Rapid Acquisition of 14N Solid‐State NMR Spectra with Broadband Cross Polarization. Issue 48 (10th October 2013)

• Record Type: Journal Article
• Authors: Harris, Kristopher J.; Veinberg, Stanislav L.; Mireault, Christopher R.; Lupulescu, Adonis; Frydman, Lucio; Schurko, Robert W.
• Is Part Of: Chemistry. Volume 19:Issue 48(2013)
• Page Start: 16469
• Page End: 16475
• Publication Date: 2013-10-10
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201301862
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Nitrogen is an element of utmost importance in chemistry, biology and materials science. Of its two NMR‐active isotopes, <sup>14</sup>N and <sup>15</sup>N, solid‐state NMR (SSNMR) experiments are rarely conducted upon the former, due to its low gyromagnetic ratio (<italic>γ</italic>) and broad powder patterns arising from first‐order quadrupolar interactions. In this work, we propose a methodology for the rapid acquisition of high quality <sup>14</sup>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 <sup>14</sup>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., <sup>1</sup>H). The <bold>BR</bold>oadband <bold>A</bold>diabatic <bold>IN</bold>version <bold>C</bold>ross‐<bold>P</bold>olarization (<bold>BRAIN–CP</bold>) pulse sequence is combined with other elements for efficient acquisition of ultra‐wideline SSNMR spectra, including <bold>W</bold>ideband <bold>U</bold>niform‐<bold>R</bold>ate <bold>S</bold>mooth‐<bold>T</bold>runcation (<bold>WURST</bold>) pulses for broadband refocusing, <bold>C</bold>arr–<bold>P</bold>urcell <bold>M</bold>eiboom–<bold>G</bold>ill (<bold>CPMG</bold>) echo trains for <italic>T</italic><sub>2</sub>‐driven S/N enhancement, and frequency‐stepped acquisitions. The feasibility of utilizing the BRAIN–CP/WURST–CPMG sequence is tested for <sup>14</sup>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 <sup>14</sup>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.</p> </abstract>