Michal Carl A, Hastings Simon P, Lee Lik Hang
Department of Physics and Astronomy, University of British Columbia, 6224 Agricultural Road, Vancouver, British Columbia V6T 1Z1, Canada.
J Chem Phys. 2008 Feb 7;128(5):052301. doi: 10.1063/1.2825593.
We present NMR signals from a strongly coupled homonuclear spin system, (1)H nuclei in adamantane, acquired with simultaneous two-photon excitation under conditions of the Lee-Goldburg experiment. Small coils, having inside diameters of 0.36 mm, are used to achieve two-photon nutation frequencies of approximately 20 kHz. The very large rf field strengths required give rise to large Bloch-Siegert shifts that cannot be neglected. These experiments are found to be extremely sensitive to inhomogeneity of the applied rf field, and due to the Bloch-Siegert shift, exhibit a large asymmetry in response between the upper and lower Lee-Goldburg offsets. Two-photon excitation has the potential to enhance both the sensitivity and performance of homonuclear dipolar decoupling, but is made challenging by the high rf power required and the difficulties introduced by the inhomogeneous Bloch-Siegert shift. We briefly discuss a variation of the frequency-switched Lee-Goldburg technique, called four-quadrant Lee-Goldburg (4QLG) that produces net precession in the x-y plane, with a reduced chemical shift scaling factor of 13.
我们展示了来自强耦合同核自旋系统(金刚烷中的(1)H核)的核磁共振信号,这些信号是在李 - 戈德堡实验条件下通过同时双光子激发获得的。内径为0.36毫米的小线圈用于实现约20千赫兹的双光子章动频率。所需的非常大的射频场强会产生不可忽略的大布洛赫 - 西格特位移。这些实验被发现对所施加射频场的不均匀性极其敏感,并且由于布洛赫 - 西格特位移,在上下李 - 戈德堡偏移之间的响应中表现出很大的不对称性。双光子激发有潜力提高同核偶极去耦的灵敏度和性能,但由于所需的高射频功率以及由不均匀布洛赫 - 西格特位移引入的困难而具有挑战性。我们简要讨论了频率切换李 - 戈德堡技术的一种变体,称为四象限李 - 戈德堡(4QLG),它在x - y平面中产生净进动,化学位移缩放因子减小到13。