NMR Studies of the Lanthanide(III) Complexes of 1,4,7,10-Tetraazacyclododecane-l,4,7,10-tetrakis(methanephosphonic acid mono(2',2',2'-trifluoroethyl) ester)

Won D. Kim, Garry E. Kiefer, Jurriaan Huskens, A. Dean Sherry

Research output: Contribution to journalArticle

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Abstract

A new macrocyclic ligand 1,4.7.10,-tetraazacyclododecane-1.4,7,10-telrakis(methanephosphonic acid mono(2′,2′,2′trifluoroethyl) ester) (F-DOTPME) has been prepared and some of its metal binding properties examined. The ligand protonation constants (log K1 = 10.5. log K2 = 6.7) and its stability constant with CaII (log KCL = 8.4) were determined by pH potentiometry. The stability of the La complex could not be determined by potentiometry so it was evaluated in an EDTA competition experiment using 31P NMR to monitor the reaction. The dissociation kinetics of La(F-DOTPME)- was slow, with a K of only 1.0 × 10-7 s-1 A series of Ln(F-DOTPME)- complexes (LnIII = La, Gd, Dy, Tm, and Yb) were examined by multinuclear NMR. The spectra show that these complexes exist in aqueous solution as a mixture of stereoisomers of nearly equal energy (energy differences of less than 1 kJ/mol). Several resolved 19F resonances in the NMR spectra of the Dy(F-DOTPME)-, Tm(F-DOTPMEF, and Yb(F-DOTPME)" complexes have been assigned to specific diastereomers by comparing resonance integrals, assuming an interaction model between neighboring pendant arms, and the magnitude and direction of the hyperfme |l!F NMR shifts induced by the paramagnetic lanthanide cation. Cationic detergents added to two different Ln(F-DOTPME)" complexes altered the distribution of isomers in favor of the symmetrical A-SSSS isomer, while neutral polyethylene glycol affected the |l'F chemical shifts of some isomers without altering their populations. Gd(F-DOTPME)- displayed a water proton relaxivity (R1) of 2.5 mM- s-1 at 25 °C and 40 MHz, typical of complexes lacking an inner-sphere-coordinated water molecule. 17O NMR was used to confirm that Dy(F-DOTPME)- does not have an inner-sphere-coordinated water molecule. Addition of human serum albumin to aqueous solutions of Gd(F-DOTPME)- produced a 4-fold increase in water relaxivity, and an analysis of binding curves indicated the fluorinated complex binds to HSA with a binding constant of about 0.17 mM.

Original languageEnglish (US)
Pages (from-to)4128-4134
Number of pages7
JournalInorganic Chemistry
Volume36
Issue number18
StatePublished - 1997

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Lanthanoid Series Elements
esters
Esters
Nuclear magnetic resonance
nuclear magnetic resonance
acids
Acids
Isomers
potentiometric analysis
isomers
Water
water
Ligands
aqueous solutions
ligands
Molecules
Stereoisomerism
detergents
ethylenediaminetetraacetic acids
Protonation

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

NMR Studies of the Lanthanide(III) Complexes of 1,4,7,10-Tetraazacyclododecane-l,4,7,10-tetrakis(methanephosphonic acid mono(2',2',2'-trifluoroethyl) ester). / Kim, Won D.; Kiefer, Garry E.; Huskens, Jurriaan; Dean Sherry, A.

In: Inorganic Chemistry, Vol. 36, No. 18, 1997, p. 4128-4134.

Research output: Contribution to journalArticle

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abstract = "A new macrocyclic ligand 1,4.7.10,-tetraazacyclododecane-1.4,7,10-telrakis(methanephosphonic acid mono(2′,2′,2′trifluoroethyl) ester) (F-DOTPME) has been prepared and some of its metal binding properties examined. The ligand protonation constants (log K1 = 10.5. log K2 = 6.7) and its stability constant with CaII (log KCL = 8.4) were determined by pH potentiometry. The stability of the La complex could not be determined by potentiometry so it was evaluated in an EDTA competition experiment using 31P NMR to monitor the reaction. The dissociation kinetics of La(F-DOTPME)- was slow, with a K of only 1.0 × 10-7 s-1 A series of Ln(F-DOTPME)- complexes (LnIII = La, Gd, Dy, Tm, and Yb) were examined by multinuclear NMR. The spectra show that these complexes exist in aqueous solution as a mixture of stereoisomers of nearly equal energy (energy differences of less than 1 kJ/mol). Several resolved 19F resonances in the NMR spectra of the Dy(F-DOTPME)-, Tm(F-DOTPMEF, and Yb(F-DOTPME){"} complexes have been assigned to specific diastereomers by comparing resonance integrals, assuming an interaction model between neighboring pendant arms, and the magnitude and direction of the hyperfme |l!F NMR shifts induced by the paramagnetic lanthanide cation. Cationic detergents added to two different Ln(F-DOTPME){"} complexes altered the distribution of isomers in favor of the symmetrical A-SSSS isomer, while neutral polyethylene glycol affected the |l'F chemical shifts of some isomers without altering their populations. Gd(F-DOTPME)- displayed a water proton relaxivity (R1) of 2.5 mM- s-1 at 25 °C and 40 MHz, typical of complexes lacking an inner-sphere-coordinated water molecule. 17O NMR was used to confirm that Dy(F-DOTPME)- does not have an inner-sphere-coordinated water molecule. Addition of human serum albumin to aqueous solutions of Gd(F-DOTPME)- produced a 4-fold increase in water relaxivity, and an analysis of binding curves indicated the fluorinated complex binds to HSA with a binding constant of about 0.17 mM.",
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T1 - NMR Studies of the Lanthanide(III) Complexes of 1,4,7,10-Tetraazacyclododecane-l,4,7,10-tetrakis(methanephosphonic acid mono(2',2',2'-trifluoroethyl) ester)

