Field Dependence of Paramagnetic Relaxation Enhancement

issue No. 13

Paramagnetic relaxation enhancement (PRE) is a useful source of information about electron-nucleus distances and also provides estimates of electron relaxation rates. Field dependence of spin relaxation in paramagnetic systems is contributed by the electronic effect and sometimes molecular dynamics. Despite ultra-low field studies, the middle to high field range contains inter and intra-molecular dynamics. The following studies have investigated paramagnetic systems in a wide field range to tens of Tesla range. The first one studied PRE data even up to the field of 32.9 Tesla. It demonstrated the intramolecular and inter-molecular motion of Ni(II) affected by water interaction by looking into the high magnetic field dependence. The second paper conducted the field-cycler to measure the relaxivity in the Teslas range for the molecular dynamics investigation of paramagnetic nanoparticles.

Related Literature

Field-dependent paramagnetic relaxation enhancement in solutions of Ni(II): What happens above the NMR proton frequency of 1 GHz?

Jozef Kowalewski, Pascal H. Fries, Danuta Kruk, Michael Odelius, Andrei V. Egorov, Steffen Krämer, Holger Stork, Mladen Horvatić, Claude Berthier (deceased)
Journal of Magnetic Resonance 314 (2020) 106737

An extended set of paramagnetic relaxation enhancement (PRE) data, up to the field of 32.9 Tesla, is reported for protons in an acidified aqueous solution of a Ni(II) salt in the presence and in the absence of added glycerol. For the 55% w/w glycerol sample, a distinct maximum in the PRE vs magnetic field curve is observed for the first time. The data are analysed using the Swedish slow-motion theory, including both the intramolecular (inner-sphere) and intermolecular (outer-sphere) contributions. The results indicate that estimating the outer-sphere part in the presence of the more efficient inner-sphere term is a difficult task.

Ultra-wide range field-dependent measurements of the relaxivity of Gd1−xEuxVO4 nanoparticle contrast agents using a mechanical sample-shuttling relaxometer

Ching-Yu Chou, Mouna Abdesselem, Cedric Bouzigues, Minglee Chu, Angelo Guiga, Tai-Huang Huang, Fabien Ferrage, Thierry Gacoin, Antigoni Alexandrou, Dimitris Sakellariou
Scientific Reports 7, 44770 (2017)

Simulation curves of r1MP and its contributing functions, r1Cand r1F, in a log plot for the magnetic-field axis.

The current trend for Magnetic Resonance Imaging points towards higher magnetic fields. Even though sensitivity and resolution are increased in stronger fields, T1 contrast is often reduced, and this represents a challenge for contrast agent design. Field-dependent measurements of relaxivity are thus important to characterize contrast agents. At present, the field-dependent curves of relaxivity are usually carried out in the field range of 0 T to 2 T, using fast field cycling relaxometers. Here, we employ a high-speed sample shuttling device to switch the magnetic fields experienced by the nuclei between virtually zero field, and the center of any commercial spectrometer. We apply this approach on rare-earth (mixed Gadolinium-Europium) vanadate nanoparticles, and obtain the dispersion curves from very low magnetic field up to 11.7 T. In contrast to the relaxivity profiles of Gd chelates, commonly used for clinical applications, which display a plateau and then a decrease for increasing magnetic fields, these nanoparticles provide maximum contrast enhancement for magnetic fields around 1–1.5 T. These field-dependent curves are fitted using the so-called Magnetic Particle (MP) model and the extracted parameters discussed as a function of particle size and composition. We finally comment on the new possibilities offered by this approach.