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Rapid Acquisition of 14 N Solid‐State NMR Spectra with Broadband Cross Polarization
Author(s) -
Harris Kristopher J.,
Veinberg Stanislav L.,
Mireault Christopher R.,
Lupulescu Adonis,
Frydman Lucio,
Schurko Robert W.
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201301862
Subject(s) - spectral line , nmr spectra database , polarization (electrochemistry) , solid state nuclear magnetic resonance , chemistry , pulse sequence , nuclear magnetic resonance spectroscopy , physics , analytical chemistry (journal) , nuclear magnetic resonance , chromatography , astronomy
Abstract Nitrogen is an element of utmost importance in chemistry, biology and materials science. Of its two NMR‐active isotopes, 14 N and 15 N, solid‐state NMR (SSNMR) experiments are rarely conducted upon the former, due to its low gyromagnetic ratio ( γ ) and broad powder patterns arising from first‐order quadrupolar interactions. In this work, we propose a methodology for the rapid acquisition of high quality 14 N SSNMR spectra that is easy to implement, and can be used for a variety of nitrogen‐containing systems. We demonstrate that it is possible to dramatically enhance 14 N NMR signals in spectra of stationary, polycrystalline samples (i.e., amino acids and active pharmaceutical ingredients) by means of broadband cross polarization (CP) from abundant nuclei (e.g., 1 H). The BR oadband A diabatic IN version C ross‐ P olarization ( BRAIN–CP ) pulse sequence is combined with other elements for efficient acquisition of ultra‐wideline SSNMR spectra, including W ideband U niform‐ R ate S mooth‐ T runcation ( WURST ) pulses for broadband refocusing, C arr– P urcell M eiboom– G ill ( CPMG ) echo trains for T 2 ‐driven S/N enhancement, and frequency‐stepped acquisitions. The feasibility of utilizing the BRAIN–CP/WURST–CPMG sequence is tested for 14 N, with special consideration given to (i) spin‐locking integer spin nuclei and maintaining adiabatic polarization transfer, and (ii) the effects of broadband polarization transfer on the overlapping satellite transition patterns. The BRAIN–CP experiments are shown to provide increases in signal‐to‐noise ranging from four to ten times and reductions of experimental times from one to two orders of magnitude compared to analogous experiments where 14 N nuclei are directly excited. Furthermore, patterns acquired with this method are generally more uniform than those acquired with direct excitation methods. We also discuss the proposed method and its potential for probing a variety of chemically distinct nitrogen environments.