A Slowly Relaxing Rigid Biradical for Efficient Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy: Expeditious Characterization of Functional Group Manipulation in Hybrid Materials
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- 作者：Alexandre Zagdoun ; Gilles Casano ; Olivier Ouari ; Giuseppe Lapadula ; Aaron J. Rossini ; Moreno Lelli ; Mathieu Baffert ; David Gajan ; Laurent Veyre ; Werner E. Maas ; Melanie Rosay ; Ralph T. Weber ; Chlo茅 Thieuleux ; Christophe Coperet ; Anne Lesage ; Paul Tordo ; Lyndon Emsley
- 刊名：The Journal of the American Chemical Society
- 出版年：2012
- 出版时间：February 1, 2012
- 年：2012
- 卷：134
- 期：4
- 页码：2284-2291
- 全文大小：429K
- 年卷期：v.134,no.4(February 1, 2012)
- ISSN：1520-5126
文摘
A new nitroxide-based biradical having a long electron spin鈥搇attice relaxation time (T1e) has been developed as an exogenous polarization source for DNP solid-state NMR experiments. The performance of this new biradical is demonstrated on hybrid silica-based mesostructured materials impregnated with 1,1,2,2-tetrachloroethane radical containing solutions, as well as in frozen bulk solutions, yielding DNP enhancement factors (蔚) of over 100 at a magnetic field of 9.4 T and sample temperatures of 100 K. The effects of radical concentration on the DNP enhancement factors and on the overall sensitivity enhancements (危鈥?/sup>) are reported. The relatively high DNP efficiency of the biradical is attributed to an increased T1e, which enables more effective saturation of the electron resonance. This new biradical is shown to outperform the polarizing agents used so far in DNP surface-enhanced NMR spectroscopy of materials, yielding a 113-fold increase in overall sensitivity for silicon-29 CPMAS spectra as compared to conventional NMR experiments at room temperature. This results in a reduction in experimental times by a factor >12鈥?00, making the acquisition of 13C and 15N one- and two-dimensional NMR spectra at natural isotopic abundance rapid (hours). It has been used here to monitor a series of chemical reactions carried out on the surface functionalities of a hybrid organic鈥搒ilica material.