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关于在固体中 I=3/2 自旋四极核的高分辨率 NMR 中使用低射频场和余弦调制的实用考虑。

Practical considerations on the use of low RF-fields and cosine modulation in high-resolution NMR of I = 3/2 spin quadrupolar nuclei in solids.

机构信息

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

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

出版信息

J Magn Reson. 2022 Dec;345:107324. doi: 10.1016/j.jmr.2022.107324. Epub 2022 Nov 9.

DOI:10.1016/j.jmr.2022.107324
PMID:36370548
Abstract

Despite its ease in experimental set up, the low sensitivity of MQMAS experiments is often a limiting factor in many practical applications. This is mainly due to the large radiofrequency (RF) field requirement of the two short hard-pulses often used for the optimum MQ excitation and conversion steps. Very recently, two novel MQMAS experiments have been proposed for I = 3/2 nuclei, namely lp-MQMAS and coslp-MQMAS, enabling an efficient MQ excitation/conversion with a reduced RF requirement, by utilizing two long pulses lasting one rotor period each, with or without cosine modulation. In this study, we focus on the practical considerations of these new methods and discuss their pros and cons to elucidate their appropriate use under both moderate and fast spinning conditions. Using four I = 3/2 (Rb, Ga, Cl and Na) nuclei at a moderate magnetic field (B = 14.1 T), we show the superior use of these experiments, especially for samples with large C values and/or low-gamma nuclei. Compared to all other existing sequences, the coslp-MQMAS method with initial WURST signal enhancement is the most robust, efficient and resolved high-resolution 2D method for spin 3/2 nuclei. Furthermore, using {Na}-H spin systems, we demonstrate the sensitivity advantage of the WURST coslp-MQ-HETCOR acquisition upon H detection and fast MAS conditions.

摘要

尽管 MQMAS 实验在实验设置上很简单,但由于通常用于最佳 MQ 激发和转换步骤的两个短硬脉冲需要较大的射频 (RF) 场,其灵敏度通常是许多实际应用的限制因素。最近,针对 I=3/2 核提出了两种新的 MQMAS 实验,即 lp-MQMAS 和 coslp-MQMAS,通过使用持续一个转子周期的两个长脉冲(带有或不带有余弦调制),可以有效地进行 MQ 激发/转换,从而减少 RF 要求。在这项研究中,我们重点研究了这些新方法的实际考虑因素,并讨论了它们的优缺点,以阐明它们在中速和高速旋转条件下的适当用途。使用四个 I=3/2(Rb、Ga、Cl 和 Na)核在中等磁场(B=14.1 T)下,我们展示了这些实验的优越用途,特别是对于 C 值较大和/或低γ核的样品。与所有其他现有序列相比,具有初始 WURST 信号增强的 coslp-MQMAS 方法是用于自旋 3/2 核的最稳健、高效和分辨率高的 2D 方法。此外,使用 {Na}-H 自旋系统,我们证明了在 H 检测和快速 MAS 条件下,WURST coslp-MQ-HETCOR 采集在灵敏度方面具有优势。

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