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Synthesis of Two Derivatives of 3,6,9‐tri(carboxymethyl)‐3,6,9‐triazaundecanedioic Acid and the Stabilities of Their Complexes with Ca 2+ , Cu 2+ , Zn 2+ , Dy 3+ and Gd 3+
Author(s) -
Wang YunMing,
Cheng TsannHwang,
Liu GinChung
Publication year - 2000
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.200000146
Subject(s) - chemistry , protonation , potentiometric titration , stability constants of complexes , titration , lanthanide , metal , divalent , inorganic chemistry , metal ions in aqueous solution , selectivity , inner sphere electron transfer , zinc , nuclear chemistry , ion , aqueous solution , biochemistry , organic chemistry , catalysis
Two N ‐2‐hydroxy‐1‐phenylethyl and N ‐2‐hydroxy‐2‐phenylethyl derivatives of DTPA (3,6,9‐tri(carboxymethyl)‐3,6,9‐triazaundecanedioic acid), DTPA‐H1P = 3,9‐di(carboxymethyl)‐6‐2‐hydroxy‐1‐phenylethyl‐3,6,9‐triazaundecanedioic acid, and DTPA‐H2P = 3,9‐di(carboxymethyl)‐6‐2‐hydroxy‐2‐phenylethyl‐3,6,9‐triazaundecanedioic acid were synthesized. Their protonation constants were determined by Potentiometric titration in 0.10 M Me 4 NNO 3 and by NMR pH titration at 25.0 ± 0.1°C. The formations of lanthanide(III), copper(II), zinc(II) and calcium(II) complexes were investigated quantitatively by potentiometry. The stability constant for Gd(III) complex is larger than those for Ca(II), Zn(II) and Cu(II) complexes with these two ligands. The selectivity constants and modified selectivity constants of the DTPA‐H1P and DTPA‐H2P for Gd(III) over endogenously available metal ions were calculated. Comparing pM values at physiological pH 7.4 assesses effectiveness of these two ligands in binding divalent and trivalent metal ions in biological media. The observed water proton relaxivity values of [Gd(DTPA‐H1P)] − and [Gd(DTPA‐H2P)] − became constant with respect to pH changes over the range of 4‐10. 17 O NMR shifts showed that the [Dy(DTPA‐H1P)] − and [Dy(DTPA‐H2P)] − complexes at pH 6.30 had 1.91 and 2.28 inner‐sphere water molecules, respectively. Water proton spin‐lattice relaxation rates of [Gd(DTPA‐H1P)] − and [Gd(DTPA‐H2P)] − complexes were also consistent with the inner‐sphere Gd(III) coordination.