Standalone 2-D Nanosheets and the Consequent Hydrogel and Coacervate Phases Formed by 2.5 nm Spherical U60Molecular Clusters in Dilute Aqueous Solution

Yuqing Yang; Yifan Zhou; Jiahui Chen; Tsuyoshi Kohlgruber; Travis Smith; Bowen Zheng; Jennifer E.S. Szymanowski; Peter C. Burns; Tianbo Liu

doi:10.1021/acs.jpcb.1c08019

Standalone 2-D Nanosheets and the Consequent Hydrogel and Coacervate Phases Formed by 2.5 nm Spherical U₆₀Molecular Clusters in Dilute Aqueous Solution

Yuqing Yang
, Yifan Zhou
, Jiahui Chen
, Tsuyoshi Kohlgruber
, Travis Smith
, Bowen Zheng
, Jennifer E.S. Szymanowski
, Peter C. Burns
, Tianbo Liu

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

Unexpected hydrogel and coacervate are observed for dilute (1 mM) uranyl peroxide molecular cluster (Li₆₈K₁₂(OH)₂₀[UO₂(O₂)(OH)]₆₀, U₆₀) solution in the presence of di- or trivalent salts. We report the mechanism as the formation of anisotropic two-dimensional (2-D) single-layer nanosheets, driven by counterion-mediated attraction due to the size disparity between U₆₀and small counterions. With weak monovalent cations, the nanosheets are bendable, resulting in hollow, spherical blackberry-type supramolecular assemblies in a homogeneous solution. With extra strong divalent or trivalent cations, the tough, free-standing sheets lead to gelation at ∼1 mM U₆₀. These stiff nanosheets are difficult to bend into spherical blackberry-type structures; instead, they stay in solution and form hydrogel based on their significant excluded volumes. At higher ionic strength, the large, thin filmlike nanosheet structures stack together more compactly and consequently lead to the transition from gel phase to a coacervate phase, another surprise since it was formed without the presence of bulky polycations.

Original language	English
Pages (from-to)	12392-12397
Number of pages	6
Journal	Journal of Physical Chemistry B
Volume	125
Issue number	44
DOIs	https://doi.org/10.1021/acs.jpcb.1c08019
State	Published - Nov 11 2021
Externally published	Yes

Funding

T.L. acknowledges support from the National Science Foundation (NSF CHE1904397) and the University of Akron. P.C.B. acknowledges support from the National Nuclear Security Administration, Department of Energy, under Award No. DE-Na0003763, and the University of Notre Dame. The National Science Foundation (NSF CHE1904397) and the National Nuclear Security Administration, Department of Energy, under Award No. DE-Na0003763A.

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Yang, Y., Zhou, Y., Chen, J., Kohlgruber, T., Smith, T., Zheng, B., Szymanowski, J. E. S., Burns, P. C., & Liu, T. (2021). Standalone 2-D Nanosheets and the Consequent Hydrogel and Coacervate Phases Formed by 2.5 nm Spherical U₆₀Molecular Clusters in Dilute Aqueous Solution. Journal of Physical Chemistry B, 125(44), 12392-12397. https://doi.org/10.1021/acs.jpcb.1c08019

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title = "Standalone 2-D Nanosheets and the Consequent Hydrogel and Coacervate Phases Formed by 2.5 nm Spherical U60Molecular Clusters in Dilute Aqueous Solution",

abstract = "Unexpected hydrogel and coacervate are observed for dilute (1 mM) uranyl peroxide molecular cluster (Li68K12(OH)20[UO2(O2)(OH)]60, U60) solution in the presence of di- or trivalent salts. We report the mechanism as the formation of anisotropic two-dimensional (2-D) single-layer nanosheets, driven by counterion-mediated attraction due to the size disparity between U60and small counterions. With weak monovalent cations, the nanosheets are bendable, resulting in hollow, spherical blackberry-type supramolecular assemblies in a homogeneous solution. With extra strong divalent or trivalent cations, the tough, free-standing sheets lead to gelation at ∼1 mM U60. These stiff nanosheets are difficult to bend into spherical blackberry-type structures; instead, they stay in solution and form hydrogel based on their significant excluded volumes. At higher ionic strength, the large, thin filmlike nanosheet structures stack together more compactly and consequently lead to the transition from gel phase to a coacervate phase, another surprise since it was formed without the presence of bulky polycations.",

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doi = "10.1021/acs.jpcb.1c08019",

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AU - Yang, Yuqing

AU - Zhou, Yifan

AU - Chen, Jiahui

AU - Kohlgruber, Tsuyoshi

AU - Smith, Travis

AU - Zheng, Bowen

AU - Szymanowski, Jennifer E.S.

AU - Burns, Peter C.

AU - Liu, Tianbo

PY - 2021/11/11

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N2 - Unexpected hydrogel and coacervate are observed for dilute (1 mM) uranyl peroxide molecular cluster (Li68K12(OH)20[UO2(O2)(OH)]60, U60) solution in the presence of di- or trivalent salts. We report the mechanism as the formation of anisotropic two-dimensional (2-D) single-layer nanosheets, driven by counterion-mediated attraction due to the size disparity between U60and small counterions. With weak monovalent cations, the nanosheets are bendable, resulting in hollow, spherical blackberry-type supramolecular assemblies in a homogeneous solution. With extra strong divalent or trivalent cations, the tough, free-standing sheets lead to gelation at ∼1 mM U60. These stiff nanosheets are difficult to bend into spherical blackberry-type structures; instead, they stay in solution and form hydrogel based on their significant excluded volumes. At higher ionic strength, the large, thin filmlike nanosheet structures stack together more compactly and consequently lead to the transition from gel phase to a coacervate phase, another surprise since it was formed without the presence of bulky polycations.

AB - Unexpected hydrogel and coacervate are observed for dilute (1 mM) uranyl peroxide molecular cluster (Li68K12(OH)20[UO2(O2)(OH)]60, U60) solution in the presence of di- or trivalent salts. We report the mechanism as the formation of anisotropic two-dimensional (2-D) single-layer nanosheets, driven by counterion-mediated attraction due to the size disparity between U60and small counterions. With weak monovalent cations, the nanosheets are bendable, resulting in hollow, spherical blackberry-type supramolecular assemblies in a homogeneous solution. With extra strong divalent or trivalent cations, the tough, free-standing sheets lead to gelation at ∼1 mM U60. These stiff nanosheets are difficult to bend into spherical blackberry-type structures; instead, they stay in solution and form hydrogel based on their significant excluded volumes. At higher ionic strength, the large, thin filmlike nanosheet structures stack together more compactly and consequently lead to the transition from gel phase to a coacervate phase, another surprise since it was formed without the presence of bulky polycations.

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Standalone 2-D Nanosheets and the Consequent Hydrogel and Coacervate Phases Formed by 2.5 nm Spherical U₆₀Molecular Clusters in Dilute Aqueous Solution

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