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针对自旋大于 3/2 的四极核的高分辨率固态 NMR,讨论余弦调制脉冲的适用性。

On the applicability of cosine-modulated pulses for high-resolution solid-state NMR of quadrupolar nuclei with spin > 3/2.

机构信息

Bruker Japan K.K, 3-9, Moriya-cho, Kanagawa-ku, Yokohama-shi, Kanagawa, 221-0022, Japan; Interdisciplinary Research Center for Catalytic Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki, 305-8565, Japan.

Univ. Lille, CNRS, INRAE, Centrale Lille, Univ. Artois, FR 2638 - IMEC - Institut Michel-Eugène Chevreul, F-59000, Lille, France.

出版信息

Solid State Nucl Magn Reson. 2023 Jun;125:101863. doi: 10.1016/j.ssnmr.2023.101863. Epub 2023 Apr 6.

DOI:10.1016/j.ssnmr.2023.101863
PMID:37060799
Abstract

In MQMAS-based high-resolution solid-state NMR experiments of half-integer spin quadrupolar nuclei, the high radiofrequency (RF) field requirement for the MQ excitation and conversion steps with two hard-pulses is often a sensitivity limiting factor in many practical applications. Recently, the use of two cosine-modulated (cos) low-power (lp) pulses, lasting one-rotor period each, was successfully introduced for efficient MQ excitation and conversion of spin-3/2 nuclei with a reduced RF amplitude. In this study, we extend our previous investigations of spin-3/2 nuclei to systems with higher spin values and discuss the applicability of coslp-MQ excitation and conversion in MQMAS and MQ-HETCOR experiments under slow and fast spinning conditions. For the numerical simulations and experiments we used a moderate magnetic field of 14.1 T. Two spin-5/2 nuclei (Rb and Al) are mainly employed with a large variety of C values, but we show that the practical set up is also available for higher spin values, such as spin-9/2 with Nb in CsNbO. We demonstrate for nuclei with spin value larger than 3/2 a preferential use of coslp-MQ acquisition for low-gamma nuclei and/or large C values with a much reduced RF-field with respect to that of hard-pulses used with conventional methods.

摘要

在基于半整数自旋核的多量子魔角旋转(MQMAS)高分辨率固态 NMR 实验中,对于使用两个硬脉冲进行 MQ 激发和转换步骤的高射频(RF)场要求通常是许多实际应用中的灵敏度限制因素。最近,成功引入了两个余弦调制(cos)低功率(lp)脉冲,每个脉冲持续一个转子周期,用于有效激发自旋-3/2 核的 MQ,并降低 RF 幅度转换。在这项研究中,我们将之前对自旋-3/2 核的研究扩展到具有更高自旋值的系统,并讨论 coslp-MQ 激发和转换在慢转和快转条件下 MQMAS 和 MQ-HETCOR 实验中的适用性。对于数值模拟和实验,我们使用了 14.1 T 的中等磁场。主要使用两个自旋-5/2 核(Rb 和 Al),具有各种 C 值,但我们表明,该实用装置也可用于更高的自旋值,例如在 CsNbO 中的 Nb 自旋-9/2。我们证明了对于自旋值大于 3/2 的核,与使用传统方法的硬脉冲相比,对于低伽马核和/或大 C 值,coslp-MQ 采集具有更低的 RF 场,因此更倾向于使用 coslp-MQ 采集。

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