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Expanding the Ligand Classes Used for Mn(II) Complexation: Oxa-aza Macrocycles Make the Difference

We report two macrocyclic ligands based on a 1,7-diaza-12-crown-4 platform functionalized with acetate (tO2DO2A(2−)) or piperidineacetamide (tO2DO2AM(Pip)) pendant arms and a detailed characterization of the corresponding Mn(II) complexes. The X−ray structure of [Mn(tO2DO2A)(H(2)O)]·2H(2)O shows tha...

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Autores principales: Kálmán, Ferenc K., Nagy, Viktória, Uzal-Varela, Rocío, Pérez-Lourido, Paulo, Esteban-Gómez, David, Garda, Zoltán, Pota, Kristof, Mezei, Roland, Pallier, Agnès, Tóth, Éva, Platas-Iglesias, Carlos, Tircsó, Gyula
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7998310/
https://www.ncbi.nlm.nih.gov/pubmed/33802241
http://dx.doi.org/10.3390/molecules26061524
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author Kálmán, Ferenc K.
Nagy, Viktória
Uzal-Varela, Rocío
Pérez-Lourido, Paulo
Esteban-Gómez, David
Garda, Zoltán
Pota, Kristof
Mezei, Roland
Pallier, Agnès
Tóth, Éva
Platas-Iglesias, Carlos
Tircsó, Gyula
author_facet Kálmán, Ferenc K.
Nagy, Viktória
Uzal-Varela, Rocío
Pérez-Lourido, Paulo
Esteban-Gómez, David
Garda, Zoltán
Pota, Kristof
Mezei, Roland
Pallier, Agnès
Tóth, Éva
Platas-Iglesias, Carlos
Tircsó, Gyula
author_sort Kálmán, Ferenc K.
collection PubMed
description We report two macrocyclic ligands based on a 1,7-diaza-12-crown-4 platform functionalized with acetate (tO2DO2A(2−)) or piperidineacetamide (tO2DO2AM(Pip)) pendant arms and a detailed characterization of the corresponding Mn(II) complexes. The X−ray structure of [Mn(tO2DO2A)(H(2)O)]·2H(2)O shows that the metal ion is coordinated by six donor atoms of the macrocyclic ligand and one water molecule, to result in seven-coordination. The Cu(II) analogue presents a distorted octahedral coordination environment. The protonation constants of the ligands and the stability constants of the complexes formed with Mn(II) and other biologically relevant metal ions (Mg(II), Ca(II), Cu(II) and Zn(II)) were determined using potentiometric titrations (I = 0.15 M NaCl, T = 25 °C). The conditional stabilities of Mn(II) complexes at pH 7.4 are comparable to those reported for the cyclen-based tDO2A(2−) ligand. The dissociation of the Mn(II) chelates were investigated by evaluating the rate constants of metal exchange reactions with Cu(II) under acidic conditions (I = 0.15 M NaCl, T = 25 °C). Dissociation of the [Mn(tO2DO2A)(H(2)O)] complex occurs through both proton− and metal−assisted pathways, while the [Mn(tO2DO2AM(Pip))(H(2)O)] analogue dissociates through spontaneous and proton-assisted mechanisms. The Mn(II) complex of tO2DO2A(2−) is remarkably inert with respect to its dissociation, while the amide analogue is significantly more labile. The presence of a water molecule coordinated to Mn(II) imparts relatively high relaxivities to the complexes. The parameters determining this key property were investigated using (17)O NMR (Nuclear Magnetic Resonance) transverse relaxation rates and (1)H nuclear magnetic relaxation dispersion (NMRD) profiles.
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spelling pubmed-79983102021-03-28 Expanding the Ligand Classes Used for Mn(II) Complexation: Oxa-aza Macrocycles Make the Difference Kálmán, Ferenc K. Nagy, Viktória Uzal-Varela, Rocío Pérez-Lourido, Paulo Esteban-Gómez, David Garda, Zoltán Pota, Kristof Mezei, Roland Pallier, Agnès Tóth, Éva Platas-Iglesias, Carlos Tircsó, Gyula Molecules Article We report two macrocyclic ligands based on a 1,7-diaza-12-crown-4 platform functionalized with acetate (tO2DO2A(2−)) or piperidineacetamide (tO2DO2AM(Pip)) pendant arms and a detailed characterization of the corresponding Mn(II) complexes. The X−ray structure of [Mn(tO2DO2A)(H(2)O)]·2H(2)O shows that the metal ion is coordinated by six donor atoms of the macrocyclic ligand and one water molecule, to result in seven-coordination. The Cu(II) analogue presents a distorted octahedral coordination environment. The protonation constants of the ligands and the stability constants of the complexes formed with Mn(II) and other biologically relevant metal ions (Mg(II), Ca(II), Cu(II) and Zn(II)) were determined using potentiometric titrations (I = 0.15 M NaCl, T = 25 °C). The conditional stabilities of Mn(II) complexes at pH 7.4 are comparable to those reported for the cyclen-based tDO2A(2−) ligand. The dissociation of the Mn(II) chelates were investigated by evaluating the rate constants of metal exchange reactions with Cu(II) under acidic conditions (I = 0.15 M NaCl, T = 25 °C). Dissociation of the [Mn(tO2DO2A)(H(2)O)] complex occurs through both proton− and metal−assisted pathways, while the [Mn(tO2DO2AM(Pip))(H(2)O)] analogue dissociates through spontaneous and proton-assisted mechanisms. The Mn(II) complex of tO2DO2A(2−) is remarkably inert with respect to its dissociation, while the amide analogue is significantly more labile. The presence of a water molecule coordinated to Mn(II) imparts relatively high relaxivities to the complexes. The parameters determining this key property were investigated using (17)O NMR (Nuclear Magnetic Resonance) transverse relaxation rates and (1)H nuclear magnetic relaxation dispersion (NMRD) profiles. MDPI 2021-03-10 /pmc/articles/PMC7998310/ /pubmed/33802241 http://dx.doi.org/10.3390/molecules26061524 Text en © 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Kálmán, Ferenc K.
Nagy, Viktória
Uzal-Varela, Rocío
Pérez-Lourido, Paulo
Esteban-Gómez, David
Garda, Zoltán
Pota, Kristof
Mezei, Roland
Pallier, Agnès
Tóth, Éva
Platas-Iglesias, Carlos
Tircsó, Gyula
Expanding the Ligand Classes Used for Mn(II) Complexation: Oxa-aza Macrocycles Make the Difference
title Expanding the Ligand Classes Used for Mn(II) Complexation: Oxa-aza Macrocycles Make the Difference
title_full Expanding the Ligand Classes Used for Mn(II) Complexation: Oxa-aza Macrocycles Make the Difference
title_fullStr Expanding the Ligand Classes Used for Mn(II) Complexation: Oxa-aza Macrocycles Make the Difference
title_full_unstemmed Expanding the Ligand Classes Used for Mn(II) Complexation: Oxa-aza Macrocycles Make the Difference
title_short Expanding the Ligand Classes Used for Mn(II) Complexation: Oxa-aza Macrocycles Make the Difference
title_sort expanding the ligand classes used for mn(ii) complexation: oxa-aza macrocycles make the difference
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7998310/
https://www.ncbi.nlm.nih.gov/pubmed/33802241
http://dx.doi.org/10.3390/molecules26061524
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