Structures and Dynamics of Lanthanide(III) Complexes of Sugar-Based DTPA-bis(amides) in Aqueous Solution: A Multinuclear NMR Study
journal contributionposted on 1997-06-04, 00:00 authored by Hendrik Lammers, Frédéric Maton, Dirk Pubanz, Martijn W. van Laren, Herman van Bekkum, André E. Merbach, Robert N. Muller, Joop A. Peters
The structure and dynamics of the lanthanide(III) complexes of DTPA-BGLUCA3- (DTPA-bis(glucamide)), DTPA-BENGALAA3- (DTPA-bis(ethylenegalactamine−amide)), DTPA-BEA3- (DTPA-bis(ethanolamide)), and DTPA-BPDA3- (DTPA-bis(propanediolamide)) in water have been investigated. These complexes are of relevance as potential MRI contrast agents. 13C relaxation times of the Nd(III) complexes show octadentate binding of the organic ligand via the three amines, the three carboxylates, and the two amide oxygens. 17O NMR measurements indicate that the coordination sphere is completed by one water ligand. Eight diastereomeric pairs of isomers are observed for the DTPA-bis(sugaramides). Data sets obtained from variable-temperature and -pressure 17O NMR at 9.4 T and variable-temperature 1H nuclear magnetic relaxation dispersion (NMRD) on the Gd(III) complexes were fitted simultaneously to give insight into the parameters governing the water 1H relaxivity. The water exchange rates, kex298, on [Gd(DTPA-BPDA)(H2O)], [Gd(DTPA-BGLUCA)(H2O)] and [Gd(DTPA-BENGALAA)(H2O)] are 3.6 ± 0.3, 3.8 ± 0.2, and 2.2 ± 0.1 × 105 s-1, and the activation volumes are +6.7, +6.8, and +5.6 cm3 mol-1 (±0.2 cm3 mol-1), respectively, indicating a strongly dissociatively activated mechanism. The sugar moieties have no significant influence on the coordination of the Gd(III) ion and on the parameters governing the relaxivity, apart from the expected increase in the rotational correlation time. The relaxivity under the usual MRI conditions is limited by the water exchange rate and the electronic relaxation. The data obtained are used to explain the relaxivity of conjugates of polysaccharides and Gd(DTPA).
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pressure 17 O NMRcorrelation timeMRI conditionsactivation volumes9.4 TGdrelaxation dispersionMRI contrast agentsMultinuclear NMR Studywater ligandwater exchange rates17 O NMR measurementsdiastereomeric pairscomplexNMRDcoordination spheresugar moietiesamide oxygens13 C relaxation timeswater 1 H relaxivitywater exchange rate