Willans Mathew J, Sears Devin N, Wasylishen Roderick E
Department of Chemistry, University of Alberta, Edmonton, Alta., Canada T6G 2G2.
J Magn Reson. 2008 Mar;191(1):31-46. doi: 10.1016/j.jmr.2007.11.012. Epub 2007 Nov 28.
The use of continuous-wave (CW) 1H decoupling has generally provided little improvement in the 13C MAS NMR spectroscopy of paramagnetic organic solids. Recent solid-state 13C NMR studies have demonstrated that at rapid magic-angle spinning rates CW decoupling can result in reductions in signal-to-noise and that 1H decoupling should be omitted when acquiring 13C MAS NMR spectra of paramagnetic solids. However, studies of the effectiveness of modern 1H decoupling sequences are lacking, and the performance of such sequences over a variety of experimental conditions must be investigated before 1H decoupling is discounted altogether. We have studied the performance of several commonly used advanced decoupling pulse sequences, namely the TPPM, SPINAL-64, XiX, and eDROOPY sequences, in 13C MAS NMR experiments performed under four combinations of the magnetic field strength (7.05 or 11.75T), rotor frequency (15 or 30kHz), and 1H rf-field strength (71, 100, or 140kHz). The effectiveness of these sequences has been evaluated by comparing the 13C signal intensity, linewidth at half-height, LWHH, and coherence lifetimes, T2('), of the methine carbon of copper(II) bis(dl-alanine) monohydrate, Cu(ala)(2).H2O, and methylene carbon of copper(II) bis(dl-2-aminobutyrate), Cu(ambut)(2), obtained with the advanced sequences to those obtained without 1H decoupling, with CW decoupling, and for fully deuterium labelled samples. The latter have been used as model compounds with perfect 1H decoupling and provide a measure of the efficiency of the 1H decoupling sequence. Overall, the effectiveness of 1H decoupling depends strongly on the decoupling sequence utilized, the experimental conditions and the sample studied. Of the decoupling sequences studied, the XiX sequence consistently yielded the best results, although any of the advanced decoupling sequences strongly outperformed the CW sequence and provided improvements over no 1H decoupling. Experiments performed at 7.05T demonstrate that the XiX decoupling sequence is the least sensitive to changes in the 1H transmitter frequency and may explain the superior performance of this decoupling sequence. Overall, the most important factor in the effectiveness of 1H decoupling was the carbon type studied, with the methylene carbon of Cu(ambut)(2) being substantially more sensitive to 1H decoupling than the methine carbon of Cu(ala)(2).H2O. An analysis of the various broadening mechanisms contributing to 13C linewidths has been performed in order to rationalize the different sensitivities of the two carbon sites under the four experimental conditions.
在顺磁性有机固体的13C 魔角旋转核磁共振(MAS NMR)光谱中,连续波(CW)1H去耦的应用通常未带来显著改善。最近的固态13C NMR研究表明,在快速魔角旋转速率下,CW去耦会导致信噪比降低,并且在采集顺磁性固体的13C MAS NMR光谱时应省略1H去耦。然而,目前缺乏对现代1H去耦序列有效性的研究,在完全摒弃1H去耦之前,必须研究这些序列在各种实验条件下的性能。我们研究了几种常用的先进去耦脉冲序列,即TPPM、SPINAL - 64、XiX和eDROOPY序列,在由磁场强度(7.05或11.75T)、转子频率(15或30kHz)和1H射频场强(71、100或140kHz)的四种组合所构成的实验条件下进行的13C MAS NMR实验中的性能。通过比较使用先进序列获得的一水合铜(II)双(dl - 丙氨酸),即Cu(ala)(2).H2O的次甲基碳以及铜(II)双(dl - 2 - 氨基丁酸),即Cu(ambut)(2)的亚甲基碳的13C信号强度、半高宽(LWHH)和相干寿命T2('),与不进行1H去耦、使用CW去耦以及全氘代样品所获得的结果,来评估这些序列的有效性。后者已被用作具有完美1H去耦的模型化合物,并提供了1H去耦序列效率的一种度量。总体而言,1H去耦的有效性在很大程度上取决于所使用的去耦序列、实验条件以及所研究的样品。在所研究的去耦序列中,XiX序列始终产生最佳结果,尽管任何一种先进去耦序列都明显优于CW序列,并且比不进行1H去耦有所改进。在7.05T下进行的实验表明,XiX去耦序列对1H发射机频率的变化最不敏感,这可能解释了该去耦序列的优越性能。总体而言,1H去耦有效性中最重要的因素是所研究的碳类型,Cu(ambut)(2)的亚甲基碳对1H去耦的敏感度远高于Cu(ala)(2).H2O的次甲基碳。为了合理化在四种实验条件下两个碳位点的不同敏感度,对导致13C线宽的各种展宽机制进行了分析。