Relaxation effects in a system of a spin-1/2 nucleus coupled to a quadrupolar spin subjected to RF irradiation: evaluation of broadband decoupling schemes.

ABSTRACT

We have investigated the suitability and performance of various decoupling methods on systems in which an observed spin-1/2 nucleus I (13C or 15N) is scalar-coupled to a quadrupolar spin S (2H). Simulations and experiments have been conducted by varying the strength of the irradiating radiofrequency (RF) field, RF offset, relaxation times, and decoupling schemes applied in the vicinity of the S-spin resonance. The T1 relaxation of the quadrupolar spin has previously been shown to influence the efficiency of continuous wave (CW) decoupling applied on resonance in such spin systems. Similarly, the performance of broadband decoupling sequences should also be affected by relaxation. However, virtually all of the more commonly used broadband decoupling schemes have been developed without consideration of relaxation effects. As a consequence, it is not obvious how one selects a suitable sequence for decoupling quadrupolar nuclei with exotic relaxation behavior. Herein we demonstrate that, despite its simplicity, WALTZ-16 decoupling is relatively robust under a wide range of conditions. In these systems it performs as well as the more recently developed decoupling schemes for wide bandwidth applications such as GARP-1 and CHIRP-95. It is suggested that in macromolecular motional regimes, broadband deuterium decoupling can be achieved with relatively low RF amplitudes (500-700 Hz) using WALTZ-16 multiple pulse decoupling.