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The addition of stationary phases or sample modifiers can be used to modify the separation achievable in the diffusion domain of diffusion NMR experiments or provide information on the nature of the analyte-sample modifier interaction. Unfortunately, the addition of insoluble chromatographic stationary phases can lead to line broadening and degradation in spectral resolution, largely because of differences in magnetic susceptibility between the sample and the stationary phase. High-resolution magic angle spinning (HR-MAS) techniques can be used to remove this broadening. Here, we attempt the application of HR-MAS to size-exclusion chromatographic NMR with limited success. Observed diffusion coefficients for polymer molecular weight reference standards are shown to be larger than those obtained on static samples. Further investigation reveals that under HR-MAS it is possible to obtain reasonably accurate estimates of diffusion coefficients, using either full rotor synchronisation or sophisticated pulse sequences. The requirement for restricting the sample to the centre of the MAS rotor to ensure homogeneous magnetic and RF fields is also tested. Copyright © 2016 John Wiley & Sons, Ltd., (Copyright © 2016 John Wiley & Sons, Ltd.)

The use of chromatographic stationary phases or solvent modifiers to modulate diffusion properties in NMR experiments is now well established. Their use can be to improve resolution in the diffusion domain or to provide an insight into analyte-modifier interactions and, hence, the chromatography process. Here, we extend previous work using size-exclusion chromatographic stationary phases to the investigation of polymer mixtures. We demonstrate that similar diffusion modulation behaviour is observed with a size-exclusion chromatographic stationary phase that can be understood in terms of size-exclusion behaviour., (Copyright © 2014 John Wiley & Sons, Ltd.)