Methods for the straightforward, room temperature synthesis of UO 2+ x nanoparticles and thin films using solution processable, molecular uranium( iv ) compounds is described. Ultra-small uranium dioxide nanoparticles are synthesized from the hydrolysis of either U(ditox) 4 (ditox = − OCH t Bu 2 ) (1) or U(CH 2 SiMe 2 NSiMe 3 )[N(SiMe 3 ) 2 ] 2 (2) via addition of water to stirring solutions of the compounds in non-polar solvents to give UO 2 -1 and UO 2 -2, respectively. The structural characteristics of the uranium dioxide nanoparticles were characterized using powder X-ray diffraction (pXRD), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. The pXRD results affirm the cubic fluorite structure expected for UO 2 nanoparticles. The nanocrystallinity of UO 2 -1 and UO 2 -2 were substantiated by bright-field HRTEM images and fast Fourier transform (FFT) patterns. The HRTEM analysis also shows the nanoparticles fall within the ultra-small regime possessing sizes of ∼3 nm with uniform distribution. Additionally, we demonstrate the versatility of 1 as a uranium dioxide precursor, showing that it can be readily sublimed onto glass or silicon substrates and subsequently hydrolyzed to give UO 2+ x thin films.
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Combined ab initio and empirical model of the thermal conductivity of uranium, uranium-zirconium, and uranium-molybdenum
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Abstract Geobacter bacteria produce conductive pili appendages and an outer membrane‐anchored lipopolysaccharide to immobilize uranium extracellularly. Yet, some radionuclide enters the cell envelope, where is rapidly mineralized by periplasmicc ‐cytochromes. To investigate this reaction, we constructed cell envelope biomimetic interfaces containing PpcA, the most conserved and abundant periplasmicc ‐cytochrome inGeobacter species. Cyclic voltammograms revealed much higher rate constants for uranium than for iron, the natural electron acceptor ofGeobacter , independently of the metal‐ligand complexation. These results are consistent with a much higher affinity of PpcA for uranium than for iron, providing a plausible explanation for the rapid mineralization of the radionuclide inside the cell envelope. The studies highlight the value of electrochemical biomimetic interfaces to dissect the contribution of cell envelope cytochromes to metal reduction and identify redox‐active proteins with the affinity needed for sensory applications. -
null (Ed.)We investigated the mechanisms of uranium (U) uptake by Tamarix (salt cedars) growing along the Rio Paguate, which flows throughout the Jackpile mine near Pueblo de Laguna, New Mexico. Tamarix were selected for this study due to the detection of U in the roots and shoots of field collected plants (0.6–58.9 mg kg −1 ), presenting an average bioconcentration factor greater than 1. Synchrotron-based micro X-ray fluorescence analyses of plant roots collected from the field indicate that the accumulation of U occurs in the cortex of the root. The mechanisms for U accumulation in the roots of Tamarix were further investigated in controlled-laboratory experiments where living roots of field plants were macerated for 24 h or 2 weeks in a solution containing 100 μM U. The U concentration in the solution decreased 36–59% after 24 h, and 49–65% in two weeks. Microscopic and spectroscopic analyses detected U precipitation in the root cell walls near the xylems of the roots, confirming the initial results from the field samples. High-resolution TEM was used to study the U fate inside the root cells, and needle-like U–P nanocrystals, with diameter <7 nm, were found entrapped inside vacuoles in cells. EXAFS shell-by-shell fitting suggest that U is associated with carbon functional groups. The preferable binding of U to the root cell walls may explain the U retention in the roots of Tamarix , followed by U–P crystal precipitation, and pinocytotic active transport and cellular entrapment. This process resulted in a limited translocation of U to the shoots in Tamarix plants. This study contributes to better understanding of the physicochemical mechanisms affecting the U uptake and accumulation by plants growing near contaminated sites.more » « less
