skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: A macrocycle directed total synthesis of di- O -methylendiandrin A
The total synthesis of the lignan-based cyclobutane di- O -methylendiandrin A has been achieved using diastereoselective, vicinal alkylation and transannular McMurry reactions of a macrocyclic 1,4-diketone as key transformations for establishing relative stereochemistry and furnishing the strained 4-membered ring of the natural product.  more » « less
Award ID(s):
1654691
PAR ID:
10228706
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Chemical Communications
Volume:
56
Issue:
62
ISSN:
1359-7345
Page Range / eLocation ID:
8747 to 8749
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. We report on temperature-dependent dielectric behavior of disordered ternary A6B2O17 (A = Zr, Hf; B = Nb, Ta)-form oxides in the GHz frequency range. The microwave dielectric properties including relative permittivity, dielectric loss, and temperature-dependent relative permittivity were characterized using cylindrical dielectric resonators using a resonant post measurement technique. Dielectric measurements through the resonant post method approach generally agree with dielectric measurements of A6B2O17 bulk ceramics measured through standard resonant post techniques. Coefficients describing the temperature-dependent relative permittivity for ternary A6B2O17 phases are strongly positive, suggesting contributions to polarizability arising from long-range mechanisms potentially associated with structural disorder. These observations support the working hypothesis that material functionality can be engineered by the chemical diversity and structural disorder possible in high configurational entropy A6B2O17 phases. 
    more » « less
  2. We outline a method to synthesize (ATiO3)nAO Ruddlesden–Popper phases with high-n, where the A-site is a mixture of barium and strontium, by molecular-beam epitaxy. The precision and consistency of the method described is demonstrated by the growth of an unprecedented (SrTiO3)50SrO epitaxial film. We proceed to investigate barium incorporation into the Ruddlesden–Popper structure, which is limited to a few percent in bulk, and we find that the amount of barium that can be incorporated depends on both the substrate temperature and the strain state of the film. At the optimal growth temperature, we demonstrate that as much as 33% barium can homogeneously populate the A-site when films are grown on SrTiO3 (001) substrates, whereas up to 60% barium can be accommodated in films grown on TbScO3 (110) substrates, which we attribute to the difference in strain. This detailed synthetic study of high n, metastable Ruddlesden–Popper phases is pertinent to a variety of fields from quantum materials to tunable dielectrics. 
    more » « less
  3. null (Ed.)
    ABSTRACT X-ray observations provide a unique probe of the accretion disc corona of supermassive black holes (SMBHs). In this paper, we present a uniform Chandra X-ray data analysis of a sample of 152 z ≥ 4.5 quasars. We firmly detect 46 quasars of this sample in 0.5–2 keV above 3σ and calculate the upper limits of the X-ray flux of the remaining. We also estimate the power-law photon index of the X-ray spectrum of 31 quasars. 24 of our sample quasars are detected in the FIRST or NVSS radio surveys; all of them are radio-loud. We statistically compare the X-ray properties of our z ≥ 4.5 quasars to other X-ray samples of active galactic nuclei (AGNs) at different redshifts. The relation between the rest-frame X-ray luminosity and other quasar parameters, such as the bolometric luminosity, UV luminosity, or SMBH mass, shows large scatters. These large scatters can be attributed to the narrow luminosity range at the highest redshift, the large measurement error based on relatively poor X-ray data, and the inclusion of radio-loud quasars in the sample. The LX–LUV relationship is significantly sublinear. We do not find a significant redshift evolution of the LX–LUV relation, expressed either in the slope of this relation, or the departure of individual AGNs from the best-fitting αOX–LUV relation (ΔαOX). The median value of the X-ray photon index is Γ ≈ 1.79, which does not show redshift evolution from z = 0 to z ∼ 7. The X-ray and UV properties of the most distant quasars could potentially be used as a standard candle to constrain cosmological models. The large scatter of our sample on the Hubble diagram highlights the importance of future large unbiased deep X-ray and radio surveys in using quasars in cosmological studies. 
    more » « less
  4. This work raises a fundamental question about the “real” structure of molecular compounds containing three different metals: whether they consist of genuine hetero tri metallic species or of a mixture of parent hetero bi metallic species. Heterotrimetallic complex Li 2 CoNi(tbaoac) 6 ( 1 , tbaoac = tert -butyl acetoacetate) has been designed based on the model tetranuclear structure featuring two transition metal sites in order to be utilized as a molecular precursor for the low-temperature preparation of the LiCo 0.5 Ni 0.5 O 2 battery cathode material. An investigation of the structure of 1 appeared to be very challenging, since the Co and Ni atoms have very similar atomic numbers, monoisotopic masses, and radii as well as the same oxidation state and coordination number/environment. Using a statistical analysis of heavily overlaid isotope distribution patterns of the [Li 2 MM′L 5 ] + (M/M′ = Co 2 , Ni 2 , and CoNi) ions in DART mass spectra, it was concluded that the reaction product 1 contains both heterotrimetallic and bimetallic species. A structural analogue approach has been applied to obtain Li 2 MMg(tbaoac) 6 (M = Co ( 2 ) and Ni ( 3 )) complexes that contain lighter, diamagnetic magnesium in the place of one of the 3d transition metals. X-ray crystallography, mass spectrometry, and NMR spectroscopy unambiguously confirmed the presence of three types of molecules in the reaction mixture that reaches an equilibrium, Li 2 M 2 L 6 + Li 2 Mg 2 L 6 ↔ 2Li 2 MMgL 6 , upon prolonged reflux in solution. The equilibrium mixture was shown to have a nearly statistical distribution of the three molecules, and this is fully supported by the results of theoretical calculations revealing that the stabilization energies of hetero tri metallic assemblies fall exactly in between those for the parent hetero bi metallic species. The LiCo 0.5 Ni 0.5 O 2 quaternary oxide has been obtained in its phase-pure form by thermal decomposition of heterometallic precursor 1 at temperatures as low as 450 °C. Its chemical composition, structure, morphology, and transition metal distribution have been studied by X-ray and electron diffraction techniques and compositional energy-dispersive X-ray mapping with nanometer resolution. The work clearly illustrates the advantages of heterometallic single-source precursors over the corresponding multi-source precursors. 
    more » « less
  5. The genus Phaeocystis is globally distributed, with blooms commonly occurring on continental shelves. This unusual phytoplankter has two major morphologies: solitary cells and cells embedded in a gelatinous matrix. Only colonies form blooms. Their large size (commonly 2 mm but up to 3 cm) and mucilaginous envelope allow the colonies to escape predation, but data are inconsistent as to whether colonies are grazed. Cultured Phaeocystis can also inhibit the growth of co-occurring phytoplankton or the feeding of potential grazers. Colonies and solitary cells use nitrate as a nitrogen source, although solitary cells can also grow on ammonium. Phaeocystis colonies might be a major contributor to carbon flux to depth, but in most cases, colonies are rapidly remineralized in the upper 300 m. The occurrence of large Phaeocystis blooms is often associated with environments with low and highly variable light and high nitrate levels, with Phaeocystis antarctica blooms being linked additionally to high iron availability. Emerging results indicate that different clones of Phaeocystis have substantial genetic plasticity, which may explain its appearance in a variety of environments, Given the evidence of Phaeocystis appearing in new systems, this trend will likely continue in the near future. Expected final online publication date for the Annual Review of Marine Science, Volume 16 is January 2024. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates. 
    more » « less