Thermal Responsive Ion Selectivity of Uranyl Peroxide Nanocages: An Inorganic Mimic of K<sup>+</sup> Ion Channels

Gao, Yunyi; Szymanowski, Jennifer E. S.; Sun, Xinyu; Burns, Peter C.; Liu, Tianbo

doi:10.1002/ange.201601852

Cited by 16 publications

(9 citation statements)

References 37 publications

(14 reference statements)

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“…This −5 ppm peak suggests there remains a more hydrated impurity phase. In fact, −5 ppm is a similar chemical shift as the average of lattice Li exchanging with encapsulated lithium in the previously reported solid-state 7 Li MAS NMR of Li-U 24 . The 2D 1 H– 7 Li NMR heteronuclear (HETCOR) correlation spectrum (Figure B) shows a small correlation (due to the reduced dipolar coupling from dynamic averaging the external 7 Li ∼ 0 ppm) associated with bridging hydroxyls ( 1 H ∼ +9.8 ppm) of the U 24 capsule.…”

Section: Resultsmentioning

confidence: 99%

“…When dissolved in water, uranyl POMs exchange encapsulated alkali cations, which pass through the square, pentagonal, and hexagonal faces of the cage between the capsule and the surrounding medium . Moreover, recent magic-angle-spinning nuclear magnetic resonance (MAS NMR) studies revealed a high-rate solid-state exchange of Li + and aqua species between the uranyl capsule of solid U 24 ([UO 2 (O 2 )(OH)] 24 24– ), , and U 60 ([UO 2 (O 2 )(OH)] 60 60– ) clusters, and the external lattice containing hydrated alkalis.…”

Section: Introductionmentioning

confidence: 99%

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Resolving Confined ⁷Li Dynamics of Uranyl Peroxide Capsule U₂₄

et al. 2018

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We obtained a kerosene-soluble form of the lithium salt [UO(O)(OH)] phase (Li-U), by adding cetyltrimethylammonium bromide surfactant to aqueous Li-U. Interestingly, its variable-temperature solution Li NMR spectroscopy resolves two narrowly spaced resonances down to -10 °C, which shift upfield with increasing temperature, and finally coalesce at temperatures> 85 °C. Comparison with solid-state NMR demonstrates that the Li dynamics in the Li-U-CTA phase involves only exchange between different local encapsulated environments. This behavior is distinct from the rapid Li exchange dynamics observed between encapsulated and external Li environments for Li-U in both the aqueous and the solid-state phases. Density functional theory calculations suggest that the two experimental Li NMR chemical shifts are due to Li cations coordinated within the square and hexagonal faces of the U cage, and they can undergo exchange within the confined environment, as the solution is heated. Very different than U in aqueous media, there is no evidence that the Li cations exit the cage, and therefore, this represents a truly confined space.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Resolving Confined ⁷Li Dynamics of Uranyl Peroxide Capsule U₂₄

et al. 2018

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“…In its crystalline form, each U 60 cluster carries approximately 60 charges, balanced by about 12 K + and around 48 Li + . The U 60 clusters can be easily dissolved in aqueous solutions and be stable for months . They do not quickly spontaneously self‐assemble or aggregate in dilute aqueous solutions without adding large amount of additional salts, due to their high charge density.…”

Section: Figurementioning

confidence: 99%

“…They tend to fully precipitate from the solution when the ionic strength becomes very high . However, for comparison, when a 1.0 mg mL −1 U 60 solution is titrated with monovalent alkali cations, for example, K + , to trigger the possible blackberry structure formation, the minimum KCl/U 60 molar ratio needed for assembling is about 100 and for precipitating is around 220 . This suggests that, with a CATB/U 60 ratio <10, electrostatic attraction can hardly be the major driving force for the self‐assembly of the U 60 –CTAB complexes.…”

Section: Figurementioning

confidence: 99%

Inhomogeneous Distribution of Cationic Surfactants around Anionic Molecular Clusters

Gao

Chen

Zhang

et al. 2019

Chemistry A European J

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An interesting phenomenon is reported when uranyl peroxide nanoclusters U60 (Li48+mK12(OH)m[UO2(O2)(OH)]60 (H2O)n, m≈20 and n≈310) interact with a small number of cationic surfactant molecules. Cationic surfactant molecules do not distribute evenly around the U60 clusters during the interaction as expected. Instead, a small fraction of U60 clusters attract almost all the surfactant molecules, leading to the self‐assembly into supramolecular structures by using surfactant–U60 complexes as building locks, and later further aggregate and precipitate based on hydrophobic interaction, whereas the rest of the clusters remained unbounded soluble macroions in bulk dispersion. This phenomenon nicely demonstrates a unique feature of macroion solutions. Considering that Debye–Hückel approximation is no longer valid in such solutions, the competition between the local electrostatic interaction and hydrophobic interaction becomes important to regulate the solution behaviors of macroions.

