Interaction of [Ln(DO2A)(H2O)2-3]+ and [Ln(DO2P)(H2O)2-3]- with phosphate, acetate and fluoride anions in aqueous solution

K. Kimpe, W. D'Olieslager, C. Görller-Walrand, A. Figueirinha, Z. Kovács, C. F G C Geraldes

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Mixed complexation of the lanthanide(III) chelates of the 1,7-disubstituted tetraazacyclododecane macrocycles DO2A and DO2P with phosphate, acetate and fluoride anions was studied in aqueous solutions using high resolution 1H and 31P NMR spectroscopy. The [La(DO2A)(H2O)2-3]+ and [Ce(DO2A)(H2O)2-3]+ chelates readily decompose in aqueous solutions containing phosphate anions. [Nd(DO2A)(H2O)2-3]+ and [Eu(DO2A)(H2O)2-3]+ chelates remain stable in an acetate environment. Association constants for the 1:1 adduct were obtained via 1H NMR titrations. In a fluoride environment, [La(DO2A)(H2O)2-3]+ was found to be unstable, in contrast to [Eu(DO2A)(H2O)2-3]+, for which the association constant for the 1:1 adduct was calculated. Chelate formation, as well as mixed complexation with fluoride and phosphate was studied for [Eu(DO2P)(H2O)2-3]-. The 31P chemical shifts of [Eu(DO2P)(H2O)2-3]- indicate that the DO2P macrocycle forms an 'in-cage' complex with binding through all four nitrogens. The [Eu(DO2P)(H2O)2-3]- chelate gradually decomposes in a phosphate environment, but remains stable in an fluoride environment.

Original languageEnglish (US)
Pages (from-to)828-832
Number of pages5
JournalJournal of Alloys and Compounds
Volume323-324
DOIs
StatePublished - Jul 12 2001

Fingerprint

Fluorides
Anions
Phosphates
Acetates
Negative ions
Complexation
Lanthanoid Series Elements
Chemical shift
Rare earth elements
Titration
Nuclear magnetic resonance spectroscopy
Nitrogen
Nuclear magnetic resonance
Association reactions

Keywords

  • Lanthanides
  • MRI contrast agents
  • Nuclear resonances
  • Rare earths

ASJC Scopus subject areas

  • Metals and Alloys

Cite this

Interaction of [Ln(DO2A)(H2O)2-3]+ and [Ln(DO2P)(H2O)2-3]- with phosphate, acetate and fluoride anions in aqueous solution. / Kimpe, K.; D'Olieslager, W.; Görller-Walrand, C.; Figueirinha, A.; Kovács, Z.; Geraldes, C. F G C.

In: Journal of Alloys and Compounds, Vol. 323-324, 12.07.2001, p. 828-832.

Research output: Contribution to journalArticle

Kimpe, K. ; D'Olieslager, W. ; Görller-Walrand, C. ; Figueirinha, A. ; Kovács, Z. ; Geraldes, C. F G C. / Interaction of [Ln(DO2A)(H2O)2-3]+ and [Ln(DO2P)(H2O)2-3]- with phosphate, acetate and fluoride anions in aqueous solution. In: Journal of Alloys and Compounds. 2001 ; Vol. 323-324. pp. 828-832.
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abstract = "Mixed complexation of the lanthanide(III) chelates of the 1,7-disubstituted tetraazacyclododecane macrocycles DO2A and DO2P with phosphate, acetate and fluoride anions was studied in aqueous solutions using high resolution 1H and 31P NMR spectroscopy. The [La(DO2A)(H2O)2-3]+ and [Ce(DO2A)(H2O)2-3]+ chelates readily decompose in aqueous solutions containing phosphate anions. [Nd(DO2A)(H2O)2-3]+ and [Eu(DO2A)(H2O)2-3]+ chelates remain stable in an acetate environment. Association constants for the 1:1 adduct were obtained via 1H NMR titrations. In a fluoride environment, [La(DO2A)(H2O)2-3]+ was found to be unstable, in contrast to [Eu(DO2A)(H2O)2-3]+, for which the association constant for the 1:1 adduct was calculated. Chelate formation, as well as mixed complexation with fluoride and phosphate was studied for [Eu(DO2P)(H2O)2-3]-. The 31P chemical shifts of [Eu(DO2P)(H2O)2-3]- indicate that the DO2P macrocycle forms an 'in-cage' complex with binding through all four nitrogens. The [Eu(DO2P)(H2O)2-3]- chelate gradually decomposes in a phosphate environment, but remains stable in an fluoride environment.",
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T1 - Interaction of [Ln(DO2A)(H2O)2-3]+ and [Ln(DO2P)(H2O)2-3]- with phosphate, acetate and fluoride anions in aqueous solution

