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Lanthanide-induced relaxation anisotropy

Suturina, Elizaveta A.; Mason, Kevin; Geraldes, Carlos F.G.C.; Chilton, Nicholas F.; Parker, David; Kuprov, Ilya

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Authors

Elizaveta A. Suturina

Kevin Mason

Carlos F.G.C. Geraldes

Nicholas F. Chilton

Ilya Kuprov



Abstract

Lanthanide ions accelerate nuclear spin relaxation by two primary mechanisms: dipolar and Curie. Both are commonly assumed to depend on the length of the lanthanide-nucleus vector, but not on its direction. Here we show experimentally that this is wrong – careful proton relaxation data analysis in a series of isostructural lanthanide complexes (Ln = Tb, Dy, Ho, Er, Tm, Yb) reveals angular dependence in both Curie and dipolar relaxation. The reasons are: (a) that magnetic susceptibility anisotropy can be of the same order of magnitude as the isotropic part (contradicting the unstated assumption in Guéron‘s theory of the Curie relaxation process), and (b) that zero-field splitting can be much stronger than the electron Zeeman interaction (Bloembergen's original theory of the lanthanide-induced dipolar relaxation process makes the opposite assumption). These factors go beyond the well researched cross-correlation effects; they alter the relaxation theory treatment and make strong angular dependencies appear in the nuclear spin relaxation rates. Those dependencies are impossible to ignore – this is now demonstrated both theoretically and experimentally, and suggests that a major revision is needed of the way lanthanide-induced relaxation data are used in structural biology.

Citation

Suturina, E. A., Mason, K., Geraldes, C. F., Chilton, N. F., Parker, D., & Kuprov, I. (2018). Lanthanide-induced relaxation anisotropy. Physical Chemistry Chemical Physics, 20(26), 17676-17686. https://doi.org/10.1039/c8cp01332b

Journal Article Type Article
Acceptance Date Jun 6, 2018
Online Publication Date Jun 8, 2018
Publication Date Jul 14, 2018
Deposit Date Jul 18, 2018
Publicly Available Date Jul 18, 2018
Journal Physical Chemistry Chemical Physics
Print ISSN 1463-9076
Electronic ISSN 1463-9084
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 20
Issue 26
Pages 17676-17686
DOI https://doi.org/10.1039/c8cp01332b

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