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Understanding paramagnetic relaxation phenomena for water-soluble gadofullerenes

Laus, Sabrina and Sitharaman, Balaji and Toth, Eva and Bolskar, Robert D. and Helm, Lothar and Wilson, Lon J. and Merbach, Andre E. (2007) Understanding paramagnetic relaxation phenomena for water-soluble gadofullerenes. JOURNAL OF PHYSICAL CHEMISTRY C, 111 (15). pp. 5633-5639.

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Water-soluble, endohedral gadofullerenes exhibit considerably higher relaxivities than clinically used Gd3+-chelates and are currently explored as potential magnetic resonance imaging (MRI) contrast agents. The relaxivities of Gd@C-60(OH)(x) (x approximate to 27) and Gd@C-60[C(COOHyNa1-y)(2)](10) were previously found to vary with pH because of pH-dependent aggregation. By relaxometric measurements, we proved that aggregation can be suppressed by salt addition (75-100 equiv of sodium phosphate). In the aim of better understanding paramagnetic relaxation mechanisms in water-soluble gadofullerenes, we recorded variable-temperature and multiple-field O-17 and H-1 relaxation rates for Gd@C-60(OH)(x) and Gd@C-60[C(COOHyNa1-y)(2)](10) in both aggregated and disaggregated state (monomers). In the aggregated solutions, the O-17 T-1 and T-2 values are very different. This proves the confinement of water molecules in the interstices of the aggregates which is more important for the OH than for the malonate derivative. The rapid exchange of these water molecules with bulk contributes to the high relaxivity of the aggregated gadofullerenes. After disruption of the aggregates into distinct gadofullerene molecules, the temperature-dependent proton relaxivities could be described as the sum of an outer-sphere and an inner-sphere-like mechanism. The inner-sphere-like term originates from proton exchange between the bulk and protonated OH or COOH sites. The relaxivity peak observed between 10 and 300 MHz in the nuclear magnetic relaxation dispersion (NMRD) profile evidences that the malonate groups are at least partially protonated at pH 7.4. The rotational correlation times are long (similar to 1.2 ns) and identical for the two gadofullerenes. The larger relaxivity of Gd@C-60(OH)(x) as compared to Gd@ C-60[C(COOHxNa1-x)(2)](10) at frequencies above 20 MHz is related to the larger number of protonated sites.

Item Type:Article
Subjects:Physical Science > Nano objects
Physical Science > Nanomagnetics
ID Code:2797
Deposited By:Farnush Anwar
Deposited On:13 Jan 2009 16:57
Last Modified:13 Jan 2009 16:57

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