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@article{1439557,
author = {Kubicek, Vojtěch and Bohmova, Zuzana and Ševčíková, Romana and Vaněk, Jakub and Lubal, Přemysl and Polakova, Zuzana and Michalicová, Romana and Kotek, Jan and Hermann, Petr},
article_location = {Washington},
article_number = {6},
doi = {http://dx.doi.org/10.1021/acs.inorgchem.7b02929},
keywords = {MACROCYCLIC CHELATORS; BIFUNCTIONAL CHELATOR; TRIAZACYCLONONANE-TRIACETIC ACID; FORMATION AND DISSOCIATION KINETICS},
language = {eng},
issn = {0020-1669},
journal = {Inorganic Chemistry},
title = {NOTA Complexes with Copper(II) and Divalent Metal Ions: Kinetic and Thermodynamic Studies},
url = {http://dx.doi.org/10.1021/acs.inorgchem.7b02929},
volume = {57},
year = {2018}
}
TY - JOUR
ID - 1439557
AU - Kubicek, Vojtěch - Bohmova, Zuzana - Ševčíková, Romana - Vaněk, Jakub - Lubal, Přemysl - Polakova, Zuzana - Michalicová, Romana - Kotek, Jan - Hermann, Petr
PY - 2018
TI - NOTA Complexes with Copper(II) and Divalent Metal Ions: Kinetic and Thermodynamic Studies
JF - Inorganic Chemistry
VL - 57
IS - 6
SP - 3061-3072
EP - 3061-3072
PB - American Chemical Society
SN - 00201669
KW - MACROCYCLIC CHELATORS
KW - BIFUNCTIONAL CHELATOR
KW - TRIAZACYCLONONANE-TRIACETIC ACID
KW - FORMATION AND DISSOCIATION KINETICS
UR - http://dx.doi.org/10.1021/acs.inorgchem.7b02929
N2 - H(3)nota derivatives are among the most studied macrocyclic ligands and are widely used for metal ion binding in biology and medicine. Despite more than 40 years of chemical research on H(3)nota, the comprehensive study of its solution chemistry has been overlooked. Thus, the coordination behavior of H(3)nota with several divalent metal ions was studied in detail with respect to its application as a chelator for copper radioisotopes in medical imaging and therapy. In the solid-state structure of the free ligand in zwitterionic form, one proton is bound in the macrocyclic cavity through a strong intramolecular hydrogen-bond system supporting the high basicity of the ring amine groups (log K-a = 13.17). The high stability of the [Cu(nota)](-) complex (log K-ML = 23.33) results in quantitative complex formation, even at pH <1.5. The ligand is moderately selective for Cu(II) over other metal ions (e.g., log K-ML(Zn) = 22.32 and log K-ML(Ni) = 19.24). This ligand forms a more stable complex with Mg(II) than with Ca(II) and forms surprisingly stable complexes with alkali-metal ions (stability order Li(I) > Na(I) > K(I)). Thus, H(3)nota shows high selectivity for small metal ions. The [Cu(nota)](-) complex is hexacoordinated at neutral pH, and the equatorial N2O2 interaction is strengthened by complex protonation. Detailed kinetic studies showed that the Cu(II) complex is formed quickly (millisecond time scale at c(Cu) approximate to 0.1 mM) through an out-of-cage intermediate. Conversely, conductivity measurements revealed that the Zn(II) complex is formed much more slowly than the Cu(II) complex. The Cu(II) complex has medium kinetic inertness (tau(1/2) 46 s; pH 0, 25 degrees C) and is less resistant to acid-assisted decomplexation than Cu(II) complexes with H(4)dota and H(4)teta. Surprisingly, [Cu(nota)](-) decomplexation is decelerated in the presence of Zn(II) ions due to the formation of a stable dinuclear complex. In conclusion, H(3)nota is a good carrier of copper radionuclides because the [Cu(nota)](-) complex is predominantly formed over complexes with common impurities in radiochemical formulations, Zn(II) and Ni(II), for thermodynamic and, primarily, for kinetic reasons. Furthermore, the in vivo stability of the [Cu(nota)](-) complex may be increased due to the formation of dinuclear complexes when it interacts with biometals.
ER -
KUBICEK, Vojtěch, Zuzana BOHMOVA, Romana ŠEVČÍKOVÁ, Jakub VANĚK, Přemysl LUBAL, Zuzana POLAKOVA, Romana MICHALICOVÁ, Jan KOTEK a Petr HERMANN. NOTA Complexes with Copper(II) and Divalent Metal Ions: Kinetic and Thermodynamic Studies. \textit{Inorganic Chemistry}. Washington: American Chemical Society, 2018, roč.~57, č.~6, s.~3061-3072. ISSN~0020-1669. Dostupné z: https://dx.doi.org/10.1021/acs.inorgchem.7b02929.
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