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Lanthanide(III) complexes of tris(amide) PCTA derivatives as potential bimodal magnetic resonance and optical imaging agents.

ABSTRACT: Lanthanide complexes of two tris(amide) derivatives of PCTA were synthesized and characterized. The relaxometric and luminescence properties of their lanthanide complexes were investigated as bimodal magnetic resonance (MR) and optical imaging agents. Luminescence studies show that one of the Tb(III) complexes dimerizes in solution at low millimolar concentrations, whereas the other may have a higher than expected coordination number in solution. The corresponding Gd(III) complexes display unusually high T(1) relaxivities and enhanced kinetic inertness compared to GdPCTA. These features suggest that these new chelates may be suitable for in vivo applications. The fast water-exchange rates observed for these complexes make them unsuitable as paramagnetic chemical exchange saturation transfer (PARACEST) agents.

SUBMITTER: Rojas-Quijano FA

PROVIDER: S-EPMC2907668 | biostudies-literature | 2009 Dec

REPOSITORIES: biostudies-literature

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Lanthanide(III) complexes of tris(amide) PCTA derivatives as potential bimodal magnetic resonance and optical imaging agents.

Rojas-Quijano Federico A FA Benyó Eniko Tircsóné ET Tircsó Gyula G Kálmán Ferenc K FK Baranyai Zsolt Z Aime Silvio S Sherry A Dean AD Kovács Zoltán Z

Chemistry (Weinheim an der Bergstrasse, Germany) 20091201 47

Lanthanide complexes of two tris(amide) derivatives of PCTA were synthesized and characterized. The relaxometric and luminescence properties of their lanthanide complexes were investigated as bimodal magnetic resonance (MR) and optical imaging agents. Luminescence studies show that one of the Tb(III) complexes dimerizes in solution at low millimolar concentrations, whereas the other may have a higher than expected coordination number in solution. The corresponding Gd(III) complexes display unusu ...[more]

PMID: 19882595

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Project description:The protonation constants () of 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-3,6,9-triacetic acid (PCTA) and stability constants of complexes formed between this pyridine-containing macrocycle and several different metal ions have been determined in 1.0 M KCl at 25 degrees C and compared to previous literature values. The first protonation constant was found to be 0.5-0.6 log units higher than the value reported previously, and a total of five protonation steps were detected (log = 11.36, 7.35, 3.83, 2.12, and 1.29). The stability constants of complexes formed between PCTA and Mg2+, Ca2+, Cu2+, and Zn2+ were also somewhat higher than those previously reported, but this difference could be largely attributed to the higher first protonation constant of the ligand. Stability constants of complexes formed between PCTA and the Ln3+ series of ions and Y3+ were determined by using an "out-of-cell" potentiometric method. These values ranged from log K = 18.15 for Ce(PCTA) to log K = 20.63 for Yb(PCTA), increasing along the Ln series in proportion to decreasing Ln3+ cation size. The rates of complex formation for Ce(PCTA), Eu(PCTA), Y(PCTA), and Yb(PCTA) were followed by conventional UV-vis spectroscopy in the pH range 3.5-4.4. First-order rate constants (saturation kinetics) obtained for different ligand-to-metal ion ratios were consistent with the rapid formation of a diprotonated intermediate, Ln(H(2)PCTA)(2+). The stabilities of the intermediates as determined from the kinetic data were 2.81, 3.12, 2.97, and 2.69 log K units for Ce(H(2)PCTA), Eu(H(2)PCTA), Y(H(2)PCTA), and Yb(H(2)PCTA), respectively. Rearrangement of these intermediates to the fully chelated complexes was the rate-determining step, and the rate constant (k(r)) for this process was found to be inversely proportional to the proton concentration. The formation rates (k(OH)) increased with a decrease in the lanthanide ion size [9.68 x 10(7), 1.74 x 10(8), 1.13 x 10(8), and 1.11 x 10(9) M(-1) s(-1) for Ce(PCTA), Eu(PCTA), Y(PCTA), and Yb(PCTA), respectively]. These data indicate that the Ln(PCTA) complexes exhibit the fastest formation rates among all lanthanide macrocyclic ligand complexes studied to date. The acid-catalyzed dissociation rates (k1) varied with the cation from 9.61 x 10(-4), 5.08 x 10(-4), 1.07 x 10(-3), and 2.80 x 10(-4) M(-1) s(-1) for Ce(PCTA), Eu(PCTA), Y(PCTA), and Yb(PCTA), respectively.

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Lanthanide(III) complexes of tris(amide) PCTA derivatives as potential bimodal magnetic resonance and optical imaging agents.

Publications

Lanthanide(III) complexes of tris(amide) PCTA derivatives as potential bimodal magnetic resonance and optical imaging agents.

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