화학공학소재연구정보센터
Journal of Chemical Physics, Vol.117, No.4, 1700-1707, 2002
C-13 nuclear Overhauser polarization nuclear magnetic resonance in rotating solids: Replacement of cross polarization in uniformly C-13 labeled molecules with methyl groups
A new C-13 polarization technique in solids is presented on the basis of a recently proposed C-13-C-13 recoupling sequence [C-13-H-1 dipolar-assisted rotational resonance (DARR), K. Takegoshi, S. Nakamura, and T. Terao, Chem. Phys. Lett. 344, 631 (2001)] operative under fast magic angle spinning (MAS), in which a rf field is applied to H-1 with a rotary resonance condition but none to C-13. The H-1 irradiation in DARR saturates H-1 signals, leading to the C-13 signal enhancement due to the nuclear Overhauser effect for fast rotating methyl groups, if any. If we use a uniformly C-13 labeled sample, C-13-C-13 polarization transfer enhanced by DARR successively distributes the enhanced methyl carbon polarization to the other C-13 spins, leading to uniform enhancement for all C-13 spins even under very fast MAS. In uniformly C-13 labeled rotating samples, the enhancement factor in cross polarization (CP) is about 2.4, while in the present nuclear Overhauser polarization (NOP), it is 3.0 in the fast rotation limit of the methyl groups. While the CP enhancement becomes smaller for molecules with short T-1rho of H-1 or C-13, NOP would work well for such mobile molecules, and also NOP enables us to acquire a signal with a short repetition time even if H-1 T-1 is long. Further, NOP has the advantage of quantitativeness, and is very easy to carry out, being insensitive to the adjustment of rf field intensity and requiring only very low rf power. These features are demonstrated for uniformly C-13, N-15-labeled L-threonine and uniformly C-13, N-15-labeled glycylisoleucine. NOP-MAS is also applied for a naturally abundant C-13 sample.