Exploiting the Proton Exchange as an Additional Route to Enhance the Relaxivity of Paramagnetic MRI Contrast Agents

Aime, Silvio and Baroni, Simona and Delli Castelli, Daniela and Brücher, Ernő and Fábián, István and Baranyai, Zsolt (2018) Exploiting the Proton Exchange as an Additional Route to Enhance the Relaxivity of Paramagnetic MRI Contrast Agents. INORGANIC CHEMISTRY, 57 (9). pp. 5567-5574. ISSN 0020-1669

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Abstract

The relaxivity of Gd(HP-DO3A) was studied as a function of pH and buffer composition in order to identify the main factors of the observed relaxation enhancement due to the exchange of the coordinated hydroxyl proton. It was established that the paramagnetic relaxation time, T1M, of the coordinated hydroxyl proton is about 50% shorter than that of the protons in the coordinated water molecule. The control of the p K of the coordinated alcoholic -OH moiety in the ligand is fundamental to utilize the proton exchange enhanced relaxivity under physio/pathologic conditions. A new derivative of Gd(HP-DO3A) was synthesized by replacing the -CH3 group with a -CF3 moiety. In this complex, the -OH group becomes more acidic. Consequently, the maximum contribution of the proton exchange to the relaxivity is shifted to a lower pH region with the fluorinated ligand.

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