A robust technique for two-dimensional separation of undistorted chemical-shift anisotropy powder patterns in magic-angle-spinning NMR

J Magn Reson. 2002 Mar;155(1):15-28. doi: 10.1006/jmre.2002.2503.

Abstract

A robust magic-angle-spinning experiment for separating undistorted, quasi-static chemical-shift powder patterns is presented. It is derived from the technique of R. Tycko, G. Dabbagh, and P. Mirau (1989, J. Magn. Reson. 85, 265), but uses 360 degrees instead of 180 degrees pulses. In combination with a suitable phase sequence, this makes the spectral patterns very insensitive to pulse-length errors and other imperfections, as demonstrated both experimentally and theoretically. This method, termed separation of undistorted powder patterns by effortless recoupling (SUPER), can be used at standard spinning speeds, between 2.5 and 5 kHz, and with standard radiofrequency power levels (in particular, for protons, a decoupling field strength gammaB(1)/2pi of less than 80 kHz). No significant artifacts are observed even for samples extending to the ends of the radiofrequency coil. The method has been applied to samples containing various sp(2)- and sp(3)-hybridized carbon sites. Even for the methylene groups in polyethylene, a system with very strong C-H and H-H dipolar couplings and only moderate chemical-shift anisotropy (CSA), a useful CSA powder pattern has been obtained. With a CSA scaling factor of 0.155, accuracies of +/-5, +/-3, and +/-1 ppm of the principal values can be achieved for protonated aromatic carbons, unprotonated sp(2)-hybridized groups, and aliphatic sites, respectively. Examples of CSA-based assignment of COOC vs other COO or CON groups, and of aromatic vs olefinic C=C carbons are shown, for both small molecules and polymers.