Complexation properties of N,N′,N″,N‴-[1,4,7,10- tetraazacyclododecane-1,4,7,10-tetrayltetrakis(1-oxoethane-2,1-diyl)] tetrakis[glycine] (H4dotagl). Equilibrium, kinetic, and relaxation behavior of the lanthanide(III) complexes

Z. Baranyai, E. Brücher, Tímea Iványi, R. Király, István Lázár, László Zékány

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Abstract

Eu3+, Dy3+, and Yb3+ complexes of the dota-derived tetramide N,N′,N″,N‴-[1,4,7,10- tetraazacyclododecane-1,4,7,10-tetrayltetrakis(1-oxoethane-2,1-diyl)] tetrakis[glycine] (H4dotagl) are potential CEST contrast agents in MRI. In the [Ln(dotagl)] complexes, the Ln3+ ion is in the cage formed by the four ring N-atoms and the amide O-atom donor atoms, and a H 2O molecule occupies the ninth coordination site. The stability constants of the [Ln(dotagl)] complexes are ca. 10 orders of magnitude lower than those of the [Ln(dota)] analogues (H4dota=1,4,7,10- tetraazacyclododecane-1,4,7,10-tetraacetic acid). The free carboxylate groups in [Ln-(dotagl)] are protonated in the pH range 1-5, resulting in mono-, di-, tri-, and tetraprotonated species. Complexes with divalent metals (Mg 2+, Ca2+, and Cu2+) are also of relatively low stability. At pH>8, Cu2+ forms a hydroxo complex; however, the amide H-atom(s) does not dissociate due to the absence of anchor N-atom(s), which is the result of the rigid structure of the ring. The relaxivities of [Gd(dotagl)] decrease from 10 to 25°, then increase between 30-50°. This unusual trend is interpreted with the low H2O-exchange rate. The [Ln(dotagl)] complexes form slowly, via the equilibrium formation of a monoprotonated intermediate, which deprotonates and rearranges to the product in a slow. OH--catalyzed reaction. The formation rates are lower than those for the corresponding Ln(dota) complexes. The dissociation rate of [Eu(dotagl)] is directly proportional to [H+] (0.1-1.0M HClO 4); the proton-assisted dissociation rate is lower for [Eu(H 4dotagl)] (k1 = 8.1·10-6 M-1 S-1) than for [Eu(dota)] (k1 = 1.4·10-5 M-1 S-1).

Original languageEnglish
Pages (from-to)604-617
Number of pages14
JournalHelvetica Chimica Acta
Volume88
Issue number3
DOIs
Publication statusPublished - 2005

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Lanthanoid Series Elements
glycine
Rare earth elements
Complexation
Amides
Glycine
Amino acids
Atoms
Kinetics
kinetics
Contrast Media
atoms
Protons
Metals
amides
Ions
dissociation
Rigid structures
Hydrogen
rings

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{1e8685b518954a2c9ca573813565fa3f,
title = "Complexation properties of N,N′,N″,N‴-[1,4,7,10- tetraazacyclododecane-1,4,7,10-tetrayltetrakis(1-oxoethane-2,1-diyl)] tetrakis[glycine] (H4dotagl). Equilibrium, kinetic, and relaxation behavior of the lanthanide(III) complexes",
abstract = "Eu3+, Dy3+, and Yb3+ complexes of the dota-derived tetramide N,N′,N″,N‴-[1,4,7,10- tetraazacyclododecane-1,4,7,10-tetrayltetrakis(1-oxoethane-2,1-diyl)] tetrakis[glycine] (H4dotagl) are potential CEST contrast agents in MRI. In the [Ln(dotagl)] complexes, the Ln3+ ion is in the cage formed by the four ring N-atoms and the amide O-atom donor atoms, and a H 2O molecule occupies the ninth coordination site. The stability constants of the [Ln(dotagl)] complexes are ca. 10 orders of magnitude lower than those of the [Ln(dota)] analogues (H4dota=1,4,7,10- tetraazacyclododecane-1,4,7,10-tetraacetic acid). The free carboxylate groups in [Ln-(dotagl)] are protonated in the pH range 1-5, resulting in mono-, di-, tri-, and tetraprotonated species. Complexes with divalent metals (Mg 2+, Ca2+, and Cu2+) are also of relatively low stability. At pH>8, Cu2+ forms a hydroxo complex; however, the amide H-atom(s) does not dissociate due to the absence of anchor N-atom(s), which is the result of the rigid structure of the ring. The relaxivities of [Gd(dotagl)] decrease from 10 to 25°, then increase between 30-50°. This unusual trend is interpreted with the low H2O-exchange rate. The [Ln(dotagl)] complexes form slowly, via the equilibrium formation of a monoprotonated intermediate, which deprotonates and rearranges to the product in a slow. OH--catalyzed reaction. The formation rates are lower than those for the corresponding Ln(dota) complexes. The dissociation rate of [Eu(dotagl)] is directly proportional to [H+] (0.1-1.0M HClO 4); the proton-assisted dissociation rate is lower for [Eu(H 4dotagl)] (k1 = 8.1·10-6 M-1 S-1) than for [Eu(dota)] (k1 = 1.4·10-5 M-1 S-1).",
author = "Z. Baranyai and E. Br{\"u}cher and T{\'i}mea Iv{\'a}nyi and R. Kir{\'a}ly and Istv{\'a}n L{\'a}z{\'a}r and L{\'a}szl{\'o} Z{\'e}k{\'a}ny",
year = "2005",
doi = "10.1002/hlca.200590042",
language = "English",
volume = "88",
pages = "604--617",
journal = "Helvetica Chimica Acta",
issn = "0018-019X",
publisher = "Verlag Helvetica Chimica Acta AG",
number = "3",

