Chemical Sciences: A Manual for CSIR-UGC National Eligibility Test for Lectureship and JRF/Magic angle spinning

In nuclear magnetic resonance, magic angle spinning (MAS) is a technique often used to perform experiments in solid-state NMR spectroscopy.

By spinning the sample (usually at a frequency of 1 to 70 kHz) at the magic angle θm (ca. 54.74°, where cos2θm=1/3) with respect to the direction of the magnetic field, the normally broad lines become narrower, increasing the resolution for better identification and analysis of the spectrum.

In any condensed phase, a nuclear spin experiences a great number of interactions. The main three interactions (dipolar, chemical shift anisotropy, quadrupolar) often lead to very broad and featureless lines. However, these three interactions in solids are time-dependent and can be averaged by MAS. The nuclear dipole-dipole interaction, between magnetic moments of nuclei averages to zero only at the magic angle, θm. The chemical shift anisotropy, a nuclear-electron interaction, averages to a non-zero value. The quadrupolar interaction is only partially averaged by MAS leaving a residual secondary quadrupolar interaction. In liquids, e.g. a solution of an organic compound, most of these interactions will average out because of the rapid time-averaged molecular motion that occurs. This orientation averaging in solution is mimicked by MAS of a solid. This causes the signal to become much narrower, giving rise to the isotropic value (which is of interest for structural determination of solid materials and compounds) and spinning sidebands which occur at multiples of the spinning speed and can be used to determine the chemical shift anisotropy of the nuclei.

The physical spinning of the sample is achieved via an air turbine mechanism. These turbines (or rotors) come in a variety of diameters (outside diameter), from 2.0-15.0 mm, and are usually spun on air or nitrogen gas. The rotors are made from a number of different materials such as ceramics e.g. zirconia, silicon nitride or polymers such as poly-methyl-methacrylate (PMMA), polyoxymethylene (POM). The cylindrical rotors are axially symmetric about the axis of rotation. Samples are packed into the rotors and these are then sealed with a single or double end cap. These caps are made from number of different materials e.g. Kel-F, Vespel, zirconia or boron nitride depending on the application required.