He Tian, Zur Yuval, Montrazi Elton T, Frydman Lucio
Department of Chemical and Biological Physics, Weizmann Institute, 7610001 Rehovot, Israel.
Department of Chemistry, Zhejiang University, Hangzhou 310058, China.
J Am Chem Soc. 2024 Feb 14;146(6):3615-3621. doi: 10.1021/jacs.3c12954. Epub 2024 Jan 30.
Pulsed Fourier transform nuclear magnetic resonance (FT-NMR) has reigned supreme in high-resolution, high-field spectroscopy─particularly when targeting complex liquid-state samples involving multiple sharp peaks spread over large spectral bandwidths. It is known, however, that if spectral resolution is not a must, the FT-based approach is not necessarily the optimal route for maximizing NMR sensitivity: if ≈ , as often found in solutions, Carr's steady-state free-precession (SSFP) approach can in principle provide a superior signal-to-noise ratio per √(acquisition_time) (SNR). A rapid train of pulses will then lead to a transverse component that reaches up to 50% of the thermal equilibrium magnetization, provided that pulses are applied at repetition times TR ≪ , , and that a single suitable offset is involved. It is generally assumed that having to deal with multiple chemical shifts deprives SSFP from its advantages. The present study revisits this assumption by introducing an approach whereby arbitrarily short SSFP-derived free induction decays (FIDs) can deliver high-resolution spectra, without suffering from peak broadenings or phase distortions. To achieve discrimination among nearby frequencies, signals arising from a series of regularly phase-increased excitation pulses are collected. Given SSFP's amplitude and phase sensitivity to the spins' offset, this enables the resolution of sites according to their chemical shift position. In addition, the extreme fold-over associated with SSFP acquisitions is dealt with by a customized discrete FT of the interpulse time-domain signal. Solution-state C NMR spectra which compare well with FT-NMR data in terms of sensitivity, bandwidth, and resolution can then be obtained.
脉冲傅里叶变换核磁共振(FT-NMR)在高分辨率、高场光谱学领域一直占据主导地位,特别是在针对涉及多个尖锐峰且分布在大光谱带宽上的复杂液态样品时。然而,众所周知,如果光谱分辨率不是必需的,基于傅里叶变换的方法不一定是最大化NMR灵敏度的最佳途径:如果 ≈ ,这在溶液中经常出现,卡尔稳态自由进动(SSFP)方法原则上可以提供每√(采集时间)(SNR)更高的信噪比。然后,快速的脉冲序列将导致一个横向分量,该分量可达热平衡磁化强度的50%,前提是脉冲以重复时间TR ≪ , 施加,并且涉及单个合适的偏移量。通常认为,必须处理多个化学位移会使SSFP失去其优势。本研究通过引入一种方法重新审视了这一假设,即任意短的源自SSFP的自由感应衰减(FID)都可以提供高分辨率光谱,而不会出现峰展宽或相位失真。为了实现对附近频率的区分,收集了由一系列相位有规律增加的激发脉冲产生的信号。鉴于SSFP对自旋偏移的幅度和相位敏感性,这使得能够根据化学位移位置分辨位点。此外,通过对脉冲间时域信号进行定制的离散傅里叶变换来处理与SSFP采集相关的极端折叠问题。然后可以获得在灵敏度、带宽和分辨率方面与FT-NMR数据相当的溶液态碳核磁共振光谱。