Magnetic resonance (MR) is one of the most versatile and useful physical effects used for human imaging, chemical analysis, and the elucidation of molecular structures. However, its full potential is rarely used, because only a small fraction of the nuclear spin ensemble is polarized, that is, aligned with the applied static magnetic field. Hyperpolarization methods seek other means to increase the polarization and thus the MR signal. A unique source of pure spin order is the entangled singlet spin state of dihydrogen, parahydrogen (pH ), which is inherently stable and long-lived. When brought into contact with another molecule, this "spin order on demand" allows the MR signal to be enhanced by several orders of magnitude. Considerable progress has been made in the past decade in the area of pH -based hyperpolarization techniques for biomedical applications. It is the goal of this Review to provide a selective overview of these developments, covering the areas of spin physics, catalysis, instrumentation, preparation of the contrast agents, and applications.
These initial results demonstrate that (31)P 3D CSI is feasible at 9.4 T and could be performed successfully in healthy subjects and tumor patients in under 30 min.
Parahydrogen (pH 2 ) is a convenient and cost‐efficient source of spin order to enhance the magnetic resonance signal. Previous work showed that transient interaction of pH 2 with a metal organic complex in a signal amplification by reversible exchange (SABRE) experiment enabled more than 10 % polarization for some 15 N molecules. Here, we analyzed a variant of SABRE, consisting of a magnetic field alternating between a low field of ∼1 μT, where polarization transfer is expected to take place, and a higher field >50 μT (alt‐SABRE). These magnetic fields affected the amplitude and frequency of polarization transfer. Deviation of a lower magnetic field from a “perfect” condition of level anti‐crossing increases the frequency of polarization transfer that can be exploited for polarization of short‐lived transient SABRE complexes. Moreover, the coherences responsible for polarization transfer at a lower field persisted during magnetic field variation and continued their spin evolution at higher field with a frequency of 2.5 kHz at 54 μT. The latter should be taken into consideration for an efficient alt‐SABRE. Theoretical and experimental findings were exemplified with Iridium N‐heterocyclic carbene SABRE complex and 15 N‐acetonitrole, where a 30 % higher 15 N polarization with alt‐SABRE compared to common SABRE was reached.
We present in vivo images of the human brain acquired with an ultralow field MRI (ULFMRI) system operating at a magnetic field B 0 ∼ 130 μT. The system features prepolarization of the proton spins at B p ∼ 80 mT and detection of the NMR signals with a superconducting, second-derivative gradiometer inductively coupled to a superconducting quantum interference device (SQUID). We report measurements of the longitudinal relaxation time T 1 of brain tissue, blood, and scalp fat at B 0 and B p , and cerebrospinal fluid at B 0 . We use these T 1 values to construct inversion recovery sequences that we combine with Carr-Purcell-Meiboom-Gill echo trains to obtain images in which one species can be nulled and another species emphasized. In particular, we show an image in which only blood is visible. Such techniques greatly enhance the already high intrinsic T 1 contrast obtainable at ULF. We further present 2D images of T 1 and the transverse relaxation time T 2 of the brain and show that, as expected at ULF, they exhibit similar contrast. Applications of brain ULFMRI include integration with systems for magnetoencephalography. More generally, these techniques may be applicable, for example, to the imaging of tumors without the need for a contrast agent and to modalities recently demonstrated with T 1ρ contrast imaging (T 1 in the rotating frame) at fields of 1.5 T and above. . 3D magnetic field gradients specify a unique magnetic field and thus an NMR frequency or phase in each voxel of the subject, so that with appropriate signal decoding one can acquire a 3D image (4).Clinical MRI systems with B 0 = 1:5 T achieve a spatial resolution of typically 1 mm; 3-T systems are becoming increasingly widespread in clinical practice (5), offering a higher signal-tonoise ratio (SNR) and thus higher spatial resolution. Nonetheless, there is ongoing interest in less expensive MRI systems operating at lower fields. Commercially available 0.2-to 0.5-T systems based on permanent magnets offer both lower cost and wider patient aperture than their higher field counterparts, at the expense of spatial resolution. At the still lower field of 0.03 T maintained by a room temperature solenoid, Connolly and coworkers (6, 7) obtained clinically useful SNR and spatial resolution by prepolarizing the protons in a field B p of 0.3 T. Prepolarization (8) enhances the magnetization of the proton ensemble over that produced by the lower precession field; after the polarizing field is removed, the higher magnetization produces a correspondingly larger signal during its precession in B 0 . Using the same method, Stepisnik et al. (9) obtained MR images in the Earth's magnetic field (∼ 50 μT).In recent years there has been increasing interest (10-36) in NMR and MRI at fields ranging from a few nanotesla to the order of 100 μT. The enormous reduction in the detected signal amplitude compared with the high field value is overcome partly by using prepolarization and partly by detecting the signal with an untuned superconducting input circuit inductively coupl...
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