论文标题

Sabre-Relay方法中超极化形成的理论描述

Theoretical Description of Hyperpolarization Formation in the SABRE-relay Method

论文作者

Knecht, Stephan, Barskiy, Danila A., Buntkowsky, Gerd, Ivanov, Konstantin L.

论文摘要

SABER(通过可逆交换进行信号扩增)已成为一种广泛使用的超极化核自旋的方法,从而通过数量级增强其核磁共振(NMR)信号。在SABER实验中,在瞬时有机金属络合物中将非平衡自旋顺序从偏二氢转移到底物。 SABER的适用性通过Sabre-Relay的方法扩展,在该方法中,可以通过直接化学交换超极化核的直接化学交换或通过第二个有机金属络合物中两个底物之间的极化转移将极化传递到第二个底物。为了了解极化转移的机制并研究了转移效率,我们提出了一种理论方法,可以治疗旋转动力学和化学动力学以及它们之间的相互作用。该方法基于涉及的自旋系统的自旋密度矩阵(即Saber底物和复合物)的一组方程,可以通过数值求解。使用这种方法,我们对极化形成进行详细研究,并详细分析可达到的极化水平对各种化学动力学和自旋动态参数的依赖性。我们预见了本方法的应用,以优化Sabre-Relay实验,其最终目标是实现感兴趣的基材的最大NMR信号增强。

SABRE (Signal Amplification By Reversible Exchange) has become a widely used method for hyper-polarizing nuclear spins, thereby enhancing their Nuclear Magnetic Resonance (NMR) signals by orders of magnitude. In SABRE experiments, non-equilibrium spin order is transferred from parahydrogen to a substrate in a transient organometallic complex. Applicability of SABRE is expanded by the methodology of SABRE-relay, in which polarization can be relayed to a second substrate either by direct chemical exchange of hyperpolarized nuclei or by polarization transfer between two substrates in a second organometallic complex. To understand the mechanism of the polarization transfer and study the transfer efficiency, we propose a theoretical approach to SABRE-relay, which can treat both spin dynamics and chemical kinetics as well as the interplay between them. The approach is based on a set of equations for the spin density matrices of the spin systems involved (i.e., SABRE substrates and complexes), which can be solved numerically. Using this method, we perform a detailed study of polarization formation and analyse in detail the dependence of attainable polarization level on various chemical kinetic and spin dynamic parameters. We foresee applications of the present approach for optimizing SABRE-relay experiments with the ultimate goal of achieving maximal NMR signal enhancements for substrates of interest.

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