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Article

Longitudinal and Transverse 1H Nuclear Magnetic Resonance Relaxivities of Lanthanide Ions in Aqueous Solution up to 1.4 GHz/33 T

by
Rami Nasser Din
1,†,
Aiswarya Chalikunnath Venu
2,
Thomas Rudszuck
3,‡,
Alicia Vallet
4,
Adrien Favier
4,
Annie K. Powell
2,5,6,
Gisela Guthausen
3,7,
Masooma Ibrahim
2 and
Steffen Krämer
1,*
1
Université Grenoble Alpes, LNCMI-EMFL, CNRS, INSA-T, and UPS, CEDEX 9, 38042 Grenoble, France
2
Institute of Nanotechnology, Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany
3
Institute of Mechanical Process Engineering and Mechanics, Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany
4
Université Grenoble Alpes, CNRS, CEA, Institut de Biologie Structurale (IBS), 38044 Grenoble, France
5
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany
6
Institute for Quantum Materials and Technologies, Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany
7
Chair of Water Chemistry and Water Technology, Engler-Bunte-Institut, Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany
*
Author to whom correspondence should be addressed.
†
Current affiliation: Université Clermont Auvergne, INRAE, UR QuaPA and INRAE, AgroResonance Facility, 63122 Saint-Genès-Champanelle, France.
‡
Current affiliation: Vulcan Energie Ressourcen GmbH, 76227 Karlsruhe, Germany.
Molecules 2024, 29(20), 4956; https://doi.org/10.3390/molecules29204956
Submission received: 26 July 2024 / Revised: 8 October 2024 / Accepted: 10 October 2024 / Published: 19 October 2024
(This article belongs to the Special Issue Advanced Magnetic Resonance Methods in Materials Chemistry Analysis)
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Abstract

The longitudinal and transverse nuclear magnetic resonance relaxivity dispersion (NMRD) of 1H in water induced by the paramagnetic relaxation enhancement (PRE) of dissolved lanthanide ions (Ln3+) can become very strong. Longitudinal and transverse 1H NMRD for Gd3+, Dy3+, Er3+ and Ho3+ were measured from 20 MHz/0.47 T to 1382 MHz/32.5 T, which extended previous studies by a factor of more than two in the frequency range. For the NMRD above 800 MHz, we used a resistive magnet, which exhibits reduced field homogeneity and stability in comparison to superconducting and permanent NMR magnets. These drawbacks were addressed by dedicated NMRD methods. In a comparison of NMRD measurements between 800 MHz and 950 MHz performed in both superconducting and resistive magnets, it was found that the longitudinal relaxivities were almost identical. However, the magnetic field fluctuations of the resistive magnet strongly perturbed the transverse relaxation. The longitudinal NMRDs are consistent with previous work up to 600 MHz. The transverse NMRD nearly scales with the longitudinal one with a factor close to one. The data can be interpreted within a PRE model that comprises the dipolar hyperfine interactions between the 1H and the paramagnetic ions, as well as a Curie spin contribution that is dominant at high magnetic fields for Dy3+, Er3+ and Ho3+. Our findings provide a solid methodological basis and valuable quantitative insights for future high-frequency NMRD studies, enhancing the measurement accuracy and applicability of PRE models for paramagnetic ions in aqueous solutions.
Keywords: nuclear magnetic resonance relaxation dispersion; paramagnetic relaxation enhancement; lanthanide ions; ultra-high magnetic fields; magnetic field homogeneity; magnetic field stability nuclear magnetic resonance relaxation dispersion; paramagnetic relaxation enhancement; lanthanide ions; ultra-high magnetic fields; magnetic field homogeneity; magnetic field stability
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MDPI and ACS Style

Nasser Din, R.; Venu, A.C.; Rudszuck, T.; Vallet, A.; Favier, A.; Powell, A.K.; Guthausen, G.; Ibrahim, M.; Krämer, S. Longitudinal and Transverse 1H Nuclear Magnetic Resonance Relaxivities of Lanthanide Ions in Aqueous Solution up to 1.4 GHz/33 T. Molecules 2024, 29, 4956. https://doi.org/10.3390/molecules29204956

AMA Style

Nasser Din R, Venu AC, Rudszuck T, Vallet A, Favier A, Powell AK, Guthausen G, Ibrahim M, Krämer S. Longitudinal and Transverse 1H Nuclear Magnetic Resonance Relaxivities of Lanthanide Ions in Aqueous Solution up to 1.4 GHz/33 T. Molecules. 2024; 29(20):4956. https://doi.org/10.3390/molecules29204956

Chicago/Turabian Style

Nasser Din, Rami, Aiswarya Chalikunnath Venu, Thomas Rudszuck, Alicia Vallet, Adrien Favier, Annie K. Powell, Gisela Guthausen, Masooma Ibrahim, and Steffen Krämer. 2024. "Longitudinal and Transverse 1H Nuclear Magnetic Resonance Relaxivities of Lanthanide Ions in Aqueous Solution up to 1.4 GHz/33 T" Molecules 29, no. 20: 4956. https://doi.org/10.3390/molecules29204956

APA Style

Nasser Din, R., Venu, A. C., Rudszuck, T., Vallet, A., Favier, A., Powell, A. K., Guthausen, G., Ibrahim, M., & Krämer, S. (2024). Longitudinal and Transverse 1H Nuclear Magnetic Resonance Relaxivities of Lanthanide Ions in Aqueous Solution up to 1.4 GHz/33 T. Molecules, 29(20), 4956. https://doi.org/10.3390/molecules29204956

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