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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