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Updated: Mar 13, 2026

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Hadamard Homonuclear Broadband Decoupled TOCSY NMR: Improved Efficacy in Detecting Long-range Chemical Shift
Veera Mohana Rao Kakita1, Ramakrishna V Hosur1,2
1UM-DAE-Centre for Excellence in Basic Sciences, University of Mumbai, Kalina Campus, Santa Cruz, Mumbai, 400 098, India.
Abstract:
The importance of Hadamard encoding pulses in one-dimensional pure shift yielded by the chirp excitation version of selective total correlation spectroscopy (1D PSYCHE-TOCSY) experiments is discussed for chemical-shift analysis of complex natural products at ultrahigh resolution. Herein, we adapted Hn Hadamard matrices to 1D PSYCHE-TOCSY and observed an overall circa square root of n-fold enhancement in the signal-to-noise (S/N) ratio when compared to conventional 1D PSYCHE-TOCSY recorded by refocusing only one spin at a time. This enhancement in S/N facilitates the observation of very weak long-range chemical-shift correlations from Hadamard-encoded PSYCHE-TOCSY (HE-PSYCHE-TOCSY). The proposed method will have a significant impact on structure determination of complex isolated/ synthetic natural products.
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