The structure and dynamics of the lanthanide(III) complexes of DTPA BGLUCA(3-) (DTPA-bis(glucamide)), DTPA-BENGALAA(3-) (DTPA-bis(ethylenegalactamine-amide)), DTPA-BEA(3-) (DTPA-bis(ethanolamide)), and DTPA-BPDA(3-) (DTPA-bis(propanediolamide)) in water have been investigated. These complexes are of relevance as potential MRT contrast agents. C-13 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. O-17 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 O-17 NMR at 9.4 T and variable-temperature H-1 nuclear magnetic relaxation dispersion (NMRD) on the Gd(III) complexes were fitted simultaneously to give insight into the parameters governing the water H-1 relaxivity. The water exchange rates, k(ex)(298), 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 x 10(5) s(-1), and the activation volumes are +6.7, +6.8, and +5.6 cm(3) mol(-1) (+/-0.2 cm(3) 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).