Europium(III) DOTA-derivatives having ketone donor pendant arms display dramatically slower water exchange

Kayla N. Green, Subha Viswanathan, Federico A. Rojas-Quijano, Zoltan Kovacs, A. Dean Sherry

Research output: Contribution to journalArticle

26 Scopus citations

Abstract

A series of new 1,4,7,10-tetraazacyclododecane-derivatives having a combination of amide and ketone donor groups as side-arms were prepared, and their complexes with europium(III) studied in detail by high resolution NMR spectroscopy. The chemical shift of the Eu3+-bound water resonance, the chemical exchange saturation transfer (CEST) characteristics of the complexes, and the bound water residence lifetimes (τm) were found to vary dramatically with the chemical structure of the side-arms. Substitution of ketone oxygen donor atoms for amide oxygen donor atoms resulted in an increase in residence water lifetimes (τm) and a decrease in chemical shift of the Eu3+-bound water molecule (Δω). These experimental results along with density functional theory (DFT) calculations demonstrate that introduction of weakly donating oxygen atoms in these complexes results in a much weaker ligand field, more positive charge on the Eu3+ ion, and an increased water residence lifetime as expected for a dissociative mechanism. These results provide new insights into the design of paramagnetic CEST agents with even slower water exchange kinetics that will make them more efficient for in vivo imaging applications.

Original languageEnglish (US)
Pages (from-to)1648-1655
Number of pages8
JournalInorganic Chemistry
Volume50
Issue number5
DOIs
Publication statusPublished - Mar 7 2011

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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