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Homo- and Heterobinuclear Cu2+ and Zn2+ Complexes of Ditopic Aza Scorpiand Ligands as Superoxide Dismutase Mimics.
Inorg Chem. 2017 Nov 20; 56(22):13748-13758.IC

Abstract

Two polytopic aza-scorpiand-like ligands, 6-[7-(diaminoethyl)-3,7-diazaheptyl]-3,6,9-triaza-1-(2,6-pyridina)cyclodecaphane (L1) and 6-[6'-[3,6,9-triaza-1-(2,6-pyridina)cyclodecaphan-6-yl]-3-azahexyl]-3,6,9-triaza-1-(2,6-pyridina)cyclodecaphane (L2), have been synthesized. The acid-base behavior and Cu2+, Zn2+, and Cu2+/Zn2+ mixed coordination have been analyzed by potentiometry, cyclic voltammetry, and UV-vis spectroscopy. The resolution of the crystal structures of [Cu2L2Cl2](ClO4)2·1.67H2O (1), [Cu2HL2Br2](ClO4)3·1.5H2O (2), and [CuZnL2Cl2](ClO4)2·1.64H2O (3) shows, in agreement with the solution data, the formation of homobinuclear Cu2+/Cu2+ and heterobinuclear Cu2+/Zn2+ complexes. The metal ions are coordinated within the two macrocyclic cavities of the ligand with the involvement of a secondary amino group of the bridge in the case of 1 and 3. Energy-dispersive X-ray spectroscopy confirms the 1:1 Cu2+/Zn2+ stoichiometry of 3. The superoxide dismutase (SOD) activities of the Cu2+/Cu2+ and Cu2+/Zn2+ complexes of L1 and L2 have been evaluated using nitro blue tetrazolium assays at pH 7.4. The IC50 and kcat values obtained for the [Cu2L1]4+ complex rank among the best values reported in the literature for Cu-SOD mimics. Interestingly, the binuclear Cu2+ complexes of L1 and L2 have low toxicity in cultures of mammalian cell lines and show significant antioxidant activity in a copper-dependent SOD (SOD1)-defective yeast model. The results are rationalized by taking into account the binding modes of the Cu2+ ions in the different complexes.

Authors+Show Affiliations

Instituto de Ciencia Molecular , c/Catedrático José Beltrán 2, 46980 Paterna, Valencia, Spain.Instituto de Ciencia Molecular , c/Catedrático José Beltrán 2, 46980 Paterna, Valencia, Spain.Instituto de Ciencia Molecular , c/Catedrático José Beltrán 2, 46980 Paterna, Valencia, Spain.Departamento de Química Analítica, Universidad de Valencia , c/Dr. Moliner 50, 46100 Burjassot, Valencia, Spain.Unitat de Recerca, Hospital Joan XXIII, Institut d'Investigació Sanitària Pere Virgili, Universitat Rovira i Virgili , 43007 Tarragona, Spain.Unitat de Recerca, Hospital Joan XXIII, Institut d'Investigació Sanitària Pere Virgili, Universitat Rovira i Virgili , 43007 Tarragona, Spain.Instituto de Ciencia Molecular , c/Catedrático José Beltrán 2, 46980 Paterna, Valencia, Spain.Unitat de Recerca, Hospital Joan XXIII, Institut d'Investigació Sanitària Pere Virgili, Universitat Rovira i Virgili , 43007 Tarragona, Spain.Instituto de Ciencia Molecular , c/Catedrático José Beltrán 2, 46980 Paterna, Valencia, Spain.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

