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research article

Dynamic nuclear polarisation enhanced N-14 overtone MAS NMR spectroscopy

Rossini, Aaron J.  
•
Emsley, Lyndon  
•
O'Dell, Luke A.
2014
Physical Chemistry Chemical Physics

Dynamic nuclear polarisation (DNP) has been used to obtain magic angle spinning (NOT)-N-14 (nitrogen-14 overtone) solid-state NMR spectra from several model amino acids, with both direct and indirect observation of the (NOT)-N-14 signal. The crystalline solids were impregnated with biradical solutions of organic liquids that do not dissolve the crystalline phase. The bulk phase was then polarized via H-1 spin diffusion from the highly-polarized surface H-1 nuclei, resulting in H-1 DNP signal enhancements of around two orders of magnitude. Cross polarisation from H-1 nuclei directly to the N-14 overtone transition is demonstrated under magic angle spinning, using a standard pulse sequence with a relatively short contact time (on the order of 100 ms). This method can be used to acquire N-14 overtone MAS powder patterns that match closely with simulated line shapes, allowing isotropic chemical shifts and quadrupolar parameters to be measured. DNP enhancement also allows the rapid acquisition of D-2 (NOT)-N-14 heteronuclear correlation spectra from natural abundance powder samples. H-1-(NOT)-N-14 HETCOR and C-13-(NOT)-N-14 HMQC pulse sequences were used to observe all single-bond H-N and C-N correlations in histidine hydrochloride monohydrate, with the spectra obtained in a matter of hours. Due to the high natural abundance of the N-14 isotope (99.6%) and the advantages of observing the overtone transition, these methods provide an attractive route to the observation of C-N correlations from samples at natural isotopic abundance and enable the high resolution measurement of N-14 chemical shifts and quadrupolar interaction parameters.

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Type
research article
DOI
10.1039/c4cp00590b
Web of Science ID

WOS:000337127100028

Author(s)
Rossini, Aaron J.  
Emsley, Lyndon  
O'Dell, Luke A.
Date Issued

2014

Published in
Physical Chemistry Chemical Physics
Volume

16

Issue

25

Start page

12890

End page

12899

Editorial or Peer reviewed

REVIEWED

Written at

OTHER

EPFL units
LRM  
Available on Infoscience
January 8, 2015
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/109958
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