Hyperfine coupling constants on inner‐sphere water molecules of GdIII‐based MRI contrast agents
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Hyperfine coupling constants on inner‐sphere water molecules of GdIII‐based MRI contrast agentsAutor(es)
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2012-11-02Cita bibliográfica
Esteban‐Gómez, D. , de Blas, A. , Rodríguez‐Blas, T. , Helm, L. and Platas‐Iglesias, C. (2012), Hyperfine Coupling Constants on Inner‐Sphere Water Molecules of GdIII‐Based MRI Contrast Agents. ChemPhysChem, 13: 3640-3650.
Resumo
[Abstract] Herein we present a theoretical investigation of the hyperfine coupling constants (HFCCs) on the inner‐sphere water molecules of [Gd(H2O)8]3+ and different GdIII‐based magnetic resonance imaging contrast agents such as [Gd(DOTA)(H2O)]−, [Gd(DTPA)(H2O)]2−, [Gd(DTPA‐BMA)(H2O)] and [Gd(HP‐DO3A)(H2O)]. DFT calculations performed on the [Gd(H2O)8]3+ model system show that both hybrid‐GGA functionals (BH&HLYP, B3PW91 and PBE1PBE) and the hybrid meta‐GGA functional TPSSh provide 17O HFCCs in close agreement with the experimental data. The use of all‐electron relativistic approaches based on the DKH2 approximation and the use of relativistic effective core potentials (RECP) provide results of essentially the same quality. The accurate calculation of HFCCs on the [Gd(DOTA)(H2O)]−, [Gd(DTPA)(H2O)]2−, [Gd(DTPA‐BMA)(H2O)] and [Gd(HP‐DO3A)(H2O)] complexes requires an adequate description of solvent effects. This was achieved by using a mixed cluster/continuum approach that includes explicitly two second‐sphere water molecules. The calculated isotropic 17O HFCCs (Aiso) fall within the range 0.40–0.56 MHz, and show deviations from the corresponding experimental values typically lower than 0.05 MHz. The Aiso values are significantly affected by the distance between the oxygen atom of the coordinated water molecule and the GdIII ion, as well as by the orientation of the water molecule plane with respect to the Gd‐O vector. 1H HFCCs of coordinated water molecules and 17O HFCCs of second‐sphere water molecules take values close to zero.
Palabras chave
Density functional calculations
F‐group elements
Hyperfine couplings
Lanthanides
MRI contrast agents
F‐group elements
Hyperfine couplings
Lanthanides
MRI contrast agents
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Dereitos
This is the peer reviewed version of the following article: Esteban‐Gómez, D. , de Blas, A. , Rodríguez‐Blas, T. , Helm, L. and Platas‐Iglesias, C. (2012), Hyperfine Coupling Constants on Inner‐Sphere Water Molecules of GdIII‐Based MRI Contrast Agents. ChemPhysChem, 13: 3640-3650 which has been published in final form at https://doi.org/10.1002/cphc.201200417. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
ISSN
1439-7641