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Article Dans Une Revue Microporous and Mesoporous Materials Année : 2019

Biomimetic Cu, Zn and Cu2 complexes inserted in mesoporous silica as catalysts for superoxide dismutation

Résumé

Three CuZn-superoxide dismutase (SOD) functional mimics, [CuZn(dien)2(μ-Im)](ClO4)3 (1), [Cu2(dien)2(μ-Im)](ClO4)3 (2) (Im = imidazole, dien = diethylenetriamine), and [CuZn(salpn)Cl2] (3) (H2salpn = 1,3-bis(salicylideneamino)propane), were successfully inserted into the nanochannels of SBA-15 type mesoporous silica with retention of the silica mesostructure. X-ray absorption spectroscopic studies indicate that the encapsulated complexes keep unchanged the first-shell environment of Cu(II) and Zn(II) ions. Magnetic measurements suggest that the nanochannels constrain the geometry of the μ-imidazolate-Cu(II)2 core modifying the relative orientation of the two copper coordination planes. Confinement imposed by the silica nanochannels upon encapsulation of complexes 1 and 2 leads to stable hybrid materials at physiological pH with enhanced SOD activity relative to the free complexes. Unlike the imidazolato-bridged compounds, insertion of 3 in mesoporous silica leads to a less stable hybrid material exhibiting partial release into the aqueous solution and O2•− dismutation rate slower than the free complex. The covalent binding of a mononuclear Cu(dien)Im+ moiety to the mesoporous silica showed lower SOD activity than encapsulated imidazolato-bridged CuZn and Cu2 complexes. The results emphasize the positive effect of encapsulation on SOD activity of imidazolato-bridged dinuclear complexes.
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Dates et versions

hal-02335038 , version 1 (02-12-2020)

Identifiants

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Matías Patriarca, Veronica Daier, Gerardo Camí, Nora Pellegri, Eric Rivière, et al.. Biomimetic Cu, Zn and Cu2 complexes inserted in mesoporous silica as catalysts for superoxide dismutation. Microporous and Mesoporous Materials, 2019, 279, pp.133-141. ⟨10.1016/j.micromeso.2018.12.027⟩. ⟨hal-02335038⟩
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