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TY - JOUR

T1 - Complexation properties of N,N′,N″,N‴-[1,4,7,10- tetraazacyclododecane-1,4,7,10-tetrayltetrakis(1-oxoethane-2,1-diyl)] tetrakis[glycine] (H4dotagl). Equilibrium, kinetic, and relaxation behavior of the lanthanide(III) complexes

AU - Baranyai, Z.

AU - Brücher, E.

AU - Iványi, Tímea

AU - Király, R.

AU - Lázár, István

AU - Zékány, László

PY - 2005

Y1 - 2005

N2 - Eu3+, Dy3+, and Yb3+ complexes of the dota-derived tetramide N,N′,N″,N‴-[1,4,7,10- tetraazacyclododecane-1,4,7,10-tetrayltetrakis(1-oxoethane-2,1-diyl)] tetrakis[glycine] (H4dotagl) are potential CEST contrast agents in MRI. In the [Ln(dotagl)] complexes, the Ln3+ ion is in the cage formed by the four ring N-atoms and the amide O-atom donor atoms, and a H 2O molecule occupies the ninth coordination site. The stability constants of the [Ln(dotagl)] complexes are ca. 10 orders of magnitude lower than those of the [Ln(dota)] analogues (H4dota=1,4,7,10- tetraazacyclododecane-1,4,7,10-tetraacetic acid). The free carboxylate groups in [Ln-(dotagl)] are protonated in the pH range 1-5, resulting in mono-, di-, tri-, and tetraprotonated species. Complexes with divalent metals (Mg 2+, Ca2+, and Cu2+) are also of relatively low stability. At pH>8, Cu2+ forms a hydroxo complex; however, the amide H-atom(s) does not dissociate due to the absence of anchor N-atom(s), which is the result of the rigid structure of the ring. The relaxivities of [Gd(dotagl)] decrease from 10 to 25°, then increase between 30-50°. This unusual trend is interpreted with the low H2O-exchange rate. The [Ln(dotagl)] complexes form slowly, via the equilibrium formation of a monoprotonated intermediate, which deprotonates and rearranges to the product in a slow. OH--catalyzed reaction. The formation rates are lower than those for the corresponding Ln(dota) complexes. The dissociation rate of [Eu(dotagl)] is directly proportional to [H+] (0.1-1.0M HClO 4); the proton-assisted dissociation rate is lower for [Eu(H 4dotagl)] (k1 = 8.1·10-6 M-1 S-1) than for [Eu(dota)] (k1 = 1.4·10-5 M-1 S-1).

AB - Eu3+, Dy3+, and Yb3+ complexes of the dota-derived tetramide N,N′,N″,N‴-[1,4,7,10- tetraazacyclododecane-1,4,7,10-tetrayltetrakis(1-oxoethane-2,1-diyl)] tetrakis[glycine] (H4dotagl) are potential CEST contrast agents in MRI. In the [Ln(dotagl)] complexes, the Ln3+ ion is in the cage formed by the four ring N-atoms and the amide O-atom donor atoms, and a H 2O molecule occupies the ninth coordination site. The stability constants of the [Ln(dotagl)] complexes are ca. 10 orders of magnitude lower than those of the [Ln(dota)] analogues (H4dota=1,4,7,10- tetraazacyclododecane-1,4,7,10-tetraacetic acid). The free carboxylate groups in [Ln-(dotagl)] are protonated in the pH range 1-5, resulting in mono-, di-, tri-, and tetraprotonated species. Complexes with divalent metals (Mg 2+, Ca2+, and Cu2+) are also of relatively low stability. At pH>8, Cu2+ forms a hydroxo complex; however, the amide H-atom(s) does not dissociate due to the absence of anchor N-atom(s), which is the result of the rigid structure of the ring. The relaxivities of [Gd(dotagl)] decrease from 10 to 25°, then increase between 30-50°. This unusual trend is interpreted with the low H2O-exchange rate. The [Ln(dotagl)] complexes form slowly, via the equilibrium formation of a monoprotonated intermediate, which deprotonates and rearranges to the product in a slow. OH--catalyzed reaction. The formation rates are lower than those for the corresponding Ln(dota) complexes. The dissociation rate of [Eu(dotagl)] is directly proportional to [H+] (0.1-1.0M HClO 4); the proton-assisted dissociation rate is lower for [Eu(H 4dotagl)] (k1 = 8.1·10-6 M-1 S-1) than for [Eu(dota)] (k1 = 1.4·10-5 M-1 S-1).

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DO - 10.1002/hlca.200590042

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JO - Helvetica Chimica Acta

JF - Helvetica Chimica Acta

SN - 0018-019X

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