Real-time homonuclear broadband and band-selective decoupled pure-shift ROESY.
Unambiguous spectral assignments in (1)H solution-state NMR are central, for accurate structural elucidation of complex molecules, which is often hampered by signal overlap, primarily because of scalar coupling multiplets, even at typical high magnetic fields. The recent advances in homodecoupling methods have shown powerful means of achieving high resolution pure-shift (1)H spectra in 1D and also in 2D J-correlated experiments, by effectively collapsing the multiplet structures. The present work extends these decoupling strategies to through-space correlation experiments as well and describes two new pure-shift ROESY pulse schemes with homodecoupling during acquisition, viz., homodecoupled broadband (HOBB)-ROESY and homodecoupled band-selective (HOBS)-ROESY. Furthermore, the ROESY blocks suppress the undesired interferences of TOCSY cross peaks and other offsets. Despite the reduced signal sensitivity and prolonged experimental times, the HOBB-ROESY is particularly useful for molecules that exhibit an extensive scalar coupling network spread over the entire (1)H chemical shift range, such as natural/synthetic organic molecules. On the other hand, the HOBS-ROESY is useful for molecules that exhibit well-separated chemical shift regions such as peptides (NH, Hα and side-chain protons). The HOBS-ROESY sensitivities are comparable with the conventional ROESY, thereby saves the experimental time significantly. The power of these pure-shift ROESY sequences is demonstrated for two different organic molecules, wherein complex conventional ROE cross peaks are greatly simplified with high resolution and sensitivity. The enhanced resolution allows deriving possibly more numbers of ROEs with better accuracy, thereby facilitating superior means of structural characterization of medium-size molecules.
Centre for NMR and Structural Chemistry, CSIR-Indian Institute of Chemical Technology, Uppal Road, Tarnaka, Hyderabad, 500 007, India; School of Chemistry, University of Hyderabad, Hyderabad, 500 046, India.
Veera Mohana Rao
VM
Kakita
Jagadeesh
J
Bharatam
D000465:Algorithms; D003199:Computer Systems; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D012815:Signal Processing, Computer-Assisted
band selective; broadband; direct dimension; homodecoupling; real-time pure-shift ROESY; structure elucidation