Francis Bitter Magnet Laboratory, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA.
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA.
Angew Chem Int Ed Engl. 2017 Jun 6;56(24):6744-6748. doi: 10.1002/anie.201700032. Epub 2017 May 12.
The efficiency of continuous wave dynamic nuclear polarization (DNP) experiments decreases at the high magnetic fields used in contemporary high-resolution NMR applications. To recover the expected signal enhancements from DNP, we explored time domain experiments such as NOVEL which matches the electron Rabi frequency to the nuclear Larmor frequency to mediate polarization transfer. However, satisfying this matching condition at high frequencies is technically demanding. As an alternative we report here frequency-swept integrated solid effect (FS-ISE) experiments that allow low power sweeps of the exciting microwave frequencies to constructively integrate the negative and positive polarizations of the solid effect, thereby producing a polarization efficiency comparable to (±10 % difference) NOVEL. Finally, the microwave frequency modulation results in field profiles that exhibit new features that we coin the "stretched" solid effect.
连续波动态核极化 (DNP) 实验的效率在当代高分辨率 NMR 应用中使用的高磁场下会降低。为了从 DNP 中恢复预期的信号增强,我们探索了时域实验,如 NOVEL,它将电子拉比频率与核拉莫尔频率匹配以介导极化转移。然而,在高频下满足此匹配条件在技术上具有挑战性。作为替代方案,我们在这里报告频率扫描集成固态效应 (FS-ISE) 实验,该实验允许对激励微波频率进行低功率扫描,以建设性地整合固态效应的负极化和正极化,从而产生与 NOVEL 相当的极化效率(相差±10%)。最后,微波频率调制会导致场分布呈现出我们称之为“拉伸”固态效应的新特征。