Abstract
We use the second data releases of the European Space AgencyGaia astrometric survey and the high-resolution Galactic Archaeology with HERMES (GALAH) spectroscopic survey to analyse the ...structure of our Galaxy’s disc components. With GALAH, we separate the α-rich and α-poor discs (with respect to Fe), which are superposed in both position and velocity space, and examine their distributions in action space. We study the distribution of stars in the zV$\mathrm{ z}$ phase plane, for both Vϕ and VR, and recover the remarkable ‘phase spiral’ discovered by Gaia. We identify the anticipated quadrupole signature in zV$\mathrm{ z}$ of a tilted velocity ellipsoid for stars above and below the Galactic plane. By connecting our work with earlier studies, we show that the phase spiral is likely to extend well beyond the narrow solar neighbourhood cylinder in which it was found. The phase spiral is a signature of corrugated waves that propagate through the disc, and the associated non-equilibrium phase mixing. The radially asymmetric distribution of stars involved in the phase spiral reveals that the corrugation, which is mostly confined to the α-poor disc, grows in z-amplitude with increasing radius. We present new simulations of tidal disturbance of the Galactic disc by the Sagittarius (Sgr) dwarf. The effect on the zV$\mathrm{ z}$ phase plane lasts ${\gtrsim } 2\, \mathrm{Gyr}$, but a subsequent disc crossing wipes out the coherent structure. We find that the phase spiral was excited ${\lesssim } 0.5\, \mathrm{Gyr}$ ago by an object like Sgr with total mass ∼3 × 1010 M⊙ (stripped down from ∼5 × 1010 M⊙ when it first entered the halo) passing through the plane.
ABSTRACT
We report the discovery of the only very nitrogen-enhanced metal-poor star known in a Galactic globular cluster. This star, in the very metal-poor cluster ESO280−SC06 , has ...$\textrm{N}/\textrm{Fe}\, \gt +2.5$, while the other stars in the cluster show no obvious enhancement in nitrogen. Around 80 NEMP stars are known in the field, and their abundance patterns are believed to reflect mass transfer from a binary companion in the asymptotic giant branch phase. The dense environment of globular clusters is detrimental to the long term survival of binary systems, resulting in a low observed binary fraction among red giants and the near absence of NEMP stars. We also identify the first known horizontal branch members of ESO280−SC06 , which allow for a much better constraint on its distance. We calculate an updated orbit for the cluster based on our revised distance of 20.6 ± 0.5 kpc, and find no significant change to its orbital properties.
Alkyldiamine-functionalized variants of the metal–organic framework Mg2(dobpdc) (dobpdc4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) are promising for CO2 capture applications owing to their unique ...step-shaped CO2 adsorption profiles resulting from the cooperative formation of ammonium carbamate chains. Primary,secondary (1°,2°) alkylethylenediamine-appended variants are of particular interest because of their low CO2 step pressures (≤1 mbar at 40 °C), minimal adsorption/desorption hysteresis, and high thermal stability. Herein, we demonstrate that further increasing the size of the alkyl group on the secondary amine affords enhanced stability against diamine volatilization, but also leads to surprising two-step CO2 adsorption/desorption profiles. This two-step behavior likely results from steric interactions between ammonium carbamate chains induced by the asymmetrical hexagonal pores of Mg2(dobpdc) and leads to decreased CO2 working capacities and increased water co-adsorption under humid conditions. To minimize these unfavorable steric interactions, we targeted diamine-appended variants of the isoreticularly expanded framework Mg2(dotpdc) (dotpdc4− = 4,4′′-dioxido-1,1′:4′,1′′-terphenyl-3,3′′-dicarboxylate), reported here for the first time, and the previously reported isomeric framework Mg-IRMOF-74-II or Mg2(pc-dobpdc) (pc-dobpdc4− = 3,3′-dioxidobiphenyl-4,4′-dicarboxylate, pc = para-carboxylate), which, in contrast to Mg2(dobpdc), possesses uniformally hexagonal pores. By minimizing the steric interactions between ammonium carbamate chains, these frameworks enable a single CO2 adsorption/desorption step in all cases, as well as decreased water co-adsorption and increased stability to diamine loss. Functionalization of Mg2(pc-dobpdc) with large diamines such as N-(n-heptyl)ethylenediamine results in optimal adsorption behavior, highlighting the advantage of tuning both the pore shape and the diamine size for the development of new adsorbents for carbon capture applications.
