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Title: Uranyl Peroxide Capsule Self-assembly in Slow Motion Ana Arteaga,1 Lei Zhang,2 Sarah Hickam,2 Mateusz Dembowski,2,3 Peter C. Burns 2 and May Nyman1*

Abstract

Uranyl-peroxide capsules are the newest family of polyoxometalates. Although discovered 13 years prior with over 70 topologies reported, we lack fundamental understanding of assembly mechanisms, particularly the role of the alkali countercations. Herein, we report the reaction pathway and assembly of uranyl peroxide capsules by tracking the conversion from K + uranyl triperoxide monomer to the K + uranyl-peroxide U28 capsule via Small Angle X-Ray Scattering and Raman Spectroscopy. For the first time, the K + uranyl-peroxide pentamer face is isolated and structurally characterized, giving credence to the long-held belief that these geometric faces serve as building blocks to the fully formed capsules. Once isolated and redissolved, the pentamer face undergoes rapid conversion to capsule forms, underlining its high reactivity that challenges its isolation. Calorimetric measurements of the studied species confirms the pentamer lies on the energy landscape between the monomer and capsule.

Authors:
 [1];  [2];  [2];  [2];  [2];  [1]
  1. Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry
  2. Univ. of Notre Dame, Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences
Publication Date:
Research Org.:
Univ. of Notre Dame, Notre Dame, IN (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1502931
Alternate Identifier(s):
OSTI ID: 1503928
Grant/Contract Number:  
NA0003763; SC0001089
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Name: Chemistry - A European Journal; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; uranyl; Polyoxometalates; X-ray scattering; Calorimetry; crystal structure

Citation Formats

Arteaga, Ana, Zhang, Lei, Hickam, Sarah, Dembowski, Mateusz, Burns, Peter, and Nyman, May. Uranyl Peroxide Capsule Self-assembly in Slow Motion Ana Arteaga,1 Lei Zhang,2 Sarah Hickam,2 Mateusz Dembowski,2,3 Peter C. Burns 2 and May Nyman1*. United States: N. p., 2019. Web. doi:10.1002/chem.201806227.
Arteaga, Ana, Zhang, Lei, Hickam, Sarah, Dembowski, Mateusz, Burns, Peter, & Nyman, May. Uranyl Peroxide Capsule Self-assembly in Slow Motion Ana Arteaga,1 Lei Zhang,2 Sarah Hickam,2 Mateusz Dembowski,2,3 Peter C. Burns 2 and May Nyman1*. United States. doi:10.1002/chem.201806227.
Arteaga, Ana, Zhang, Lei, Hickam, Sarah, Dembowski, Mateusz, Burns, Peter, and Nyman, May. Wed . "Uranyl Peroxide Capsule Self-assembly in Slow Motion Ana Arteaga,1 Lei Zhang,2 Sarah Hickam,2 Mateusz Dembowski,2,3 Peter C. Burns 2 and May Nyman1*". United States. doi:10.1002/chem.201806227.
@article{osti_1502931,
title = {Uranyl Peroxide Capsule Self-assembly in Slow Motion Ana Arteaga,1 Lei Zhang,2 Sarah Hickam,2 Mateusz Dembowski,2,3 Peter C. Burns 2 and May Nyman1*},
author = {Arteaga, Ana and Zhang, Lei and Hickam, Sarah and Dembowski, Mateusz and Burns, Peter and Nyman, May},
abstractNote = {Uranyl-peroxide capsules are the newest family of polyoxometalates. Although discovered 13 years prior with over 70 topologies reported, we lack fundamental understanding of assembly mechanisms, particularly the role of the alkali countercations. Herein, we report the reaction pathway and assembly of uranyl peroxide capsules by tracking the conversion from K+ uranyl triperoxide monomer to the K+ uranyl-peroxide U28 capsule via Small Angle X-Ray Scattering and Raman Spectroscopy. For the first time, the K+ uranyl-peroxide pentamer face is isolated and structurally characterized, giving credence to the long-held belief that these geometric faces serve as building blocks to the fully formed capsules. Once isolated and redissolved, the pentamer face undergoes rapid conversion to capsule forms, underlining its high reactivity that challenges its isolation. Calorimetric measurements of the studied species confirms the pentamer lies on the energy landscape between the monomer and capsule.},
doi = {10.1002/chem.201806227},
journal = {Chemistry - A European Journal},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {3}
}

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This content will become publicly available on March 6, 2020
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