS₂nanosheets have been used for the removal of various heavy metals, but usually in either in complex geometries and composites, or in the chemically exfoliated metallic 1T-MoS₂phase. However, the interaction of heavy metals dissolved in water with unmodified semiconducting 2H-MoS₂is not well studied. In this paper, we report a detailed fundamental investigation of how Pb²⁺ions interact with 2H-MoS₂. We observe small solid clusters that form on the MoS₂surfaces after exposing them to Pb(NO₃)₂aqueous solutions as shown by atomic force microscopy and transmission electron microscopy, and for liquid phase exfoliated MoS₂we observe the nanosheets precipitating out of dispersion along with insoluble solid granules. We use a combination of x-ray photoelectron spectroscopy and x-ray diffraction to identify these solid clusters and granules as primarily PbSO₄with some PbMoO₄. We put forth an interaction mechanism that involves MoS₂defects acting as initiation sites for the partial dissolution in aqueous oxygenated conditions which produces MoO₄²⁻and SO₄²⁻ions to form the solids with Pb²⁺. These results are an important contribution to our fundamental understanding of how MoS₂interacts with metal ions and will influence further efforts to exploit MoS₂for water remediation applications.

    

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3. The role of Ca 2+ and protein scaffolding in the formation of nature’s water oxidizing complex

   https://doi.org/10.1073/pnas.2011315117  

   Avramov, Anton P. ; Hwang, Hong J. ; Burnap, Robert L. ( November 2020 , Proceedings of the National Academy of Sciences)

   null (Ed.)

   Photosynthetic O 2 evolution is catalyzed by the Mn 4 CaO 5 cluster of the water oxidation complex of the photosystem II (PSII) complex. The photooxidative self-assembly of the Mn 4 CaO 5 cluster, termed photoactivation, utilizes the same highly oxidizing species that drive the water oxidation in order to drive the incorporation of Mn 2+ into the high-valence Mn 4 CaO 5 cluster. This multistep process proceeds with low quantum efficiency, involves a molecular rearrangement between light-activated steps, and is prone to photoinactivation and misassembly. A sensitive polarographic technique was used to track the assembly process under flash illumination as a function of the constituent Mn 2+ and Ca 2+ ions in genetically engineered membranes of the cyanobacterium Synechocystis sp. PCC6803 to elucidate the action of Ca 2+ and peripheral proteins. We show that the protein scaffolding organizing this process is allosterically modulated by the assembly protein Psb27, which together with Ca 2+ stabilizes the intermediates of photoactivation, a feature especially evident at long intervals between photoactivating flashes. The results indicate three critical metal-binding sites: two Mn and one Ca, with occupation of the Ca site by Ca 2+ critical for the suppression of photoinactivation. The long-observed competition between Mn 2+ and Ca 2+ occurs at the second Mn site, and its occupation by competing Ca 2+ slows the rearrangement. The relatively low overall quantum efficiency of photoactivation is explained by the requirement of correct occupancy of these metal-binding sites coupled to a slow restructuring of the protein ligation environment, which are jointly necessary for the photooxidative trapping of the first stable assembly intermediate. 

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4. Plant community and climatic response to mid-Miocene environmental change in the Pacific Northwest (USA) within a refined temporal framework

   https://doi.org/10.1130/abs/2021AM-367337  

   Lowe, A.J. ; Strömberg, C.A.E ; Schmitz, M. ; Dillhoff, T. ; Dillhoff, R. ; Rember, W. ( October 2021 , Geological Society of America Abstracts with Programs)

   The US Pacific Northwest (PNW), including Washington, Oregon, and Idaho, hosts an extensive suite of Oligocene–Miocene fossil plant sites that have the potential to showcase terrestrial vegetation and climate response to several pronounced environmental perturbations. These include the Mid-Miocene Climatic Optimum (MMCO; ca. 17-14 Ma), the Middle Miocene Climatic Transition (MMCT; ca. 14-13 Ma), and the eruption of the Columbia River Basalts (~95% of its volume 16.7 to 15.9 Ma). This collaborative study focuses on 18 PNW fossil plant sites spanning ca. 32 to 10 Ma, many of which have extensive pre-existing macrofossil collections. First, we radiometrically date interbedded tuffs at these sites to establish a high-resolution temporal framework, using U-Pb/CA-ID-TIMS. We present new dates for the Clarkia/Emerald Creek, Alvord Creek, Juliaetta, Pickett Creek, Whitebird, and Trout Creek fossil sites. Within this temporal framework, we are: 1) documenting regional climate change in the PNW during the MMCO and MMCT using paleobotany-based paleoclimate proxies, and 2) providing an integrated perspective on the response of plant communities to these mid-Miocene environmental changes by combining macrofossil, palynomorph, and phytolith evidence. Taken together, these data will provide a regionally-comprehensive perspective on the sensitivity of terrestrial vegetation and climate to global climatic events known more extensively from marine records. 

