Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.
Phys Chem Chem Phys. 2013 Oct 28;15(40):17233-9. doi: 10.1039/c3cp52029c.
Hyperpolarization has found many applications in Nuclear Magnetic Resonance (NMR) and Magnetic Resonance Imaging (MRI). However, its usage is still limited to the observation of relatively fast processes because of its short lifetimes. This issue can be circumvented by storing the hyperpolarization in a slowly relaxing singlet state. Symmetrical molecules hyperpolarized by Parahydrogen Induced Hyperpolarization (PHIP) provide straightforward access to hyperpolarized singlet states because the initial parahydrogen singlet state is preserved at almost any magnetic field strength. In these systems, which show a remarkably long (1)H singlet state lifetime of several minutes, the conversion of the NMR silent singlet state to observable magnetization is feasible due to the existence of singlet-triplet level anti-crossings. Here, we demonstrate that scaling the chemical shift Hamiltonian by rf irradiation is sufficient to transform the singlet into an observable triplet state. Moreover, because the application of one long rf pulse is only partially converting the singlet state, we developed a multiconversion sequence consisting of a train of long rf pulses resulting in successive singlet to triplet conversions. This sequence is used to measure the singlet state relaxation time in a simple way at two different magnetic fields. We show that this approach is valid for almost any magnetic field strength and can be performed even in the less homogeneous field of an MRI scanner, allowing for new applications of hyperpolarized NMR and MRI.
极化在核磁共振(NMR)和磁共振成像(MRI)中有许多应用。然而,由于其寿命较短,其应用仍然局限于相对较快的过程的观察。通过将极化储存在缓慢弛豫的单重态中,可以解决这个问题。通过Para 氢诱导极化(PHIP)极化的对称分子提供了直接进入极化单重态的途径,因为初始 Para 氢单重态几乎在任何磁场强度下都能被保留。在这些系统中,(1)H 单重态寿命长达几分钟,由于 singlet-triplet 能级交叉的存在,将 NMR 静默的单重态转换为可观察的磁化是可行的。在这里,我们证明通过射频辐照对化学位移哈密顿量进行缩放足以将单重态转换为可观察的三重态。此外,由于一个长射频脉冲的应用只能部分地将单重态转换,我们开发了一个由一系列长射频脉冲组成的多转换序列,导致连续的单重态到三重态转换。该序列用于在两个不同磁场下以简单的方式测量单重态弛豫时间。我们表明,该方法适用于几乎任何磁场强度,甚至可以在 MRI 扫描仪的不均匀场中进行,为极化 NMR 和 MRI 的新应用提供了可能。