Department of Chemistry, Washington University in St. Louis, One Brookings Drive, St. Louis, MO, 63130, USA.
Department of Biochemistry, Biophysics, and Biology, Washington University in St. Louis, School of Medicine, 660 S. Euclid Ave, St Louis, MO, 63110, USA.
Angew Chem Int Ed Engl. 2019 May 27;58(22):7259-7262. doi: 10.1002/anie.201900139. Epub 2019 Apr 25.
Dynamic nuclear polarization (DNP) increases NMR sensitivity by transferring polarization from electron to nuclear spins. Herein, we demonstrate that electron decoupling with chirped microwave pulses enables improved observation of DNP-enhanced C spins in direct dipolar contact with electron spins, thereby leading to an optimal delay between transients largely governed by relatively fast electron relaxation. We report the first measurement of electron longitudinal relaxation time (T ) during magic angle spinning (MAS) NMR by observation of DNP-enhanced NMR signals (T =40±6 ms, 40 mM trityl, 4.0 kHz MAS, 4.3 K). With a 5 ms DNP period, electron decoupling results in a 195 % increase in signal intensity. MAS at 4.3 K, DNP, electron decoupling, and short recycle delays improve the sensitivity of C in the vicinity of the polarizing agent. This is the first demonstration of recovery times between MAS-NMR transients being governed by short electron T and fast DNP transfer.
动态核极化(DNP)通过将极化从电子转移到核自旋来提高 NMR 灵敏度。在此,我们证明了用啁啾微波脉冲进行电子去耦可以改善与电子自旋直接偶合的 DNP 增强的 C 自旋的观测,从而导致在由相对较快的电子弛豫主导的瞬变之间的最佳延迟。我们通过观察 DNP 增强的 NMR 信号报告了在魔角旋转(MAS)NMR 中电子纵向弛豫时间(T )的首次测量(T = 40 ± 6 ms,40 mM 三苯甲基,4.0 kHz MAS,4.3 K)。在 5 ms 的 DNP 周期下,电子去耦导致信号强度增加 195%。在 4.3 K 下进行 MAS、DNP、电子去耦和短循环延迟可提高极化剂附近 C 的灵敏度。这是首次证明 MAS-NMR 瞬变之间的恢复时间由短电子 T 和快速 DNP 转移控制。