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采用重聚连续波射频照射实现稳健高效的 19F 异核双共振去耦。

Robust and efficient 19F heteronuclear dipolar decoupling using refocused continuous-wave rf irradiation.

机构信息

Center for Insoluble Protein Structures (inSPIN), Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, Aarhus C, Denmark.

出版信息

J Magn Reson. 2013 Jan;226:88-92. doi: 10.1016/j.jmr.2012.11.003. Epub 2012 Nov 16.

Abstract

Refocused continuous wave (rCW) decoupling is presented as an efficient and robust means to obtain well-resolved magic-angle-spinning solid-state NMR spectra of low-γ spins, such as (13)C dipolar coupled to fluorine. The rCW decoupling sequences, recently introduced for (1)H decoupling, are very robust towards large isotropic and anisotropic shift ranges as often encountered for (19)F spins. In rCW decoupling, the so-called refocusing pulses inserted into the CW irradiation eliminate critical residual second- and third-order dipolar coupling and dipolar-coupling against chemical shielding anisotropy cross-terms in the effective Hamiltonian through time-reversal (i.e. refocusing). As important additional assets, the rCW decoupling sequences are robust towards variations in rf amplitudes, operational at low to high spinning speeds, and easy to set-up for optimal performance experimentally. These aspects are demonstrated analytically/numerically and experimentally in comparison to state-of-the-art decoupling sequences such as TPPM, SPINAL-64, and frequency-swept variants of these.

摘要

重新聚焦连续波(rCW)去耦被提出作为一种有效且稳健的方法,可用于获得低γ自旋(如(13)C 偶极耦合到氟)的高分辨率魔角旋转固态 NMR 谱。rCW 去耦序列最近被引入用于(1)H 去耦,对于(19)F 自旋通常遇到的大各向同性和各向异性位移范围非常稳健。在 rCW 去耦中,插入 CW 照射的所谓重聚焦脉冲通过时间反转(即重聚焦)消除了有效哈密顿量中关键的剩余二阶和三阶偶极耦合以及偶极耦合与化学位移各向异性交叉项。作为重要的附加资产,rCW 去耦序列对射频幅度的变化具有鲁棒性,可在低到高旋转速度下运行,并且易于设置以获得最佳性能。这些方面通过与诸如 TPPM、SPINAL-64 以及这些的频率扫描变体等最先进的去耦序列的分析/数值和实验比较来证明。

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