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AU - Dean Sherry, A.

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N2 - A new macrocyclic ligand 1,4.7.10,-tetraazacyclododecane-1.4,7,10-telrakis(methanephosphonic acid mono(2′,2′,2′trifluoroethyl) ester) (F-DOTPME) has been prepared and some of its metal binding properties examined. The ligand protonation constants (log K1 = 10.5. log K2 = 6.7) and its stability constant with CaII (log KCL = 8.4) were determined by pH potentiometry. The stability of the La complex could not be determined by potentiometry so it was evaluated in an EDTA competition experiment using 31P NMR to monitor the reaction. The dissociation kinetics of La(F-DOTPME)- was slow, with a K of only 1.0 × 10-7 s-1 A series of Ln(F-DOTPME)- complexes (LnIII = La, Gd, Dy, Tm, and Yb) were examined by multinuclear NMR. The spectra show that these complexes exist in aqueous solution as a mixture of stereoisomers of nearly equal energy (energy differences of less than 1 kJ/mol). Several resolved 19F resonances in the NMR spectra of the Dy(F-DOTPME)-, Tm(F-DOTPMEF, and Yb(F-DOTPME)" complexes have been assigned to specific diastereomers by comparing resonance integrals, assuming an interaction model between neighboring pendant arms, and the magnitude and direction of the hyperfme |l!F NMR shifts induced by the paramagnetic lanthanide cation. Cationic detergents added to two different Ln(F-DOTPME)" complexes altered the distribution of isomers in favor of the symmetrical A-SSSS isomer, while neutral polyethylene glycol affected the |l'F chemical shifts of some isomers without altering their populations. Gd(F-DOTPME)- displayed a water proton relaxivity (R1) of 2.5 mM- s-1 at 25 °C and 40 MHz, typical of complexes lacking an inner-sphere-coordinated water molecule. 17O NMR was used to confirm that Dy(F-DOTPME)- does not have an inner-sphere-coordinated water molecule. Addition of human serum albumin to aqueous solutions of Gd(F-DOTPME)- produced a 4-fold increase in water relaxivity, and an analysis of binding curves indicated the fluorinated complex binds to HSA with a binding constant of about 0.17 mM.

AB - A new macrocyclic ligand 1,4.7.10,-tetraazacyclododecane-1.4,7,10-telrakis(methanephosphonic acid mono(2′,2′,2′trifluoroethyl) ester) (F-DOTPME) has been prepared and some of its metal binding properties examined. The ligand protonation constants (log K1 = 10.5. log K2 = 6.7) and its stability constant with CaII (log KCL = 8.4) were determined by pH potentiometry. The stability of the La complex could not be determined by potentiometry so it was evaluated in an EDTA competition experiment using 31P NMR to monitor the reaction. The dissociation kinetics of La(F-DOTPME)- was slow, with a K of only 1.0 × 10-7 s-1 A series of Ln(F-DOTPME)- complexes (LnIII = La, Gd, Dy, Tm, and Yb) were examined by multinuclear NMR. The spectra show that these complexes exist in aqueous solution as a mixture of stereoisomers of nearly equal energy (energy differences of less than 1 kJ/mol). Several resolved 19F resonances in the NMR spectra of the Dy(F-DOTPME)-, Tm(F-DOTPMEF, and Yb(F-DOTPME)" complexes have been assigned to specific diastereomers by comparing resonance integrals, assuming an interaction model between neighboring pendant arms, and the magnitude and direction of the hyperfme |l!F NMR shifts induced by the paramagnetic lanthanide cation. Cationic detergents added to two different Ln(F-DOTPME)" complexes altered the distribution of isomers in favor of the symmetrical A-SSSS isomer, while neutral polyethylene glycol affected the |l'F chemical shifts of some isomers without altering their populations. Gd(F-DOTPME)- displayed a water proton relaxivity (R1) of 2.5 mM- s-1 at 25 °C and 40 MHz, typical of complexes lacking an inner-sphere-coordinated water molecule. 17O NMR was used to confirm that Dy(F-DOTPME)- does not have an inner-sphere-coordinated water molecule. Addition of human serum albumin to aqueous solutions of Gd(F-DOTPME)- produced a 4-fold increase in water relaxivity, and an analysis of binding curves indicated the fluorinated complex binds to HSA with a binding constant of about 0.17 mM.

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