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IJS, KILJ, NUK, UL, UM, UPUK
Electron microscopy (EM) is the standard method for imaging cellular structures with nanometer resolution, but existing genetic tags are inactive in most cellular compartments or require light and ...can be difficult to use. Here we report the development of 'APEX', a genetically encodable EM tag that is active in all cellular compartments and does not require light. APEX is a monomeric 28-kDa peroxidase that withstands strong EM fixation to give excellent ultrastructural preservation. We demonstrate the utility of APEX for high-resolution EM imaging of a variety of mammalian organelles and specific proteins using a simple and robust labeling procedure. We also fused APEX to the N or C terminus of the mitochondrial calcium uniporter (MCU), a recently identified channel whose topology is disputed. These fusions give EM contrast exclusively in the mitochondrial matrix, suggesting that both the N and C termini of MCU face the matrix. Because APEX staining is not dependent on light activation, APEX should make EM imaging of any cellular protein straightforward, regardless of the size or thickness of the specimen.
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DOBA, IJS, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Metal-organic frameworks are promising materials for energy-efficient gas separations, but little is known about the diffusion of adsorbates in materials featuring one-dimensional porosity at the ...nanoscale. An understanding of the interplay between framework structure and gas diffusion is crucial for the practical application of these materials as adsorbents or in mixed-matrix membranes, since the rate of gas diffusion within the adsorbent pores impacts the required size (and therefore cost) of the adsorbent column or membrane. Here, we investigate the diffusion of CO
within the pores of Zn
(dobpdc) (dobpdc
= 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) using pulsed field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy and molecular dynamics (MD) simulations. The residual chemical shift anisotropy for pore-confined CO
allows PFG NMR measurements of self-diffusion in different crystallographic directions, and our analysis of the entire NMR line shape as a function of the applied field gradient provides a precise determination of the self-diffusion coefficients. In addition to observing CO
diffusion through the channels parallel to the crystallographic c axis (self-diffusion coefficient D
= (5.8 ± 0.1) × 10
m
s
at a pressure of 625 mbar CO
), we unexpectedly find that CO
is also able to diffuse between the hexagonal channels in the crystallographic ab plane (D
= (1.9 ± 0.2) × 10
m
s
), despite the walls of these channels appearing impermeable by single-crystal X-ray crystallography and flexible lattice MD simulations. Observation of such unexpected diffusion in the ab plane suggests the presence of defects that enable effective multidimensional CO
transport in a metal-organic framework with nominally one-dimensional porosity.
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Enzyme–mediator systems generate radical intermediates that abstract hydrogen atoms under mild conditions. These systems have been employed extensively for alcohol oxidation, primarily in biomass ...degradation, but they are underexplored for direct activation of C(sp3)–H bonds in alkyl groups. Here, we combine horseradish peroxidase (HRP), H2O2, and redox mediator N-hydroxyphthalimide (NHPI) for C(sp3)–H functionalization of alkylbenzene-type substrates. The HRP–NHPI system is >10-fold more active than existing enzyme–mediator systems in converting alkylbenzenes to ketones and aldehydes under air, and it operates from 0–50 °C and in numerous aqueous–organic solvent mixtures. The benzylic substrate radical can be trapped through a reaction with NHPI, demonstrating the formation of benzylic products beyond ketones. Furthermore, we demonstrate a one-pot, two-step enzymatic cascade for converting alkylbenzenes to benzylic amines. Overall, the HRP–NHPI system enables the selective benzylic C–H functionalization of diverse substrates under mild conditions using a straightforward procedure.
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Context. The Orion complex is arguably the most studied star-forming region in the Galaxy. While stars are still being born in the Orion nebula, the oldest part was believed to be no more than 13 Myr ...old. Aims. In order to study the full hierarchy of star formation across the Orion complex, we perform a clustering analysis of the Ori OB1a region using new stellar surveys and derive robust ages for each identified stellar aggregate. Methods. We use Gaia DR2 parameters supplemented with radial velocities from the GALAH and APOGEE surveys to perform clustering of the Ori OB1a association. Five overdensities are resolved in a six-dimensional parameter space (positions, distance, proper motions, and radial velocity). Most correspond to previously known structures (ASCC 16, 25 Orionis, ASCC 20, ASCC 21). We use Gaia DR2, Pan-STARRS1 and 2MASS photometry to fit isochrones to the colour-magnitude diagrams of the identified clusters. The ages of the clusters can thus be measured with ∼10% precision. Results. While four of the clusters have ages between 11 and 13 Myr, the ASCC 20 cluster stands out at an age of 21 ± 3 Myr. This is significantly greater than the age of any previously known component of the Orion complex. To some degree, all clusters overlap in at least one of the six phase-space dimensions. Conclusions. We argue that the formation history of the Orion complex, and its relation to the Gould belt, must be reconsidered. A significant challenge in reconstructing the history of the Ori OB1a association is to understand the impact of the newly discovered 21 Myr old population on the younger parts of the complex, including their formation.
