Synthesis of two N,N′-bis(N,N-dialkylamide) derivatives of diethylenetriaminepentaacetic acid and the stabilities of their complexes with Gd3+, Ca2+, Cu2+, and Zn2+

Yun-Ming Wang*

*Corresponding author for this work

Research output: Contribution to journalArticle

4 Scopus citations

Abstract

Two bis(N,N-dialkylamide) derivatives of DTPA [(carboxymethyl)iminobis (ethylenenitrilo) tetraacetic acid], DTPA-BDMA = the bis(N,N-dimethylamide) and DTPA-BDEA = the bis(N,N-diethylamide) 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. Stability and selectivity constants were measured to evaluate the possibility of using the corresponding gadolinium(III) complexes for magnetic resonance imaging contrast agents. The stability constants of gadolinium(III), copper(II), zinc(II), and calcium(II) complexes with DTPA-BDMA and DTPA-BDEA were investigated quantitatively by potentiometry. The stability constant for gadolinium(III) complexes is larger than those for Ca(II), Zn(II), and Cu(II) complexes. The selectivity constants and modified selectivity constants of the amides for Gd3+ over endogenously available metal ions were calculated. Effectiveness of these two ligands in binding divalent and trivalent metal ions in biological media is assessed by comparing pM values at physiological pH 7.4. Spin-lattice relaxivity values R1 for Gd(III) complexes were also determined. The observed relaxivity values were found to decrease with increasing pH in the acid range below pH 4 and relaxivity values became invariant with respect to pH changes over the range of 4-10. 17O NMR shifts showed that the [Dy(DTPA-BDMA)] and [Dy(DTPA-BDEA)] complexes had one inner-sphere water molecule. Water proton spin-lattice relaxation rates for the [Gd(DTPA-BDMA)] and [Gd(DTPA-BDEA)] complexes were also consistent with one inner-sphere gadolinium(III) coordination position.

Original languageEnglish
Pages (from-to)551-561
Number of pages11
JournalJournal of the Chinese Chemical Society
Volume46
Issue number4
DOIs
StatePublished - 1 Jan 1999

Keywords

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

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