ABSTRACT
Uranium concentrations as high as 2.94 × 105 parts per million (1.82 mol of U/1 kg of H2O) occur in water containing nanoscale uranyl cage clusters. The anionic cage clusters, with diameters of 1.5-2.5 nm, are charge-balanced by encapsulated cations, as well as cations within their electrical double layer in solution. The concentration of uranium in these systems is impacted by the countercations (K, Li, Na), and molecular dynamics simulations have predicted their distributions in selected cases. Formation of uranyl cages prevents hydrolysis reactions that would result in formation of insoluble uranyl solids under alkaline conditions, and these spherical clusters reach concentrations that require close packing in solution.
ABSTRACT
Self-assembly of ([UO2(O2)OH]60)(60-) (U60), an actinide polyoxometalate with fullerene topology, can be induced by the addition of mono- and divalent cations to aqueous U60 solutions. Dynamic light scattering and small-angle X-ray scattering lend important insights into assembly in this system, but direct imaging of U60 and its assemblies via transmission electron microscopy (TEM) has remained an elusive goal. In this work, we used cryogenic TEM to image U60 and secondary and tertiary assemblies of U60 to characterize the size, morphology, and rate of formation of the secondary and tertiary structures. The kinetics and final morphologies of the secondary and tertiary structures strongly depend on the cation employed, with monovalent cations (Na(+) and K(+)) leading to the highest rates and largest secondary and tertiary structures.
ABSTRACT
Two new hybrid uranyl-carboxyphosphonate cage clusters built from uranyl peroxide units were crystallized from aqueous solution under ambient conditions in approximately two months. The clusters are built from uranyl hexagonal bipyramids and are connected by employing a secondary metal linker, the 2-carboxyphenylphosphonate ligand. The structure of cluster A is composed of a ten-membered uranyl polyhedral belt that is capped on either end of an elongated cage by five-membered rings of uranyl polyhedra. The structure of cluster B consists of 24 uranyl cations that are arranged into 6 four-membered rings of uranyl polyhedra. Four of the corresponding topological squares are fused together to form a sixteen-membered double uranyl pseudobelt that is capped on either end by 2 topological squares. Cluster A crystallizes over a wide pH range of 4.6-6.8, while cluster B was isolated under narrower pH range of 6.9-7.8. Studies of their fate in aqueous solution upon dissolution of crystals by electrospray ionization mass spectrometry (ESI-MS) and small-angle X-ray scattering (SAXS) provide evidence for their persistence in solution. The well-established characteristic fingerprint from the absorption spectra of the uranium(VI) cations disappears and becomes a nearly featureless peak; nonetheless, the two compounds fluoresce at room temperature.
