Rational design of 19F NMR labelling sites to probe protein structure and interactions

Abstract Proteins are investigated in increasingly more complex biological systems, where 19F NMR is proving highly advantageous due to its high gyromagnetic ratio and background-free spectra. Its application has, however, been hindered by limited chemical shift dispersions and an incomprehensive re...

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Main Authors: Julian O. Streit, Sammy H. S. Chan, Saifu Daya, John Christodoulou
Format: Article
Language:English
Published: Nature Portfolio 2025-05-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-59105-6
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author Julian O. Streit
Sammy H. S. Chan
Saifu Daya
John Christodoulou
author_facet Julian O. Streit
Sammy H. S. Chan
Saifu Daya
John Christodoulou
author_sort Julian O. Streit
collection DOAJ
description Abstract Proteins are investigated in increasingly more complex biological systems, where 19F NMR is proving highly advantageous due to its high gyromagnetic ratio and background-free spectra. Its application has, however, been hindered by limited chemical shift dispersions and an incomprehensive relationship between chemical shifts and protein structure. Here, we exploit the sensitivity of 19F chemical shifts to ring currents by designing labels with direct contact to a native or engineered aromatic ring. Fifty protein variants predicted by AlphaFold and molecular dynamics simulations show 80–90% success rates and direct correlations of their experimental chemical shifts with the magnitude of the engineered ring current. Our method consequently improves the chemical shift dispersion and through simple 1D experiments enables structural analyses of alternative conformational states, including ribosome-bound folding intermediates, and in-cell measurements of protein-protein interactions and thermodynamics. Our strategy thus provides a simple and sensitive tool to extract residue contact restraints from chemical shifts for previously intractable systems.
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spelling doaj-art-201483509aee435ba7ccfa3f9cd12da72025-08-20T03:09:20ZengNature PortfolioNature Communications2041-17232025-05-0116111510.1038/s41467-025-59105-6Rational design of 19F NMR labelling sites to probe protein structure and interactionsJulian O. Streit0Sammy H. S. Chan1Saifu Daya2John Christodoulou3Institute of Structural and Molecular Biology, University College London and Birkbeck CollegeInstitute of Structural and Molecular Biology, University College London and Birkbeck CollegeInstitute of Structural and Molecular Biology, University College London and Birkbeck CollegeInstitute of Structural and Molecular Biology, University College London and Birkbeck CollegeAbstract Proteins are investigated in increasingly more complex biological systems, where 19F NMR is proving highly advantageous due to its high gyromagnetic ratio and background-free spectra. Its application has, however, been hindered by limited chemical shift dispersions and an incomprehensive relationship between chemical shifts and protein structure. Here, we exploit the sensitivity of 19F chemical shifts to ring currents by designing labels with direct contact to a native or engineered aromatic ring. Fifty protein variants predicted by AlphaFold and molecular dynamics simulations show 80–90% success rates and direct correlations of their experimental chemical shifts with the magnitude of the engineered ring current. Our method consequently improves the chemical shift dispersion and through simple 1D experiments enables structural analyses of alternative conformational states, including ribosome-bound folding intermediates, and in-cell measurements of protein-protein interactions and thermodynamics. Our strategy thus provides a simple and sensitive tool to extract residue contact restraints from chemical shifts for previously intractable systems.https://doi.org/10.1038/s41467-025-59105-6
spellingShingle Julian O. Streit
Sammy H. S. Chan
Saifu Daya
John Christodoulou
Rational design of 19F NMR labelling sites to probe protein structure and interactions
Nature Communications
title Rational design of 19F NMR labelling sites to probe protein structure and interactions
title_full Rational design of 19F NMR labelling sites to probe protein structure and interactions
title_fullStr Rational design of 19F NMR labelling sites to probe protein structure and interactions
title_full_unstemmed Rational design of 19F NMR labelling sites to probe protein structure and interactions
title_short Rational design of 19F NMR labelling sites to probe protein structure and interactions
title_sort rational design of 19f nmr labelling sites to probe protein structure and interactions
url https://doi.org/10.1038/s41467-025-59105-6
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