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Abstract
Compression of small molecules can induce solid-state reactions that are difficult or impossible under conventional, solution-phase conditions. Of particular interest is the topochemical-like reaction of arenes to produce polymeric nanomaterials. However, high reaction onset pressures and poor selectivity remain significant challenges. Herein, the incorporation of electron-withdrawing and -donating groups into pi-stacked arenes is proposed as a strategy to reduce reaction barriers to cycloaddition and onset pressures. Nevertheless, competing side-chain reactions between functional groups represent alternative viable pathways. For the case of a diaminobenzene:tetracyanobenzene cocrystal, amidine formation between amine and cyano groups occurs prior to cycloaddition with an onset pressure near 9 GPa, as determined using vibrational spectroscopy, X-ray diffraction, and first-principles calculations. This work demonstrates that reduced-barrier cycloaddition reactions are theoretically possible via strategic functionalization; however, the incorporation of pendant groups may enable alternative reaction pathways. Controlled reactions between pendant groups represent an additional strategy for producing unique polymeric nanomaterials.
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Abstract
Microbial heterotrophs (‘picoheterotrophs’) drive global carbon cycling, but how to quantitatively organize their functional complexity remains unclear. Here, we generate a global -scale, mechanistic understanding of marine picoheterotrophic functional biogeography with a novel model -data synthesis. We build picoheterotrophic diversity into a trait -based marine ecosystem model along two axes: substrate lability and optimization for growth rate (copiotrophy) vs. substrate affinity (oligotrophy). Using genetic sequences along an Alaska -to -Antarctica Pacific Ocean transect, we compile 21 picoheterotrophic guilds and estimate their degree of copiotrophy. Data and model agreement suggests that gradients in predation and substrate lability predominantly set biogeographical patterns, and identifies ‘slow copiotrophs’ subsisting at depth. Results demonstrate the predictability of the marine microbiome and connect ecological dynamics with carbon storage, crucial for projecting changes in a warming ocean.
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Abstract
Accurate and precise measurements of spectroradiometric temperature are crucial for many high pressure experiments that use diamond anvil cells or shock waves. In experiments with sub-millisecond timescales, specialized detectors such as streak cameras or photomultiplier tubes are required to measure temperature. High accuracy and precision are difficult to attain, especially at temperatures below 3000K. Here, we present a new spectroradiometry system based on multianode photomultiplier tube technology and passive readout circuitry that yields a 0.24 s rise-time for each channel. Temperature is measured using five color spectroradiometry. During high pressure pulsed Joule heating experiments in a diamond anvil cell, we document measurement precision to be ±30 K at temperatures as low as 2000K during single-shot heating experiments with 0.6 s time-resolution. Ambient pressure melting tests using pulsed Joule heating indicate that the accuracy is ±80 K in the temperature range 1800-2700K.
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Abstract
By directly altering microscopic interactions, pressure provides a powerful tuning knob for the exploration of condensed phases and geophysical phenomena1. The megabar regime represents an interesting frontier, in which recent discoveries include high-temperature superconductors, as well as structural and valence phase transitions2-6. However, at such high pressures, many conventional measurement techniques fail. Here we demonstrate the ability to perform local magnetometry inside a diamond anvil cell with sub-micron spatial resolution at megabar pressures. Our approach uses a shallow layer of nitrogen-vacancy colour centres implanted directly within the anvil7-9; crucially, we choose a crystal cut compatible with the intrinsic symmetries of the nitrogen-vacancy centre to enable functionality at megabar pressures. We apply our technique to characterize a recently discovered hydride superconductor, CeH9 (ref.10). By performing simultaneous magnetometry and electrical transport measurements, we observe the dual signatures of superconductivity: diamagnetism characteristic of the Meissner effect and a sharp drop of the resistance to near zero. By locally mapping both the diamagnetic response and flux trapping, we directly image the geometry of superconducting regions, showing marked inhomogeneities at the micron scale. Our work brings quantum sensing to the megabar frontier and enables the closed-loop optimization of superhydride materials synthesis.
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February 28, 2024
Feature Story

Carnegie celebrates the legacy of Black astronauts

Abstract
Highly potent animal stem cells either self renew or launch complex differentiation programs, using mechanisms that are only partly understood. Drosophila female germline stem cells (GSCs) perpetuate without change over evolutionary time and generate cystoblast daughters that develop into nurse cells and oocytes. Cystoblasts initiate differentiation by generating a transient syncytial state, the germline cyst, and by increasing pericentromeric H3K9me3 modification, actions likely to suppress transposable element activity. Relatively open GSC chromatin is further restricted by Polycomb repression of testis or somatic cell-expressed genes briefly active in early female germ cells. Subsequently, Neijre/CBP and Myc help upregulate growth and reprogram GSC metabolism by altering mitochondrial transmembrane transport, gluconeogenesis, and other processes. In all these respects GSC differentiation resembles development of the totipotent zygote. We propose that the totipotent stem cell state was shaped by the need to resist transposon activity over evolutionary timescales.
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Abstract
Studies of material returned from Cb asteroid Ryugu have revealed considerable mineralogical and chemical heterogeneity, stemming primarily from brecciation and aqueous alteration. Isotopic anomalies could have also been affected by delivery of exogenous clasts and aqueous mobilization of soluble elements. Here, we show that isotopic anomalies for mildly soluble Cr are highly variable in Ryugu and CI chondrites, whereas those of Ti are relatively uniform. This variation in Cr isotope ratios is most likely due to physicochemical fractionation between Cr-54-rich presolar nanoparticles and Cr-bearing secondary minerals at the millimeter-scale in the bulk samples, likely due to extensive aqueous alteration in their parent bodies that occurred 5.2(-1.4)(+1.8 )Ma after Solar System birth. In contrast, Ti isotopes were marginally affected by this process. Our results show that isotopic heterogeneities in asteroids are not all nebular or accretionary in nature but can also reflect element redistribution by water.
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