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ABSTRACT
Since the advent of Gaia astrometry, it is possible to identify massive accreted systems within the Galaxy through their unique dynamical signatures. One such system, Gaia-Sausage-Enceladus ...(GSE), appears to be an early ‘building block’ given its virial mass $\gt 10^{10}\, \mathrm{M_\odot }$ at infall (z ∼ 1−3). In order to separate the progenitor population from the background stars, we investigate its chemical properties with up to 30 element abundances from the GALAH+ Survey Data Release 3 (DR3). To inform our choice of elements for purely chemically selecting accreted stars, we analyse 4164 stars with low-α abundances and halo kinematics. These are most different to the Milky Way stars for abundances of Mg, Si, Na, Al, Mn, Fe, Ni, and Cu. Based on the significance of abundance differences and detection rates, we apply Gaussian mixture models to various element abundance combinations. We find the most populated and least contaminated component, which we confirm to represent GSE, contains 1049 stars selected via Na/Fe versus Mg/Mn in GALAH+ DR3. We provide tables of our selections and report the chrono-chemodynamical properties (age, chemistry, and dynamics). Through a previously reported clean dynamical selection of GSE stars, including $30 \lt \sqrt{J_R / \, \mathrm{kpc\, km\, s^{-1}}} \lt 55$, we can characterize an unprecedented 24 abundances of this structure with GALAH+ DR3. With our chemical selection we characterize the dynamical properties of the GSE, for example mean $\sqrt{J_R / \, \mathrm{kpc\, km\, s^{-1}}} =$$26_{-14}^{+9}$. We find only $(29\pm 1){{\ \rm per\ cent}}$ of the GSE stars within the clean dynamical selection region. Our methodology will improve future studies of accreted structures and their importance for the formation of the Milky Way.
DNA-Scaffolded Synergistic Catalysis Pimentel, Edward B; Peters-Clarke, Trenton M; Coon, Joshua J ...
Journal of the American Chemical Society,
12/2021, Volume:
143, Issue:
50
Journal Article
Peer reviewed
Open access
We report DNA-scaffolded synergistic catalysis, a concept that combines the diverse reaction scope of synergistic catalysis with the ability of DNA to precisely preorganize abiotic groups and undergo ...stimuli-triggered conformational changes. As an initial demonstration of this concept, we focus on Cu-TEMPO-catalyzed aerobic alcohol oxidation, using DNA as a scaffold to hold a copper cocatalyst and an organic radical cocatalyst (TEMPO) in proximity. The DNA-scaffolded catalyst maintained a high turnover number upon dilution and exhibited 190-fold improvement in catalyst turnover number relative to the unscaffolded cocatalysts. By incorporating the cocatalysts into a DNA hairpin-containing scaffold, we demonstrate that the rate of the synergistic catalytic reaction can be controlled through a reversible DNA conformational change that alters the distance between the cocatalysts. This work demonstrates the compatibility of synergistic catalytic reactions with DNA scaffolding, opening future avenues in reaction discovery, sensing, responsive materials, and chemical biology.
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Polymerization catalysts that activate in response to specific chemical triggers offer spatial and temporal control over polymer synthesis, facilitating the development of responsive materials and ...custom polymer coatings. However, existing catalysts switch their activity through mechanisms that are not generalizable to chemically diverse stimuli. To approach the level of control exhibited in biological polymer synthesis, switchable polymerization catalysts need to be configurable for activation in response to diverse chemical stimuli. Here, we combine synthetic photocatalysts with conformation-switching DNA aptamers to create polymerization catalysts that respond to diverse chemical stimuli. We use the secondary structure of DNA to bring a photocatalyst and quencher dye into proximity, turning off photocatalysis. The DNA structure can be precisely designed to change conformation in response to a molecular trigger, moving the photocatalyst far from the quencher and activating photocatalysis. We show these photocatalysts can initiate free-radical polymerization to form bulk hydrogels in response to complementary DNA, a metal ion (Zn2+), or small molecules (glucose and hydrocortisone). We demonstrate the biocompatibility of these switchable photocatalysts by triggering their activation on the surface of yeast cells. Finally, we perform reversible-deactivation radical polymerization through photoinduced electron/energy transfer reversible addition−fragmentation chain-transfer in a dual-stimulus manner, in which catalytic activity is regulated reversibly by photoirradiation and the conformational state of the DNA catalyst. These results demonstrate that DNA conformational changes triggered by chemically diverse stimuli can regulate the activity of radical polymerization photocatalysts. This platform offers new capabilities in spatially and temporally controlled polymer synthesis, with potential applications in diagnostics, sensing, and environmentally responsive materials.
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