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Short and long range 2D 15N–15N NMR correlations among peptide groups by novel solid state dipolar mixing schemes

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Abstract

A recently developed homonuclear dipolar recoupling scheme, Adiabatic Linearly FREquency Swept reCOupling (AL FRESCO), was applied to record two-dimensional (2D) 15N–15N correlations on uniformly 15N-labeled GB1 powders. A major feature exploited in these 15N–15N correlations was AL FRESCO’s remarkably low RF power demands, which enabled seconds-long mixing schemes when establishing direct correlations. These 15N–15N mixing schemes proved efficient regardless of the magic-angle spinning (MAS) rate and, being nearly free from dipolar truncation effects, they enabled the detection of long-range, weak dipolar couplings, even in the presence of strong short-range dipolar couplings. This led to a connectivity information that was significantly better than that obtained with spontaneously proton-driven, 15N spin-diffusion experiments. An indirect approach producing long-range 15N–15N correlations was also tested, relying on short (ms-long) 1HN–1HN mixings schemes while applying AL FRESCO chirped pulses along the 15N channel. These indirect mixing schemes produced numerous long-distance Ni–Ni±n (n = 2 − 5) correlations, that might be useful for characterizing three-dimensional arrangements in proteins. Once again, these AL FRESCO mediated experiments proved more informative than variants based on spin-diffusion-based 1HN–1HN counterparts.

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Acknowledgements

This work was performed at the National High Magnetic Field Laboratory, which is supported by National Science Foundation Cooperative Agreement No. DMR-2128556 and the State of Florida. WL acknowledges a partial support from the National Science Foundation (Grant No. DBI-2051595). Supports from the Israel Science Foundation (Grant No. 1874/22) and the Perlman Family Foundation are gratefully acknowledged by LF. LF holds the Bertha and Isadore Gudelsky Professorial Chair and heads the Clore Institute for High-Field Magnetic Resonance Imaging and Spectroscopy (Weizmann Institute) whose support is also acknowledged.

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Authors and Affiliations

  1. National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL, 32304, USA

    Sungsool Wi & Lucio Frydman

  2. Key Laboratory of Magnetic Resonance in Biological Systems, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan, 430071, People’s Republic of China

    Conggang Li

  3. Department of Chemistry, University of Colorado at Denver, Denver, CO, 80217-3364, USA

    Karen Pham & Woonghee Lee

  4. Department of Chemical and Biological Physics, Weizmann Institute of Sciences, Rehovot, Israel

    Lucio Frydman

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  1. Sungsool Wi
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  4. Woonghee Lee
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Contributions

SW performed NMR experiments, data analysis, and drafted manuscript. KP and WL carried out peak assignments of two-dimensional NMR spectra. CL provided 15N,13C-labeled GB1 sample. LF provided idea discussion and final manuscript review. All authors reviewed the manuscript.

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Correspondence to Sungsool Wi or Lucio Frydman.

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Wi, S., Li, C., Pham, K. et al. Short and long range 2D 15N–15N NMR correlations among peptide groups by novel solid state dipolar mixing schemes. J Biomol NMR 78, 19–30 (2024). https://doi.org/10.1007/s10858-023-00429-0

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