Magnetic Field Dependence of Solvent Proton Relaxation by Solute Dysprosium(III) Complexes

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Many magnetic resonance imaging (MRI) agents are Gd(III)-based; its half-filled f-shell has an S-ground state and hence a long electronic relaxation time, leading to comparably large effects on 1/T1 and 1/T2 of water protons with no shift in the water-proton resonance frequency. 1/T1 and 1/T2 nuclear magnetic relaxation dispersion (NMRD) profiles of the Dy(III) aquo ion and its chelates have been reported recently. Dy(III) ions differ magnetically from Gd(III); the large spin-orbit interaction of its non-S-ground state reduces the electronic relaxation time 100-fold, and can have a large effect on proton 1/T2 and resonance frequency. Relaxation theory is well-developed and applicable to both ions but, for Dy(III), the phenomena are more wide-ranging. Recent interpretations have suggested that the data are anomolous, requiring a new mechanism for their explanation. The authors explain published Dy(III) data in terms of known theory, guided by experience with Gd(III) agents.


For fields below 1 T, the authors incorporate the shortened electronic relaxation time into the usual low-field theory for magnetic dipolar interactions between water protons and Dy(III) magnetic moments. Both inner- and outer-sphere relaxations are included. At higher fields (and unusual for small single-ion agents) one must include dipolar interactions of protons with the magnetization of the Dy(III) moments. This "Curie magnetization" causes a quadratic dependence of 1/T1 on field, and-through dipolar-induced shifts-an even greater quadratic dependence of 1/T2.


All published data can be explained by magnetic dipolar interactions. For Dy(III), the Curie term has a longer correlation time than the low-field term, namely, the rotation of solute for 1/T1 and the even longer water exchange lifetime τM for 1/T2. This exchange modulates the shift, producing phenomena not seen with Gd(III).


Relaxation by Dy(III) chelates can be explained by the same well-established theory of dipolar interactions used for their Gd(III) analogs. Interestingly, for MRI applications, τM should be long for Dy(III)-based agents and short for Gd(III)-based agents.

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