Synthesis of two derivatives of 3,6,9-tri(carboxymethyl)-3,6,9-triazaundecanedioic acid and the stabilities of their complexes with Ca2+, Cu2+, Zn2+, Dy3+ and Gd3+

Yun-Ming Wang*, Tsann Hwang Cheng, Gin Chung Liu

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

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 Me4NNO3 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. 17O 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.

Original languageEnglish
Pages (from-to)1083-1094
Number of pages12
JournalJournal of the Chinese Chemical Society
Volume47
Issue number5
DOIs
StatePublished - 1 Jan 2000

Keywords

  • Contrast agents
  • Lanthanide complexes
  • MRI
  • Paramagnetic complexes
  • Relaxivity
  • Thermodynamics

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