Fourier Transform Study of NMR Spin–Lattice Relaxation by “Progressive Saturation”

TLDR

Repetitive strong RF pulses create a steady state where pulse effects balance spin relaxation. Under suitable pulse conditions the free‑induction signal decays exponentially with a time constant equal to T1, and Fourier transforming the transient response yields high‑resolution spectra and T1 values for individual resonances while repeated accumulation enhances sensitivity. The method was applied to eight ^13C resonances in 3,5‑dimethylcyclohex‑2‑ene‑1‑one, yielding T1 values from 2.6 to 39 s that agree with conventional 180°–t–90° measurements.

Abstract

When a nuclear spin system is subjected to a repetitive sequence of strong radiofrequency pulses, a steady state is established where there is a dynamic balance between the effect of the pulses and spin relaxation. Under certain readily satisfied pulse conditions, the deviation of the intensity of the free induction signal from its thermal equilibrium value is an exponential function of the pulse interval with time constant equal to the spin–lattice relaxation time. The determination is unaffected by spin–spin relaxation provided that the interval between pulses is long enough to permit all transverse components of magnetization to be eliminated, and provided precautions are taken to inhibit spin-echo formation. Through Fourier transformation of the transient response, high resolution spectra with many component resonances may be studied, and the spin–lattice relaxation times of the individual lines determined. The technique lends itself particularly well to repeated accumulation of the transient signal for the purpose of improving sensitivity. It has been applied to the problem of determining the spin–lattice relaxation rates of the eight different carbon-13 resonances in 3,5-dimethylcyclohex-2-ene-1-one. The results span a range from 2.6 to 39 sec, and are in good agreement with those obtained by applying 180°–t–90° sequences to the same sample.