Excitation of delocalized long-lived states of aliphatic protons at low and high magnetic fields.

Abstract

Long-lived states (LLSs) can be excited in geminal protons of aliphatic chains by mono- or poly-chromatic spin-lock-induced crossings (SLICs), i.e., by application of one or more selective radio frequency (RF) fields, to create delocalized population imbalances between states belonging to different symmetry under spin permutations. At low fields (in this work at 1.4 T or 60 MHz for proton NMR), these experiments are challenging due to the proximity of the chemical shifts and the need to consider the full untruncated $J$ -coupling Hamiltonian. Five molecules were studied in this work: ethanolamine, lysine, vitamin B1, metronidazole, and phenoxyethylamine (POEA). For POEA and metronidazole, the LLSs are reported for the first time. Measurements were carried out at low and high magnetic fields (1.4 and 11.7 T or 60 and 500 MHz for protons) using 60 MHz Magritek and 500 MHz Bruker NEO spectrometers. The rates $R_{\mathrm{LLS}}=1/T_{\mathrm{LLS}}$ and $R_1=1/T_1$ were determined using monochromatic SLIC excitation at both fields. We describe strategies for optimizing SLIC conditions in cases where the signals of neighboring CH₂ groups are relatively close to each other.