Determination of the mutual orientation between proton CSA tensors mediated through band-selective 1H–1H recoupling under fast MAS

The mutual orientation of nuclear spin interaction tensors provides critical information on the conformation and arrangement of molecules in chemicals, materials, and biological systems at an atomic level. Proton is a ubiquitous and important element in a variety of substances, and its NMR is highly sensitive due to their virtually 100% natural abundance and large gyromagnetic ratio. Nevertheless, the measurement of mutual orientation between the ¹H CSA tensors has remained largely untouched in the past due to strong ¹H–¹H homonuclear interactions in a dense network of protons. In this study, we have developed a proton-detected 3D ¹H CSA/¹H CSA/¹H CS correlation method that utilizes three techniques to manage homonuclear interactions, namely fast magic-angle spinning, windowless C-symmetry-based CSA recoupling (windowless-ROCSA), and a band-selective ¹H–¹H polarization transfer. The asymmetric ¹H CSA/¹H CSA correlated powder patterns produced by the C-symmetry-based methods are highly sensitive to the sign and asymmetry parameter of the ¹H CSA, and the Euler angle β as compared to the symmetric pattern obtained by the existing γ-encoded R-symmetry-based CSA/CSA correlation methods and allows a larger spectral area for data fitting. These features are beneficial for determining the mutual orientation between the nuclear spin interaction tensors with improved accuracy.