On the Observation of ¹⁴N Quadrupole Resonance Transitions in Water Proton NMR Relaxometry Dispersion Curves: The Case of a Labile NH Grouping in a Semirigid Molecular Moiety

Abstract

The electric field gradient tensor (considered here at the level of a nitrogen nucleus) can be described by two parameters: the largest element in the (X,Y,Z) principal axis system, denoted by VZZ (leading to the nuclear quadrupole coupling), and the asymmetry parameter η = (|VYY | – |VXX |)/|VZZ | with |VZZ | > |VYY | > |VXX |. The frequencies of the three nitrogen-14 nuclear quadrupole resonance (NQR) transitions depend on both parameters but, for sensitivity reasons, their determination may be especially difficult and time consuming. For a partly rigid NH grouping with a labile proton, water nuclear magnetic resonance (NMR) relaxometry curves may exhibit these three transitions (dubbed quadrupolar dips or quadrupole relaxation enhancement (QRE)), provided that the NH grouping belongs to a moiety possessing a sufficient degree of ordering. Their line shape leads to the correlation time describing mainly the motion of the NH grouping (the proton of which being in exchange with water protons), and their amplitude can be interpreted in terms of an effective NH distance. This approach is applied to a hydrogel, where separate NQR lines are observed for the different types of water existing in this system. Furthermore, the analysis of experimental data allows one to determine the nuclear quadrupole coupling in the protonated and deprotonated forms of this molecular moiety involving a labile NH grouping.