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一种能显著抑制R2-CPMG 15N弛豫实验中与偏移相关伪影的相位循环方案。

A phase cycle scheme that significantly suppresses offset-dependent artifacts in the R2-CPMG 15N relaxation experiment.

作者信息

Yip Grover N B, Zuiderweg Erik R P

机构信息

Department of Chemistry, University of Michigan--Biophysics Research Division 930 N. University Ave, Ann Arbor, MI 48109, USA.

出版信息

J Magn Reson. 2004 Nov;171(1):25-36. doi: 10.1016/j.jmr.2004.06.021.

Abstract

R2-CPMG 15N relaxation experiments form the basis of NMR dynamics measurements, both for analysis of nano-pico second dynamics and milli-micro second dynamics (kinetics). It has been known for some time that in the practical limit of finite pulse widths, which becomes acute when using cryogenic probes, systematic errors in the apparent R2 relaxation behavior occur for spins far off-resonance from the RF carrier. Inaccurate measurement of R2 rates propagates into quantitative models such as model-free relaxation analysis, rotational diffusion tensor analysis, and relaxation dispersion. The root of the problem stems from evolution of the magnetization vectors out of the XY-plane, both during the pulses as well as between the pulses. These deviations vary as a function of pulse length, number of applied CPMG pulses, and CPMG inter-pulse delay. Herein, we analyze these effects in detail with experimentation, numerical simulations, and analytical equations. Our work suggests a surprisingly simple change in the phase progression of the CPMG pulses, which leads to a remarkable improvement in performance. First, the applicability range of the CPMG experiment is increased by a factor of two in spectral width; second, the dynamical/kinetic processes that can be assessed are significantly extended towards the slower time scale; finally, the robustness of the relaxation dispersion experiments is greatly improved.

摘要

R2-CPMG 15N弛豫实验构成了核磁共振动力学测量的基础,可用于分析纳秒-皮秒级动力学以及毫秒-微秒级动力学(动力学过程)。一段时间以来,人们已经知道,在有限脉冲宽度的实际限制下(在使用低温探头时这种限制会变得更加突出),对于与射频载波偏离共振较远的自旋,表观R2弛豫行为会出现系统误差。R2速率的不准确测量会传播到诸如无模型弛豫分析、旋转扩散张量分析和弛豫色散等定量模型中。问题的根源在于磁化矢量在脉冲期间以及脉冲之间从XY平面演化出来。这些偏差会随着脉冲长度、所施加的CPMG脉冲数量以及CPMG脉冲间延迟而变化。在此,我们通过实验、数值模拟和解析方程详细分析了这些影响。我们的工作表明,在CPMG脉冲的相位进展上进行一个出人意料的简单改变,会带来性能上的显著提升。首先,CPMG实验的适用光谱宽度范围增加了一倍;其次,可以评估的动力学/动力学过程显著扩展到了更慢的时间尺度;最后,弛豫色散实验的稳健性得到了极大提高。

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