¹⁷ O Hyperfine Spectroscopy Reveals Hydration Structure of Nitroxide Radicals in Aqueous Solutions.

ABSTRACT: The hydration structure of nitroxide radicals in aqueous solutions is elucidated by advanced ¹⁷ O hyperfine (hf) spectroscopy with support of quantum chemical calculations and MD simulations. A piperidine and a pyrrolidine-based nitroxide radical are compared and show clear differences in the preferred directionality of H-bond formation. We demonstrate that these scenarios are best represented in ¹⁷ O hf spectra, where in-plane coordination over σ${\sigma }$ -type H-bonding leads to little spin density transfer on the water oxygen and small hf couplings, whereas π${{\rm \pi }}$ -type perpendicular coordination generates much larger hf couplings. Quantitative analysis of the spectra based on MD simulations and DFT predicted hf parameters is consistent with a distributi

SUBMITTER: Hecker F 

PROVIDER: S-EPMC10107301 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature