Generation of 1-hydroxyethyl ether (1HER) free radicals is an important step in the metabolism of ethanol in microsomes. Hydrogen-bonding interactions of 1HER with water have yet to be thoroughly investigated, despite their importance to biological systems. Computational chemistry is employed here to study micro-hydrated 1HER complexes in networks including up to 5 water molecules. 126 clusters are identified using the B3LYP DFT method and triple-z basis sets and are confirmed using the M06-2X, wB97xD, MP2, and CCSD methods. The two lowest-energy structures for each cluster size exhibit competition between forming a cyclic arrangement of hydrogen bonds and maximizing the electrostatic interaction with an unpaired electron on the central carbon atom of 1HER. Results suggest that upon interaction with water, the vulnerable 1HER radical is stabilized via a cyclic arrangement of hydrogen bonds, with delocalization of an unpaired electron in the electronic orbitals of the cyclic ring of hydrogen-bonded water molecules.

Theoretical investigation of biologically-relevant 1-hydroxyethyl radical: Preferential formation of cyclic hydrogen bonding networks versus electrostatic interaction maximization

2019 Spring National Meeting

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