Pravdivtsev Andrey N, Yurkovskaya Alexandra V, Vieth Hans-Martin, Ivanov Konstantin L
International Tomography Center, Siberian Branch of the Russian Academy of Science , Institutskaya 3a, Novosibirsk, 630090, Russia.
Novosibirsk State University , Pirogova 2, Novosibirsk, 630090, Russia.
J Phys Chem B. 2015 Oct 29;119(43):13619-29. doi: 10.1021/acs.jpcb.5b03032. Epub 2015 May 27.
A new technique is developed that allows one to carry out the signal amplification by reversible exchange (SABRE) experiments at high magnetic field. SABRE is a hyperpolarization method, which utilizes transfer of spin order from para-hydrogen to the spins of a substrate in transient iridium complexes. Previously, it has been thought that such a transfer of spin order is only efficient at low magnetic fields, notably, at level anti-crossing (LAC) regions. Here it is demonstrated that LAC conditions can also be fulfilled at high fields under the action of a RF field. The high-field RF-SABRE experiment can be implemented using commercially available nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) machines and does not require technically demanding field-cycling. The achievable NMR enhancements are around 100 for several substrates as compared to their NMR signals at thermal equilibrium conditions at 4.7 T. The frequency dependence of RF-SABRE is comprised of well pronounced peaks and dips, whose position and amplitude are conditioned solely by the magnetic resonance parameters such as chemical shifts and scalar coupling of the spin system involved in the polarization transfer and by the amplitude of the RF field. Thus, the proposed method can serve as a new sensitive tool for probing transient complexes. Simulations of the dependence of magnetization transfer (i.e., NMR signal amplifications) on the frequency and amplitude of the RF field are in good agreement with the developed theoretical approach. Furthermore, the method enables continuous re-hyperpolarization of the SABRE substrate over a long period of time, giving a straightforward way to repetitive NMR experiments.
一种新技术被开发出来,它能让人在高磁场下进行通过可逆交换实现信号放大(SABRE)实验。SABRE是一种超极化方法,它利用在瞬态铱配合物中自旋序从对氢转移到底物的自旋上。此前,人们一直认为这种自旋序转移仅在低磁场下有效,特别是在能级反交叉(LAC)区域。在此证明,在射频场的作用下,高磁场下也能满足LAC条件。高场射频 - SABRE实验可以使用市售的核磁共振(NMR)和磁共振成像(MRI)机器来实现,并且不需要技术要求苛刻的场循环。与它们在4.7 T热平衡条件下的NMR信号相比,几种底物可实现的NMR增强约为100倍。射频 - SABRE的频率依赖性由明显的峰和谷组成,其位置和幅度仅由诸如参与极化转移的自旋系统的化学位移和标量耦合等磁共振参数以及射频场的幅度决定。因此,所提出的方法可以作为探测瞬态配合物的一种新的灵敏工具。磁化转移(即NMR信号放大)对射频场频率和幅度依赖性的模拟与所发展的理论方法高度吻合。此外,该方法能够在很长一段时间内对SABRE底物进行连续的再超极化,为重复NMR实验提供了一种直接的方法。