AU - Kimpe, K.

AU - D'Olieslager, W.

AU - Görller-Walrand, C.

AU - Figueirinha, A.

AU - Kovács, Z.

AU - Geraldes, C. F G C

PY - 2001/7/12

Y1 - 2001/7/12

N2 - Mixed complexation of the lanthanide(III) chelates of the 1,7-disubstituted tetraazacyclododecane macrocycles DO2A and DO2P with phosphate, acetate and fluoride anions was studied in aqueous solutions using high resolution 1H and 31P NMR spectroscopy. The [La(DO2A)(H2O)2-3]+ and [Ce(DO2A)(H2O)2-3]+ chelates readily decompose in aqueous solutions containing phosphate anions. [Nd(DO2A)(H2O)2-3]+ and [Eu(DO2A)(H2O)2-3]+ chelates remain stable in an acetate environment. Association constants for the 1:1 adduct were obtained via 1H NMR titrations. In a fluoride environment, [La(DO2A)(H2O)2-3]+ was found to be unstable, in contrast to [Eu(DO2A)(H2O)2-3]+, for which the association constant for the 1:1 adduct was calculated. Chelate formation, as well as mixed complexation with fluoride and phosphate was studied for [Eu(DO2P)(H2O)2-3]-. The 31P chemical shifts of [Eu(DO2P)(H2O)2-3]- indicate that the DO2P macrocycle forms an 'in-cage' complex with binding through all four nitrogens. The [Eu(DO2P)(H2O)2-3]- chelate gradually decomposes in a phosphate environment, but remains stable in an fluoride environment.

AB - Mixed complexation of the lanthanide(III) chelates of the 1,7-disubstituted tetraazacyclododecane macrocycles DO2A and DO2P with phosphate, acetate and fluoride anions was studied in aqueous solutions using high resolution 1H and 31P NMR spectroscopy. The [La(DO2A)(H2O)2-3]+ and [Ce(DO2A)(H2O)2-3]+ chelates readily decompose in aqueous solutions containing phosphate anions. [Nd(DO2A)(H2O)2-3]+ and [Eu(DO2A)(H2O)2-3]+ chelates remain stable in an acetate environment. Association constants for the 1:1 adduct were obtained via 1H NMR titrations. In a fluoride environment, [La(DO2A)(H2O)2-3]+ was found to be unstable, in contrast to [Eu(DO2A)(H2O)2-3]+, for which the association constant for the 1:1 adduct was calculated. Chelate formation, as well as mixed complexation with fluoride and phosphate was studied for [Eu(DO2P)(H2O)2-3]-. The 31P chemical shifts of [Eu(DO2P)(H2O)2-3]- indicate that the DO2P macrocycle forms an 'in-cage' complex with binding through all four nitrogens. The [Eu(DO2P)(H2O)2-3]- chelate gradually decomposes in a phosphate environment, but remains stable in an fluoride environment.

KW - Lanthanides

KW - MRI contrast agents

KW - Nuclear resonances

KW - Rare earths

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