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Date for A fast magic-angle spinning three-dimensional NMR experiment for simultaneously probing H-H and N-H proximities in solids

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A fast magic-angle spinning (MAS) solid-state NMR experiment is presented that combines 1H Double-Quantum (DQ) and 14N-1H HMQC (Heteronuclear Multiple-Quantum Coherence) pulse-sequence elements, so as to simultaneously probe H-H and N-H proximities in molecular solids.

Description

The proposed experiment can be employed in both two-dimensional (2D) and three-dimensional (3D) versions: firstly, a 2D 14N HMQC-filtered 1H-DQ experiment provides specific DQ-SQ correlation peaks for proton pairs that are in close proximities to the nitrogen sites, thereby achieving spectral filtration.

Secondly, a proton-detected three-dimensional (3D) 1H(DQ)-14N(SQ)-1H(SQ) experiment correlates 1H(SQ)-1H(DQ) chemical shifts with 14N shifts such that longer range N…H-H correlations are observed between protons and nitrogen atoms with internuclear NH distances exceeding 3 Å. Both 2D and 3D versions of the proposed experiment are demonstrated for an amino acid hydrochloride salt, L-histidine.HCl.H2O, and a DNA nucleoside, guanosine.2H2O.

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In the latter case, the achieved spectral filtration ensures that DQ cross peaks are only observed for guanine NH and CH8 1H resonances and not ribose and water 1H resonances, thus providing insight into the changes in the solid-state structure of this hydrate that occur over time – significant changes are observed in the NH and NH2 1H chemical shifts as compared to the freshly recrystallized sample previously studied by Reddy et al, Cryst.

Growth Des. 15, 5945, 2015.<br><br>L-Histidine.HCl Figure 2 1D Single pulse NMR data (recorded on 05/10/2015) 2D 1H DQ-SQ Correlation NMR data (recorded on 05/10/2015) 2D 1H(DQ)- 14N(SQ)-1H(SQ) Correlation NMR data (recorded on 05/10/2015) Figure 3 2D 1H(DQ)- 14N(SQ) HMQC Correlation NMR data (recorded on 07/10/2015) 3D 1H(DQ)- 14N(SQ)-1H(SQ) Correlation NMR data (recorded on 13/10/2015) Figure S3 DFT refined crystallography information file (cif) (performed on 02/10/2015) NMR shielding calculations in .Magres format (performed on 02/10/2015) Experimental powder X-ray diffraction data (recorded on 01/01/2016) Guanosine.2H2O Figure 5 TGA-DSC data in .xls format (recorded on 29/07/2014 and 09/02/2016) Figure 6 1D Single pulse NMR data (recorded on 05/10/2015) 2D 1H DQ-SQ Correlation NMR data (recorded on 05/10/2015) 2D 1H(DQ)- 14N(SQ)-1H(SQ) Correlation NMR data (recorded on 05/10/2015) Figure 7 2D 1H(DQ)- 14N(SQ) HMQC Correlation NMR data (recorded on 05/10/2015) 3D 1H(DQ)- 14N(SQ)-1H(SQ) Correlation NMR data (recorded on 05/10/2015) Figure S4 1D 13C CPMAS NMR data (recorded on 13/02/2015, 16/04/2015 and 06/04/2016) Experimental powder X-ray diffraction data (recorded on 22/07/2016)

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