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  1. Abstract

    Vascular plants direct large amounts of carbon to produce the aromatic amino acid phenylalanine to support the production of lignin and other phenylpropanoids. Uniquely, grasses, which include many major crops, can synthesize lignin and phenylpropanoids from both phenylalanine and tyrosine. However, how grasses regulate aromatic amino acid biosynthesis to feed this dual lignin pathway is unknown. Here we show, by stable-isotope labeling, that grasses produce tyrosine >10-times faster than Arabidopsis without compromising phenylalanine biosynthesis. Detailed in vitro enzyme characterization and combinatorialin plantaexpression uncovered that coordinated expression of specific enzyme isoforms at the entry and exit steps of the aromatic amino acid pathway enables grasses to maintain high production of both tyrosine and phenylalanine, the precursors of the dual lignin pathway. These findings highlight the complex regulation of plant aromatic amino acid biosynthesis and provide novel genetic tools to engineer the interface of primary and specialized metabolism in plants.

     
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    Free, publicly-accessible full text available November 9, 2024
  2. null (Ed.)
    Robust atomic-to-meso-scale chirality is now observed in the one-dimensional form of tellurium. This enables a large and counter-intuitive circular-polarization dependent second harmonic generation response above 0.2 which is not present in two-dimensional tellurium. Orientation variations in 1D tellurium nanowires obtained by four-dimensional scanning transmission electron microscopy (4D-STEM) and their correlation with unconventional non-linear optical properties by second harmonic generation circular dichroism (SHG-CD) uncovers an unexpected circular-polarization dependent SHG response from 1D nanowire bundles – an order-of-magnitude higher than in single-crystal two-dimensional tellurium structures – suggesting the atomic- and meso-scale crystalline structure of the 1D material possesses an inherent chirality not present in its 2D form; and which is strong enough to manifest even in the aggregate non-linear optical (NLO) properties of aggregates. 
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  3. Abstract

    The interactions between uranium and non‐innocent organic species are an essential component of fundamental uranium redox chemistry. However, they have seldom been explored in the context of multidimensional, porous materials. Uranium‐based metal–organic frameworks (MOFs) offer a new angle to study these interactions, as these self‐assembled species stabilize uranium species through immobilization by organic linkers within a crystalline framework, while potentially providing a method for adjusting metal oxidation state through coordination of non‐innocent linkers. We report the synthesis of the MOFNU‐1700, assembled from U4+‐paddlewheel nodes and catecholate‐based linkers. We propose this highly unusual structure, which contains two U4+ions in a paddlewheel built from four linkers—a first among uranium materials—as a result of extensive characterization via powder X‐ray diffraction (PXRD), sorption, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA), in addition to density functional theory (DFT) calculations.

     
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  4. Abstract

    The interactions between uranium and non‐innocent organic species are an essential component of fundamental uranium redox chemistry. However, they have seldom been explored in the context of multidimensional, porous materials. Uranium‐based metal–organic frameworks (MOFs) offer a new angle to study these interactions, as these self‐assembled species stabilize uranium species through immobilization by organic linkers within a crystalline framework, while potentially providing a method for adjusting metal oxidation state through coordination of non‐innocent linkers. We report the synthesis of the MOFNU‐1700, assembled from U4+‐paddlewheel nodes and catecholate‐based linkers. We propose this highly unusual structure, which contains two U4+ions in a paddlewheel built from four linkers—a first among uranium materials—as a result of extensive characterization via powder X‐ray diffraction (PXRD), sorption, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA), in addition to density functional theory (DFT) calculations.

     
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  5. Abstract

    Actinide materials have various applications that range from nuclear energy to quantum computing. Most current efforts have focused on bulk actinide materials. Tuning functional properties by using strain engineering in epitaxial thin films is largely lacking. Using uranium dioxide (UO2) as a model system, in this work, the authors explore strain engineering in actinide epitaxial thin films and investigate the origin of induced ferromagnetism in an antiferromagnet UO2. It is found that UO2+xthin films are hypostoichiometric (x<0) with in‐plane tensile strain, while they are hyperstoichiometric (x>0) with in‐plane compressive strain. Different from strain engineering in non‐actinide oxide thin films, the epitaxial strain in UO2is accommodated by point defects such as vacancies and interstitials due to the low formation energy. Both epitaxial strain and strain relaxation induced point defects such as oxygen/uranium vacancies and oxygen/uranium interstitials can distort magnetic structure and result in magnetic moments. This work reveals the correlation among strain, point defects and ferromagnetism in strain engineered UO2+xthin films and the results offer new opportunities to understand the influence of coupled order parameters on the emergent properties of many other actinide thin films.

     
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