Properties, solution state behavior, and crystal structures of chelates of DOTMA

Silvio Aime, Mauro Botta, Zoltán Garda, Benjamin E. Kucera, Gyula Tircso, Victor G. Young, Mark Woods

Research output: Contribution to journalArticle

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Abstract

The chemistry of polyamino carboxylates and their use as ligands for Ln 3+ ions is of considerable interest from the point of view of the development of new imaging agents. Of particular interest is the chemistry of the macrocyclic ligand 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) and its derivatives. Herein we report that the tetramethylated DOTA derivative, DOTMA, possess several properties that, from an imaging agent development point of view, are more advantageous than those of the parent DOTA. In particular, the Ln 3+ chelates of DOTMA exhibit a marked preference for the monocapped twisted square antiprismatic coordination isomer which imparts more rapid water exchange kinetics on the chelates; τ M 298 was determined to be 85 ns for GdDOTMA. Differential analysis of the 17O R temperature profiles of both GdDOTA and GdDOTMA afforded the τ M 298 values for the square (SAP) and twisted square antiprismatic (TSAP) isomers of each chelate that were almost identical: 365 ns (SAP) and 52 ns (TSAP). The origin of this accelerated water exchange in the TSAP isomer appears to be the slightly longer Gd-OH 2 bond distance (2.50 Å) that is observed in the crystal structure of GdDOTMA which crystallizes in the P 2 space group as a TSAP isomer. The Ln 3+ chelates of DOTMA also exhibit high thermodynamic stabilities ranging from log K ML = 20.5 for CeDOTMA, 23.5 for EuDOTMA and YbDOTMA comparable to, but a shade lower than, those of DOTA.

Original languageEnglish (US)
Pages (from-to)7955-7965
Number of pages11
JournalInorganic Chemistry
Volume50
Issue number17
DOIs
StatePublished - Sep 5 2011

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chelates
Isomers
isomers
Crystal structure
acids
crystal structure
chemistry
Ligands
Derivatives
shades
Imaging techniques
ligands
Water
temperature profiles
water
carboxylates
Thermodynamic stability
Ions
thermodynamics
Kinetics

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Aime, S., Botta, M., Garda, Z., Kucera, B. E., Tircso, G., Young, V. G., & Woods, M. (2011). Properties, solution state behavior, and crystal structures of chelates of DOTMA. Inorganic Chemistry, 50(17), 7955-7965. https://doi.org/10.1021/ic2012827

Properties, solution state behavior, and crystal structures of chelates of DOTMA. / Aime, Silvio; Botta, Mauro; Garda, Zoltán; Kucera, Benjamin E.; Tircso, Gyula; Young, Victor G.; Woods, Mark.

In: Inorganic Chemistry, Vol. 50, No. 17, 05.09.2011, p. 7955-7965.

Research output: Contribution to journalArticle

Aime, S, Botta, M, Garda, Z, Kucera, BE, Tircso, G, Young, VG & Woods, M 2011, 'Properties, solution state behavior, and crystal structures of chelates of DOTMA', Inorganic Chemistry, vol. 50, no. 17, pp. 7955-7965. https://doi.org/10.1021/ic2012827
Aime S, Botta M, Garda Z, Kucera BE, Tircso G, Young VG et al. Properties, solution state behavior, and crystal structures of chelates of DOTMA. Inorganic Chemistry. 2011 Sep 5;50(17):7955-7965. https://doi.org/10.1021/ic2012827
Aime, Silvio ; Botta, Mauro ; Garda, Zoltán ; Kucera, Benjamin E. ; Tircso, Gyula ; Young, Victor G. ; Woods, Mark. / Properties, solution state behavior, and crystal structures of chelates of DOTMA. In: Inorganic Chemistry. 2011 ; Vol. 50, No. 17. pp. 7955-7965.
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