19 F Magic Angle Spinning NMR Spectroscopy and Density Functional Theory Calculations of Fluorosubstituted Tryptophans: Integrating Experiment and Theory for Accurate Determination of Chemical Shift Tensors

The Journal of Physical Chemistry. B
Manman LuTatyana Polenova

Abstract

The 19F chemical shift is a sensitive NMR probe of structure and electronic environment in organic and biological molecules. In this report, we examine chemical shift parameters of 4F-, 5F-, 6F-, and 7F-substituted crystalline tryptophan by magic angle spinning (MAS) solid-state NMR spectroscopy and density functional theory. Significant narrowing of the 19F lines was observed under fast MAS conditions, at spinning frequencies above 50 kHz. The parameters characterizing the 19F chemical shift tensor are sensitive to the position of the fluorine in the aromatic ring and, to a lesser extent, the chirality of the molecule. Accurate calculations of 19F magnetic shielding tensors require the PBE0 functional with a 50% admixture of a Hartree-Fock exchange term, as well as taking account of the local crystal symmetry. The methodology developed will be beneficial for 19F-based MAS NMR structural analysis of proteins and protein assemblies.

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Citations

Aug 23, 2019·Journal of Biomolecular NMR·Manman LuAngela M Gronenborn
Sep 19, 2018·Angewandte Chemie·Mingzhang WangTatyana Polenova
Mar 16, 2019·Journal of the American Chemical Society·Manman LuTatyana Polenova
Feb 6, 2019·Journal of Chemical Theory and Computation·Sean T Holmes, Robert W Schurko

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