Can proton-proton recoupling in fully protonated solids provide quantitative, selective and efficient polarization transfer?

Dipolar recoupling sequences have been used to probe spatial proximity of nuclear spins and were traditionally designed to probe rare spins such as C-13 and/or N-15 nuclei. The multi-spin dipolar-coupling net-work of the rare spins is weak due to smaller couplings and large chemical shift dispersion. Therefore, the recoupling approaches were tailored to design offset compensated or broadband sequences. In contrast, protons have a substantially stronger dipolar-coupling network and much narrower chemical shift range. Broadband recoupling sequences such as radio-frequency driven recoupling (RFDR), back-to-back (BABA), and lab frame proton-proton spin diffusion have been routinely used to characterize the structures of protein/macromolecules and small molecules. Recently selective H-1 -H-1 recoupling sequences have been proposed that combine chemical shift offset of the resolved proton spectrum (at fast MAS) with first- and second-order dipolar recoupling Hamiltonians to obtain quantitative and qualitative proton distances, respectively. Herein, we evaluate the performances of broadband and selective proton recoupling sequences such as finite pulse RFDR (fp-RFDR), band-selective spectral spin diffusion (BASS-SD), second-order cross-polarization (SOCP), and selective recoupling of proton (SERP) in terms of the selectivity and efficiency of H-1 -H-1 polarization transfers in a dense network of proton spins and explore the possibility of measuring H-1 -H-1 distances. We use theoretical considerations, numerical simulations, and experiments to support the distinct advantages and disadvantages of each recoupling sequence. Experiments were performed on L-histidine center dot HCl center dot H2O at a MAS frequency of 71.43 kHz. This study rationalizes the proper selection of H-1 -H-1 recoupling sequences when working with fully protonated solids. (C) 2020 Elsevier Inc. All rights reserved.