Macrocyclic pyclen-based Gd3+ complex with high relaxivity and pH response

dc.centroUniversidad Cardenal Herrera-CEU
dc.contributor.authorFrías Martínez, Juan Carlos
dc.contributor.authorSoriano, José
dc.contributor.authorBlasco, Salvador
dc.contributor.authorGarcía-España, Enrique
dc.contributor.authorRodríguez Rodríguez, Aurora
dc.contributor.authorEsteban Gómez, David
dc.contributor.authorCarniato, Fabio
dc.contributor.authorBotta, Mauro
dc.contributor.authorPlatas Iglesias, Carlos
dc.contributor.authorAlbelda, M. Teresa
dc.contributor.otherUCH. Departamento de Ciencias Biomédicas
dc.date.accessioned2024-01-12T19:45:29Z
dc.date.available2024-01-12T19:45:29Z
dc.date.issued2020-05-07
dc.descriptionEste es el post-print del siguiente artículo: Frías, J.C., Soriano, J., Blasco, S., García-España, E., Rodríguez-Rodríguez, A., Esteban-Gómez, D., Carniato, F., Botta, M., Platas-Iglesias, C. & Albelda, M.T. (2020). Macrocyclic pyclen-based Gd3+ complex with high relaxivity and pH response. Inorganic Chemistry, vol. 59, i. 10 (07 may.), pp. 7306–7317, que se ha publicado de forma definitiva en: https://doi.org/10.1021/acs.inorgchem.0c00690
dc.description.abstractWe report the synthesis and characterization of the macrocyclic ligand 2,2′-((2-(3,9-bis(carboxymethyl)-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane-6-yl)ethyl)azanediyl)diacetic acid (H4L) and several of its complexes with lanthanide ions. The structure of the free ligand was determined using X-ray diffraction measurements. Two N atoms of the pyclen moiety in the trans position are protonated in the solid state, together with the exocyclic N atom and one of the carboxylate groups of the ligand. The relaxivity of the Gd3+ complex was found to increase from 6.7 mM–1 s–1 at pH 8.6 to 8.5 mM–1 s–1 below pH ≈ 6.0. Luminescence lifetime measurements recorded from H2O and D2O solutions of the Eu3+ complex evidence the presence of a single complex species in solution at low pH (∼5.0) that contains two inner-sphere water molecules. DFT calculations suggest that the coordination environment of the Ln3+ ion is fulfilled by the four N atoms of the pyclen unit, two oxygen atoms of the macrocyclic acetate groups, and an oxygen atom of an exocyclic carboxylate group. The two inner-sphere water molecules complete coordination number nine around the metal ion. At high pH (∼9.3), the lifetime of the excited 5D0 level of Eu3+ displays a biexponential behavior that can be attributed to the presence of two species in solution with hydration numbers of q = 0 and q = 1. The 1H NMR and DOSY spectra recorded from solutions of the Eu3+ and Y3+ complexes reveal a structural change triggered by pH and the formation of small aggregates at high pH values.es_ES
dc.description.versionPostprint
dc.identifier.citationFrías, J.C., Soriano, J., Blasco, S., García-España, E., Rodríguez-Rodríguez, A., Esteban-Gómez, D., Carniato, F., Botta, M., Platas-Iglesias, C. & Albelda, M.T. (2020). Macrocyclic pyclen-based Gd3+ complex with high relaxivity and pH response. Inorganic Chemistry, vol. 59, i. 10 (07 may.), pp. 7306–7317. DOI: https://doi.org/10.1021/acs.inorgchem.0c00690es_ES
dc.identifier.doihttps://doi.org/10.1021/acs.inorgchem.0c00690
dc.identifier.issn0020-1669
dc.identifier.issn1520-510X (Electrónico)
dc.identifier.urihttp://hdl.handle.net/10637/14862
dc.language.isoenes_ES
dc.publisherAmerican Chemical Societyes_ES
dc.relationEste artículo de investigación ha sido financiado or el Ministerio de Economía y Competitividad del Gobierno de España (CTQ2016-76756-P) y por la Xunta de Galicia (ED431B 2017/59 y ED431D 2017/01). También, se ha recibido ayuda económica por parte de la Università del Piemonte Orientale (FAR 2019).
dc.relation.ispartofInorganic Chemistry, vol. 59, i. 10 (07 may.)
dc.relation.projectIDCTQ2016-76756-P
dc.relation.projectIDED431B 2017/59
dc.relation.projectIDED431D 2017/01
dc.relation.projectIDFAR 2019
dc.rightsopen access
dc.rights.cchttps://creativecommons.org/licenses/by-nc-nd/4.0/deed.es
dc.subjectChemistry
dc.subjectQuímica
dc.subjectQuímica inorgánica
dc.subjectInorganic chemistry
dc.titleMacrocyclic pyclen-based Gd3+ complex with high relaxivity and pH responsees_ES
dc.typeArtículoes_ES
dspace.entity.typePublicationes
relation.isAuthorOfPublicationabdd739c-3649-49e4-810c-d861fe997b9e
relation.isAuthorOfPublication.latestForDiscoveryabdd739c-3649-49e4-810c-d861fe997b9e

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