Radiation stability of cations in ionic liquids. 5. Task-specific ionic liquids consisting of biocompatible cations and the puzzle of radiation hypersensitivity

Ilya A. Shkrob, Timothy W. Marin, James F. Wishart, David Grills

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

In 1953, an accidental discovery by Melvin Calvin and co-workers provided the first example of a solid (the α-polymorph of choline chloride) showing hypersensitivity to ionizing radiation: under certain conditions, the radiolytic yield of decomposition approached 5 × 104 per 100 eV (which is 4 orders of magnitude greater than usual values), suggesting an uncommonly efficient radiation-induced chain reaction. Twenty years later, the still-accepted mechanism for this rare condition was suggested by Martyn Symons, but no validation for this mechanism has been supplied. Meanwhile, ionic liquids and deep eutectic mixtures that are based on choline, betainium, and other derivitized natural amino compounds are presently finding an increasing number of applications as diluents in nuclear separations, where the constituent ions are exposed to ionizing radiation that is emitted by decaying radionuclides. Thus, the systems that are compositionally similar to radiation hypersensitive solids are being considered for use in high radiation fields, where this property is particularly undesirable! In Part 5 of this series on organic cations, we revisit the phenomenon of radiation hypersensitivity and explore mechanistic aspects of radiation-induced reactions involving this class of task-specific, biocompatible, functionalized cations, both in ionic liquids and in reference crystalline compounds. We demonstrate that Symons' mechanism needs certain revisions and rethinking, and suggest its modification. Our reconsideration suggests that there cannot be conditions leading to hypersensitivity in ionic liquids.

Original languageEnglish
Pages (from-to)10477-10492
Number of pages16
JournalJournal of Physical Chemistry B
Volume118
Issue number35
DOIs
Publication statusPublished - Sep 4 2014

Fingerprint

Ionic Liquids
Ionic liquids
Cations
Hypersensitivity
Positive ions
Radiation
cations
choline
radiation
liquids
ionizing radiation
Ionizing radiation
Choline
Ionizing Radiation
diluents
eutectics
radioactive isotopes
radiation distribution
Polymorphism
Radioisotopes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Materials Chemistry
  • Surfaces, Coatings and Films
  • Medicine(all)

Cite this

Radiation stability of cations in ionic liquids. 5. Task-specific ionic liquids consisting of biocompatible cations and the puzzle of radiation hypersensitivity. / Shkrob, Ilya A.; Marin, Timothy W.; Wishart, James F.; Grills, David.

In: Journal of Physical Chemistry B, Vol. 118, No. 35, 04.09.2014, p. 10477-10492.

Research output: Contribution to journalArticle

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