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5. U-Pb zircon geochronology of dropstones and IRD in the Amundsen Sea, applied to the question of bedrock provenance and Miocene-Pliocene ice sheet extent in West Antarctica

   Siddoway, C. ; Thomson, S. ; Hemming, S. ; Buchband, H. ; Furlong, H. ; Hilderman, R. ; Robinson, D. ; Watkins, C. ; Cox, S. ; Licht, K. ; et al ( April 2021 , EGU General Assembly 2021)

   IODP Expedition 379 to the Amundsen Sea continental rise recovered latest Miocene-Holocene sediments from two sites on a drift in water depths >3900m. Sediments are dominated by clay and silty clay with coarser-grained intervals and ice-rafted detritus (IRD) (Gohl et al. 2021, doi:10.14379/iodp.proc.379.2021). Cobble-sized dropstones appear as fall-in, in cores recovered from sediments >5.3 Ma. We consider that abundant IRD and the sparse dropstones melted out of icebergs formed due to Antarctic ice-sheet calving events. We are using petrological and age characteristics of the clasts from the Exp379 sites to fingerprint their bedrock provenance. The results may aid in reconstruction of past changes in icesheet extent and extend knowledge of subglacial bedrock. Mapped onshore geology shows pronounced distinctions in bedrock age between tectonic provinces of West or East Antarctica (e.g. Cox et al. 2020, doi:10.21420/7SH7-6K05; Jordan et al. 2020, doi.org/10.1038/s43017-019-0013-6). This allows us to use geochronology and thermochronology of rock clasts and minerals for tracing their provenance, and ascertain whether IRD deposited at IODP379 drillsites originated from proximal or distal Antarctic sources. We here report zircon and apatite U-Pb dates from four sand samples and five dropstones taken from latest Miocene, early Pliocene, and Plio-Pleistocene-boundary sediments. Additional Hf isotope data, and apatite fission track and 40Ar/39Ar Kfeldspar ages for some of the same samples help to strengthen provenance interpretations. The study revealed three distinct zircon age populations at ca. 100, 175, and 250 Ma. Using Kolmogorov-Smirnov (K-S) statistical tests to compare our new igneous and detrital zircon (DZ) U-Pb results with previously published data, we found strong similarities to West Antarctic bedrock, but low correspondence to prospective sources in East Antarctica, implying a role for icebergs calved from the West Antarctic Ice Sheet (WAIS). The ~100 Ma age resembles plutonic ages from Marie Byrd Land and islands in Pine Island Bay. The ~250 and 175 Ma populations match published mineral dates from shelf sediments in the eastern Amundsen Sea Embayment as well as granite ages from the Antarctic Peninsula and the Ellsworth-Whitmore Mountains (EWM). The different derivation of coarse sediment sources requires changes in iceberg origin through the latest Miocene, early Pliocene, and Plio/Pleistocene, likely the result of changes in WAIS extent. One unique dropstone recovered from Exp379 Site U1533B is green quartz arenite, which yielded mostly 500-625 Ma detrital zircons. In visual appearance and dominant U-Pb age population, it resembles a sandstone dropstone recovered from Exp382 Site U1536 in the Scotia Sea (Hemming et al. 2020, https://gsa.confex.com/gsa/2020AM/meetingapp.cgi/Paper/357276). K-S tests yield high values (P ≥ 0.6), suggesting a common provenance for both dropstones recovered from late Miocene to Pliocene sediments, despite the 3270 km distance separating the sites. Comparisons to published data, in progress, narrow the group of potential on-land sources to exposures in the EWM or isolated ranges at far south latitudes in the Antarctic interior. If both dropstones originated from the same source area, they could signify dramatic shifts in the WAIS grounding line position, and the possibility of the periodic opening of a seaway connecting the Amundsen and Weddell Seas. https://meetingorganizer.copernicus.org/EGU21/EGU21-9151.html 

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