Proton nutation spectroscopy. Application to the quantitation of water in a kaolinite sample

[Display omitted] •Fourier transform methodology for obtaining multi-line spectra from nutation curves.•Improved spectra can be obtained by a least-squares analysis of nutation curves.•Line separation depends on the amplitude of the radio-frequency field.•The linewidth provides spin relaxation information.•Application to water in a kaolinite sample revealing unexpectedly two peaks. Nutation consists in monitoring the motion of nuclear magnetization under the application of a radio-frequency field. Depending on the amplitude of the rf field, the nutation frequency may be sensitive to the two longitudinal and transverse relaxation rates R1 and R2, hence the possibility of differentiating species having the same resonance frequency in the laboratory frame (the Larmor frequency) but differing by their relaxation rates, as it may occur for the composite proton NMR signal of water in complex systems. Thus, Fourier transform of the nutation curve should provide separate peaks associated with the different species involved in a composite classical NMR signal. As nutation peaks may be close to zero frequency (or even at zero frequency), their full observation requires a complex Fourier transform. This implies a second nutation curve, de-phased by 90° with respect to the first one, achieved here by a second nutation experiment preceded by a 90° hard pulse. Eventually, more accurate parameters are obtained by a non-linear least-squares analysis of the simple nutation experiment. This methodology is applied to water in a natural clay (kaolinite) and reveals the unexpected presence of two peaks which can be characterized by the relaxation rates derived from the line-widths of the nutation signals.