Perfecting band selective homo-decoupling for decoupling two signals coupled within the same band

Abstract

Recently, pure shift NMR methods have delivered ultrahigh resolution broadband proton NMR spectra that display singlet peak per chemical site. BASH/HOBS (band selective homo-decoupling/homonuclear band selective) decoupling is the only method that provides singlet only spectrum for a selected signal or a group of signals with a sensitivity higher than regular proton NMR, and an order of magnitude higher than broadband pure shift techniques. It is this aspect that makes this technique important. In the present work, we show that perfect echo (PE) when combined with band selective homo-decoupling (BASHD) permits increasing the bandwidth of the BASH/HOBS decoupling resulting in reduced experimental time for this class of experiments. Using new PE-BASHD technique two closely resonating coupled signals could be decoupled in a single experiment which otherwise demands two separate BASHD experiments. In polypeptides, it also allows decoupling of Hα and HN signals simultaneously from each other as well as from the side chain protons reducing experimental time. Further, pseudo 2D based PE-BASHD scheme provides spectrum superior to the real-time BASHD spectrum when applied to closely resonating coupled signals. Numerical simulation as well as experimental results indicate that the PE-BASHD sequence display good quality singlet only spectrum even in the presence of moderate strong coupling.