High-Relaxivity contrast agents for magnetic resonance imaging based on multisite interactions between a beta-cyclodextrin oligomer and suitably functionalized GdIII chelates.
The results reported in this work show that tightly assembled adducts formed by trisubstituted GdIII complexes and a beta-CD multimer (Poly-beta-CD, d.p. ca. 12) may represent very interesting candidates for novel MRI applications wherein a high number of paramagnetic ions endowed with high relaxivity (per GdIII ion) are necessary. The relaxivities found for the paramagnetic adducts represent a remarkable step forward on the relaxivity scale. However, a detailed investigation of the determinants of the relaxation enhancement in these systems shows that their relaxivities are still limited by a nonoptimal tauR and a relatively long exchange lifetime of the coordinated water(s). Moreover, the exchange rate of the water molecule(s) coordinated to the GdIII ion further decreases upon binding to the Poly-beta-CD. It is suggested that this finding is related to the structural properties of the supramolecule, which brings a high density of hydroxyl groups into the proximity of the "guest" complexes, and this yields an overall reinforcement of the hydrogen-bonding network involving the coordinated water(s). On the other hand, such a tight arrangement appears responsible for an enhanced contribution to the observed relaxivity arising from water molecules in the second coordination sphere of the metal center.
Aime
S
S
Dipartimento di Chimica IFM, Università di Torino, Italy. aime@ch.unito.it
Botta
I M
IM
Fedeli
F
F
Gianolio
E
E
Terreno
E
E
Anelli
P
P
D002614:Chelating Agents / Q000737:chemistry*; D003287:Contrast Media / Q000737:chemistry*; D003505:Cyclodextrins / Q000737:chemistry*; D005682:Gadolinium / Q000737:chemistry*; D008279:Magnetic Resonance Imaging; D015394:Molecular Structure; D047392:beta-Cyclodextrins
D002614:Chelating Agents; D003287:Contrast Media; D003505:Cyclodextrins; D047392:beta-Cyclodextrins; D005682:Gadolinium; C031215:betadex