NOTA Complexes with Copper(II) and Divalent Metal Ions: Kinetic
and Thermodynamic Studies

J 2018

NOTA Complexes with Copper(II) and Divalent Metal Ions: Kinetic and Thermodynamic Studies

KUBICEK, Vojtěch, Zuzana BOHMOVA, Romana ŠEVČÍKOVÁ, Jakub VANĚK, Přemysl LUBAL et. al.

Basic information

Original name

NOTA Complexes with Copper(II) and Divalent Metal Ions: Kinetic and Thermodynamic Studies

Authors

KUBICEK, Vojtěch (203 Czech Republic), Zuzana BOHMOVA (203 Czech Republic), Romana ŠEVČÍKOVÁ (203 Czech Republic, belonging to the institution), Jakub VANĚK (203 Czech Republic, belonging to the institution), Přemysl LUBAL (203 Czech Republic, guarantor, belonging to the institution), Zuzana POLAKOVA (203 Czech Republic), Romana MICHALICOVÁ (203 Czech Republic, belonging to the institution), Jan KOTEK (203 Czech Republic) and Petr HERMANN (203 Czech Republic)

Edition

Inorganic Chemistry, Washington, American Chemical Society, 2018, 0020-1669

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10402 Inorganic and nuclear chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 4.850

RIV identification code

RIV/00216224:14310/18:00103745

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1021/acs.inorgchem.7b02929

UT WoS

000428219500016

Keywords in English

MACROCYCLIC CHELATORS; BIFUNCTIONAL CHELATOR; TRIAZACYCLONONANE-TRIACETIC ACID; FORMATION AND DISSOCIATION KINETICS

Abstract

V originále

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.

Links

LQ1601, research and development project

Name: CEITEC 2020 (Acronym: CEITEC2020)

Investor: Ministry of Education, Youth and Sports of the CR

MUNI/A/1237/2016, interní kód MU

Name: Vývoj metod a instrumentace pro analýzu biologicky významných látek 2017

Investor: Masaryk University, Category A

Citovat

KUBICEK, Vojtěch, Zuzana BOHMOVA, Romana ŠEVČÍKOVÁ, Jakub VANĚK, Přemysl LUBAL, Zuzana POLAKOVA, Romana MICHALICOVÁ, Jan KOTEK and Petr HERMANN. NOTA Complexes with Copper(II) and Divalent Metal Ions: Kinetic and Thermodynamic Studies. Inorganic Chemistry. Washington: American Chemical Society, 2018, vol. 57, No 6, p. 3061-3072. ISSN 0020-1669. Available from: https://dx.doi.org/10.1021/acs.inorgchem.7b02929.

@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 and Petr HERMANN. NOTA Complexes with Copper(II) and Divalent Metal Ions: Kinetic and Thermodynamic Studies. \textit{Inorganic Chemistry}. Washington: American Chemical Society, 2018, vol.~57, No~6, p.~3061-3072. ISSN~0020-1669. Available from: https://dx.doi.org/10.1021/acs.inorgchem.7b02929.

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