29087184

Citation

Guijarro, Lluís, et al. "Homo- and Heterobinuclear Cu2+ and Zn2+ Complexes of Ditopic Aza Scorpiand Ligands as Superoxide Dismutase Mimics." Inorganic Chemistry, vol. 56, no. 22, 2017, pp. 13748-13758.
Guijarro L, Inclán M, Pitarch-Jarque J, et al. Homo- and Heterobinuclear Cu2+ and Zn2+ Complexes of Ditopic Aza Scorpiand Ligands as Superoxide Dismutase Mimics. Inorg Chem. 2017;56(22):13748-13758.
Guijarro, L., Inclán, M., Pitarch-Jarque, J., Doménech-Carbó, A., Chicote, J. U., Trefler, S., García-España, E., García-España, A., & Verdejo, B. (2017). Homo- and Heterobinuclear Cu2+ and Zn2+ Complexes of Ditopic Aza Scorpiand Ligands as Superoxide Dismutase Mimics. Inorganic Chemistry, 56(22), 13748-13758. https://doi.org/10.1021/acs.inorgchem.7b01756
Guijarro L, et al. Homo- and Heterobinuclear Cu2+ and Zn2+ Complexes of Ditopic Aza Scorpiand Ligands as Superoxide Dismutase Mimics. Inorg Chem. 2017 Nov 20;56(22):13748-13758. PubMed PMID: 29087184.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Homo- and Heterobinuclear Cu2+ and Zn2+ Complexes of Ditopic Aza Scorpiand Ligands as Superoxide Dismutase Mimics. AU - Guijarro,Lluís, AU - Inclán,Mario, AU - Pitarch-Jarque,Javier, AU - Doménech-Carbó,Antonio, AU - Chicote,Javier U, AU - Trefler,Sandra, AU - García-España,Enrique, AU - García-España,Antonio, AU - Verdejo,Begoña, Y1 - 2017/10/31/ PY - 2017/11/1/pubmed PY - 2018/3/14/medline PY - 2017/11/1/entrez SP - 13748 EP - 13758 JF - Inorganic chemistry JO - Inorg Chem VL - 56 IS - 22 N2 - Two polytopic aza-scorpiand-like ligands, 6-[7-(diaminoethyl)-3,7-diazaheptyl]-3,6,9-triaza-1-(2,6-pyridina)cyclodecaphane (L1) and 6-[6'-[3,6,9-triaza-1-(2,6-pyridina)cyclodecaphan-6-yl]-3-azahexyl]-3,6,9-triaza-1-(2,6-pyridina)cyclodecaphane (L2), have been synthesized. The acid-base behavior and Cu2+, Zn2+, and Cu2+/Zn2+ mixed coordination have been analyzed by potentiometry, cyclic voltammetry, and UV-vis spectroscopy. The resolution of the crystal structures of [Cu2L2Cl2](ClO4)2·1.67H2O (1), [Cu2HL2Br2](ClO4)3·1.5H2O (2), and [CuZnL2Cl2](ClO4)2·1.64H2O (3) shows, in agreement with the solution data, the formation of homobinuclear Cu2+/Cu2+ and heterobinuclear Cu2+/Zn2+ complexes. The metal ions are coordinated within the two macrocyclic cavities of the ligand with the involvement of a secondary amino group of the bridge in the case of 1 and 3. Energy-dispersive X-ray spectroscopy confirms the 1:1 Cu2+/Zn2+ stoichiometry of 3. The superoxide dismutase (SOD) activities of the Cu2+/Cu2+ and Cu2+/Zn2+ complexes of L1 and L2 have been evaluated using nitro blue tetrazolium assays at pH 7.4. The IC50 and kcat values obtained for the [Cu2L1]4+ complex rank among the best values reported in the literature for Cu-SOD mimics. Interestingly, the binuclear Cu2+ complexes of L1 and L2 have low toxicity in cultures of mammalian cell lines and show significant antioxidant activity in a copper-dependent SOD (SOD1)-defective yeast model. The results are rationalized by taking into account the binding modes of the Cu2+ ions in the different complexes. SN - 1520-510X UR - https://www.unboundmedicine.com/medline/citation/29087184/Homo__and_Heterobinuclear_Cu2+_and_Zn2+_Complexes_of_Ditopic_Aza_Scorpiand_Ligands_as_Superoxide_Dismutase_Mimics_ DB - PRIME DP - Unbound Medicine ER -