Journal of Magnetic Resonance
Volume 178, Issue 2 , February 2006, Pages 212-219
New opportunities for double rotation NMR of half-integer quadrupolar nuclei
Arno P.M. Kentgens a, Ernst R.H. van Eck, T.G. Ajithkumar, Tiit Anupõld, Jaan Past, Andres Reinhold and Ago Samoson
a Department of Physical Chemistry/Solid-State NMR, Institute for Molecules and Materials, Radboud University Nijmegen, Toernooiveld 1, The Netherlands
b National Institute of Chemical Physics and Biophysics, 12618 Tallinn, Estonia
A combined approach is presented which expands the applicability of double rotation (DOR) by overcoming its most prominent disadvantages: spinning stability and sensitivity. A new design using air-bearings for the inner rotor and a computer-assisted start-up procedure allows DOR operation over in principle unlimited time at outer rotor speeds of up to 2000 Hz. Sensitivity enhancement of the DOR experiment is achieved by applying amplitude-modulated adiabatic pulses such as the double frequency sweep (DFS) before pulse excitation. Repeating the DFS enhancement and signal readout several times without allowing for spin–lattice relaxation leads to sensitivity enhancements of a factor 3 for 27Al in various minerals. As a result, it becomes possible to study low sensitivity quadrupolar nuclei and various long duration 2D measurements can be performed routinely. Spinning is adequate to suppress residual homonuclear dipolar couplings in the spectral dimension of typical quadrupolar spin systems. In 2D-exchange spectroscopy, however, homonuclear correlation can still be established through dipolar–quadrupolar cross-terms.
Keywords: DOR; Repetitive DFS; Quadrupolar nuclei; MQDOR; Homonuclear correlation