The effect of ligand scaffold size on the stability of tripodal hydroxypyridonate gadolinium complexes

Brendon O'Sullivan, Dan M.J. Doble, Marlon K. Thompson, Carsten Siering, Jide Xu, Mauro Botta, Silvio Aime, Kenneth N. Raymond

Risultato della ricerca: Contributo su rivistaArticolo in rivistapeer review

Abstract

The variation of the size of the capping scaffold which connects the hydroxypyridonate (HOPO) binding units in a series of tripodal chelators for gadolinium (Gd) complexes has been investigated. A new analogue of TREN-1-Me-3,2-HOPO (1) (TREN = tri(ethylamine)amine) was synthesized: TREN-Gly-1-Me-3,2-HOPO (2) features a glycine spacer between the TREN cap and HOPO binding unit. TRPN-1-Me-3,2-HOPO (3) has a propylene-bridged cap, as compared to the ethylene bridges within the TREN cap of the parent complex. Thermodynamic equilibrium constants for the acid-base properties of 2 and the Gd3+ complexation strength of 2 and 3 were measured and are compared with that of the parent ligand. The most basic ligand is 2 while 3 is the most acidic. Both 2 and 3 form Gd3+ complexes of similar stability (pGd = 16.7 and 15.6, respectively) and are less stable than the parent complex Gd-1 (pGd = 19.2). Two of the three complexes are more stable than the bis(methylamide)diethylenetriamine pentaacetate complex Gd(DTPA-BMA) (pGd = 15.7) while the other is of comparable stability. Enlargement of the ligand scaffold decreases the stability of the Gd3+ complexes and indicates that the TREN scaffold is superior to the TRPN and TREN-Gly scaffolds. The proton relaxivity of Gd-2 is 6.6 mM-1 s-1 (20 MHz, 25 °C, pH 7.3), somewhat lower than the parent Gd-1 but higher than that of the MRI contrast agents in clinical practice. The pH-independent relaxivity of Gd-2 is uncharacteristic of this family of complexes and is discussed.

Lingua originaleInglese
pagine (da-a)2577-2583
Numero di pagine7
RivistaInorganic Chemistry
Volume42
Numero di pubblicazione8
DOI
Stato di pubblicazionePubblicato - 21 apr 2003

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