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Title: Probing activated radioprotection of simple hydrophilic phosphonic acids in aqueous solution

Abstract

Previous investigation into the radiation chemistry of the ligand octylphenyl-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO) and its analogues demonstrated their ability to undergo activated radioprotection in an organic solvent – a feature most advantageous for spent nuclear fuel reprocessing scenarios. This phenomenon was dependent on these organophosphorus compounds forming a sacrificial complex involving extracted nitric acid and the presence of an adjacent phenylphosphine oxide motif in the molecule. However, the hydrophobic nature of these compounds prevented elucidation of which components were essential for activated radioprotection; for example, does the phenylphosphine oxide motif only require protonation, or simply the presence of complexed nitrate anion(s), or both? To begin to address these questions, we report on the effect of dissolved nitrate on the radiation chemistry of a series of simple hydrophilic phosphonic acids (methyl, ethyl, phenyl, and benzyl) in aqueous solution. An extensive suite of gamma irradiations supported by high performance liquid chromatography and nuclear magnetic resonance techniques was used to demonstrate that all four compounds were unable to undergo activated radioprotection. Although some nitrate protection was observed, this was attributed to changes in the available suite of radiolysis products, and not to the formation of nitrate-phosphonic acid sacrificial complexes. The absence of activatedmore » radioprotection and evidence for the formation of a [PhPA•NO3-] complex further supports the necessity of complex formation to activate the radioprotection mechanism.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3]
+ Show Author Affiliations
  1. Idaho National Lab. (INL), Idaho Falls, ID (United States)
  2. Idaho National Lab. (INL), Idaho Falls, ID (United States); Idaho State Univ., Pocatello, ID (United States)
  3. California State Univ. (CalState), Long Beach, CA (United States)
  4. Saint Xavier Univ., Chicago, IL (United States)
Publication Date:
Research Org.:
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE), Nuclear Fuel Cycle and Supply Chain. Office of Advanced Fuels Technologies; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1593913
Alternate Identifier(s):
OSTI ID: 1580548; OSTI ID: 1656845
Report Number(s):
INL/JOU-19-56059-Rev000; INL/JOU-19-55983-Rev000
Journal ID: ISSN 0969-806X; TRN: US2101865
Grant/Contract Number:  
AC07-05ID14517; NE0008406; FC02-04ER15533
Resource Type:
Accepted Manuscript
Journal Name:
Radiation Physics and Chemistry (1993)
Additional Journal Information:
Journal Name: Radiation Physics and Chemistry (1993); Journal Volume: 170; Journal Issue: C; Journal ID: ISSN 0969-806X
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; Hydrophilic Phosphonic Acids; Gamma Radiolysis; Pulsed Electron Radiolysis; 38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; Activated Radioprotection; Phosphonic Acids

Citation Formats

Horne, Gregory P., Zarzana, Christopher A., Daubaras, Dayna L., Pilgrim, Corey D., Rae, Cathy, Faulkner, Richard F., Kiddle, James J., and Mezyk, Stephen P. Probing activated radioprotection of simple hydrophilic phosphonic acids in aqueous solution. United States: N. p., 2019. Web. doi:10.1016/j.radphyschem.2019.108636.
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Horne, Gregory P., Zarzana, Christopher A., Daubaras, Dayna L., Pilgrim, Corey D., Rae, Cathy, Faulkner, Richard F., Kiddle, James J., & Mezyk, Stephen P. Probing activated radioprotection of simple hydrophilic phosphonic acids in aqueous solution. United States. https://doi.org/10.1016/j.radphyschem.2019.108636
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Horne, Gregory P., Zarzana, Christopher A., Daubaras, Dayna L., Pilgrim, Corey D., Rae, Cathy, Faulkner, Richard F., Kiddle, James J., and Mezyk, Stephen P. Sat . "Probing activated radioprotection of simple hydrophilic phosphonic acids in aqueous solution". United States. https://doi.org/10.1016/j.radphyschem.2019.108636. https://www.osti.gov/servlets/purl/1593913.
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@article{osti_1593913,
title = {Probing activated radioprotection of simple hydrophilic phosphonic acids in aqueous solution},
author = {Horne, Gregory P. and Zarzana, Christopher A. and Daubaras, Dayna L. and Pilgrim, Corey D. and Rae, Cathy and Faulkner, Richard F. and Kiddle, James J. and Mezyk, Stephen P.},
abstractNote = {Previous investigation into the radiation chemistry of the ligand octylphenyl-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO) and its analogues demonstrated their ability to undergo activated radioprotection in an organic solvent – a feature most advantageous for spent nuclear fuel reprocessing scenarios. This phenomenon was dependent on these organophosphorus compounds forming a sacrificial complex involving extracted nitric acid and the presence of an adjacent phenylphosphine oxide motif in the molecule. However, the hydrophobic nature of these compounds prevented elucidation of which components were essential for activated radioprotection; for example, does the phenylphosphine oxide motif only require protonation, or simply the presence of complexed nitrate anion(s), or both? To begin to address these questions, we report on the effect of dissolved nitrate on the radiation chemistry of a series of simple hydrophilic phosphonic acids (methyl, ethyl, phenyl, and benzyl) in aqueous solution. An extensive suite of gamma irradiations supported by high performance liquid chromatography and nuclear magnetic resonance techniques was used to demonstrate that all four compounds were unable to undergo activated radioprotection. Although some nitrate protection was observed, this was attributed to changes in the available suite of radiolysis products, and not to the formation of nitrate-phosphonic acid sacrificial complexes. The absence of activated radioprotection and evidence for the formation of a [PhPA•NO3-] complex further supports the necessity of complex formation to activate the radioprotection mechanism.},
doi = {10.1016/j.radphyschem.2019.108636},
journal = {Radiation Physics and Chemistry (1993)},
number = C,
volume = 170,
place = {United States},
year = {2019},
month = {12}
}
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