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“…Among them, CPs based on actinide elements emerge as a new category in this arena, and there is still much room for development of actinide complexes as compared with the great deal of research on lanthanide and transition metals. Because of their unique properties in 5f orbital bonding and significance in the nuclear industry, − the study of actinide-based CPs is a fascinating research field, which is beneficial to both the exploration of intriguing physicochemical properties of actinide-based hybrid materials and the promotion of potential utilization of them. As one of the most important actinide elements, uranium has attracted special attention.…”

Section: Introductionmentioning

confidence: 99%

Mixed-Ligand Uranyl Squarate Coordination Polymers: Structure Regulation and Redox Activity

et al. 2021

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The electron-rich squarate ion (C4O4 2–, SA 2–) possesses electronic delocalization over the entire molecule and good redox activity, and the functionalization of metal–organic complexes with the SA 2– group is desirable. In this work, a mixed-ligand method is used to construct novel uranyl squarate coordination polymers utilizing 4,4′-bipyridine (bpy), 4,4′-bipyridine-N,N′-dioxide (bpydo), 1,10-phenanthroline (phen), 4,4′-vinylenedipyridine (vidpy), and in situ formed oxalate (OA 2–) as ancillary ligands. Seven mixed-ligand uranyl compounds, [(UO2)(OH)(SA)](Hbpy) (1), [(UO2)(H2O)(SA)2](H2 bpy) (2), (UO2)(H2O)(SA)(bpydo)·2H2O (3), (UO2)(H2O)(SA)(phen)·H2O (4), (UO2)(OH)(SA)0.5(phen)·H2O (5), [(UO2)(SA)(OA)0.5](Hphen) (6), and [(UO2)(SA)(OA)0.5](Hvidpy) (7), with varying crystal structures were synthesized under hydrothermal conditions. Compound 1, together with bpy molecules filling in the interlayer space as template agents, has a two-dimensional (2D) network structure, while 2 gives a one-dimensional (1D) chain based on mononuclear uranium units. Compound 3 shows a neutral 2D network through the combined linkage of SA 2– and bpydo. Both 4 and 5 have a similar chain-like structure due to the capping effect of phen motifs, while phen molecules in 6 act as templating agents after protonation. Similar to 6, compound 7 has a “sandwich-like” structure in which the Hvidpy motifs locate in the voids of layers of 2D uranyl-squarate networks. The redox properties of typical mixed-ligand uranyl-squarate compounds, 1, 4, and 5 with high phase purity, are characterized using cyclic voltammetry. All three of these uranyl coordination compounds show anode peaks (E a) at 0.777, 0.804, and 0.760 V, respectively, which correspond to the oxidation process of SA 2– → SA. Meanwhile, cathodic peaks (E c) at −0.328, −0.315, and −0.323 V corresponding to the reduction process of U(VI) → U(V) are also observed. The results reveal that all three of these uranyl coordination compounds show good redox activity and, most importantly, the interplay between two different redox-active motifs of SA 2– organic linker and uranyl node. This work enriches the library of redox-active uranyl compounds and provides a feasible mixed-ligand method for regulating the synthesis of functional actinide compounds.

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Thermal Responsive Ion Selectivity of Uranyl Peroxide Nanocages: An Inorganic Mimic of K⁺ Ion Channels

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 16 publications

References 37 publications

Resolving Confined ⁷Li Dynamics of Uranyl Peroxide Capsule U₂₄

Resolving Confined ⁷Li Dynamics of Uranyl Peroxide Capsule U₂₄

Inhomogeneous Distribution of Cationic Surfactants around Anionic Molecular Clusters

Mixed-Ligand Uranyl Squarate Coordination Polymers: Structure Regulation and Redox Activity

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Thermal Responsive Ion Selectivity of Uranyl Peroxide Nanocages: An Inorganic Mimic of K+ Ion Channels

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 16 publications

References 37 publications

Resolving Confined 7Li Dynamics of Uranyl Peroxide Capsule U24

Resolving Confined 7Li Dynamics of Uranyl Peroxide Capsule U24

Inhomogeneous Distribution of Cationic Surfactants around Anionic Molecular Clusters

Mixed-Ligand Uranyl Squarate Coordination Polymers: Structure Regulation and Redox Activity

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Product

Resources

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Thermal Responsive Ion Selectivity of Uranyl Peroxide Nanocages: An Inorganic Mimic of K⁺ Ion Channels

Resolving Confined ⁷Li Dynamics of Uranyl Peroxide Capsule U₂₄

Resolving Confined ⁷Li Dynamics of Uranyl Peroxide Capsule U₂₄