NMR Diffusion Measurements under Chemical Exchange between Sites Involving a Large Chemical Shift Difference

被引:6
作者
Leclerc, S. [3 ]
Guendouz, L. [2 ]
Retournard, A. [1 ]
Canet, D. [1 ]
机构
[1] Nancy Univ, CNRS, Fac Sci & Tech, Methodol RMN,CRM2,UMR 7036, F-54506 Vandoeuvre Les Nancy, France
[2] Lab Instrumentat Elect Nancy, F-54506 Vandoeuvre Les Nancy, France
[3] Nancy Univ, CNRS, UMR 7563, LEMTA, F-54506 Vandoeuvre Les Nancy, France
关键词
diffusion; chemical exchange; thallium; B0; gradients; B1; FIELD-GRADIENT; STIMULATED ECHO; SPECTROSCOPY; RATES; TOOL; WATER; DOSY;
D O I
10.1002/cmr.a.20154
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
This study concerns the thallium-205 cation in aqueous solution in the presence of a calixarene molecule. Although the measurement of the self-diffusion coefficient of pure thallium (without calixarene in the aqueous solution) does not pose any particular problem, major difficulties are encountered with the standard method using gradient strength increment as soon as thallium is partly complexed by calixarene. With static magnetic field gradients, the NMR signal is so weak that it prevents any reliable measurement, whereas radio frequency (rf) field gradients lead to an unrealistic value of the diffusion coefficient. This failure is explained by the fact that thallium is in fast exchange between two sites (complexed and free thallium) thus exhibiting a single NMR signal although, in the course of the experiment, two signals, with an important difference in resonance frequencies (due to the large thallium chemical shift range), are effectively involved. With the objective to understand these quite unexpected observations, the theory underlying NMR diffusion experiments is first reviewed, and criteria of fast exchange are discussed for three parameters: chemical shifts, relaxation rates, and diffusion coefficients. It turns out that off-resonance effects are responsible for unwanted defocusing due to rf pulses in the static magnetic field gradient method and for time-dependent gradients in the rf field gradient method. Concerning the latter, a remedy is proposed which consists in applying the stronger gradient and incrementing the gradient pulse durations. After correction for relaxation, the expected value of the diffusion coefficient is retrieved. (C) 2010 Wiley Periodicals, Inc. Concepts Magn Reson Part A 36A: 127-137,2010.
引用
收藏
页码:127 / 137
页数:11
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