School of Chemistry and WestCHEM, University of Glasgow, Glasgow G12 8QQ, United Kingdom.
J Magn Reson. 2012 Jan;214(1):68-75. doi: 10.1016/j.jmr.2011.10.006. Epub 2011 Oct 19.
The radiofrequency pulses used in NMR are subject to a number of imperfections such as those caused by inhomogeneity of the radiofrequency (B(1)) field and an offset of the transmitter frequency from precise resonance. The effect of these pulse imperfections upon a refocusing pulse in a spin-echo experiment can be severe. Many of the worst effects, those that distort the phase of the spin echo, can be removed completely by selecting the echo coherence pathway using either the "Exorcycle" phase cycle or magnetic field gradients. It is then tempting to go further and try to improve the amplitude of the spin-echo signal by replacing the simple refocusing pulse with a broadband composite 180° pulse that compensates for the relevant pulse imperfection. We show here that all composite pulses with a symmetric or asymmetric phase shift scheme will reintroduce phase distortions into the spin echo, despite the selection of the echo coherence pathway. In contrast, all antisymmetric composite pulses yield no phase distortion whatsoever, both on and off resonance, and are therefore the correct symmetry of composite refocusing pulse to use. These conclusions are verified using simulations and (31)P MAS NMR spin-echo experiments performed on a microporous aluminophosphate.
NMR 中使用的射频脉冲会受到多种不完美因素的影响,例如射频(B(1))场的不均匀性和发射器频率从精确共振的偏移。这些脉冲不完美对自旋回波实验中的重聚焦脉冲的影响可能很严重。许多最严重的影响,即那些会扭曲自旋回波相位的影响,可以通过使用“Exorcycle”相位循环或磁场梯度选择回波相干途径来完全消除。然后,人们很想更进一步,通过用补偿相关脉冲不完美的宽带复合 180°脉冲替换简单的重聚焦脉冲来提高自旋回波信号的幅度。我们在这里表明,尽管选择了回波相干途径,但所有具有对称或不对称相移方案的复合脉冲都会重新引入自旋回波中的相位失真。相比之下,所有不对称的复合脉冲都不会在共振和非共振时产生任何相位失真,因此是使用复合重聚焦脉冲的正确对称。这些结论通过模拟和在微孔磷酸铝上进行的 (31)P MAS NMR 自旋回波实验得到了验证。