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 ubiq-uitous 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 in-teractions 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 beta as compared to the symmetric pattern obtained by the existing gamma-encoded R-symmetry-based CSA/CSA correlation methods and allows a larger spectral area for data fitting. These features are beneficial for deter-mining the mutual orientation between the nuclear spin interaction tensors with improved accuracy.

Automated summary

The mutual orientation of nuclear spin interaction tensors is important for understanding the conformation and arrangement of molecules at an atomic level. This study presents a proton-detected 3D method that utilizes three techniques to manage homonuclear interactions and allows for improved accuracy in determining the mutual orientation between the nuclear spin interaction tensors. The method is beneficial for studying a wide range of substances due to the high sensitivity of proton NMR.