On the potential of Fourier-encoded saturation transfers for sensitizing solid-state magic-angle spinning NMR...

Chemical exchange saturation transfer (CEST) is widely used for enhancing the solution nuclear magnetic resonance (NMR) signatures of magnetically dilute spin pools, in particular, species at low concentrations undergoing chemical exchanges with an abundant spin pool. CEST's main feature involves encoding and then detecting weak NMR signals of the magnetically dilute spin pools on a magnetically abundant spin pool of much easier detection, for instance, the protons of H₂O. Inspired by this method, we propose and exemplify a methodology to enhance the sensitivity of magic-angle spinning (MAS) solid-state NMR spectra. Our proposal uses the abundant ¹H reservoir arising in organic solids as the magnetically abundant spin pool and relies on proton spin diffusion in lieu of chemical exchange to mediate polarization transfer between a magnetically dilute spin pool and this magnetically abundant spin reporter. As an initial test of this idea, we target the spectroscopy of naturally abundant ¹³C and rely on a Fourier-encoded version of the CEST experiment for achieving broadbandness in coordination with both MAS and heteronuclear decoupling, features normally absent in CEST. Arbitrary evolutions of multiple ¹³C sites can, thus, be imprinted on the entire ¹H reservoir, which is subsequently detected. Theoretical predictions suggest that orders-of-magnitude signal enhancements should be achievable in this manner, on the order of the ratio between the ¹³C and the ¹H reservoirs' abundances. Experiments carried out under magic-angle spinning conditions evidenced 5-10× gains in signal amplitudes. Further opportunities and challenges arising in this Fourier-encoded saturation transfer MAS NMR approach are briefly discussed.