Effect of Metal Environment and Immobilization on the Catalytic Activity of a Cu Superoxide Dismutase Mimic

Author:

Richezzi Micaela1,Ferreyra Joaquín1ORCID,Signorella Sharon1,Palopoli Claudia1,Terrestre Gustavo1,Pellegri Nora2,Hureau Christelle3ORCID,Signorella Sandra R.1ORCID

Affiliation:

1. IQUIR (Instituto de Química Rosario), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, Rosario 2000, Argentina

2. IFIR (Instituto de Física Rosario), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Facultad de Ciencias Exactas, Ingeniería y Agrimensura, Universidad Nacional de Rosario, 27 de Febrero 210 bis, Rosario 2000, Argentina

3. LCC (Laboratoire de Chimie de Coordination) CNRS, Université de Toulouse, 205 Route de Narbonne, 31077 Toulouse, France

Abstract

The Cu(II)/Cu(I) conversion involves variation in the coordination number and geometry around the metal center. Therefore, the flexibility/rigidity of the ligand plays a critical role in the design of copper superoxide dismutase (SOD) mimics. A 1,3-Bis[(pyridin-2-ylmethyl)(propargyl)amino]propane (pypapn), a flexible ligand with an N4-donor set, was used to prepare [Cu(pypapn)(ClO4)2], a trans-Cu(II) complex whose structure was determined by the X-ray diffraction. In DMF or water, perchlorate anions are exchanged with solvent molecules, affording [Cu(pypan)(solv)2]2+ that catalyzes O2•− dismutation with a second-order rate constant kMcF = 1.26 × 107 M−1 s−1, at pH 7.8. This high activity results from a combination of ligand flexibility, total charge, and labile binding sites, which places [Cu(pypapn)(solv)2]2+ above other mononuclear Cu(II) complexes with more favorable redox potentials. The covalent anchoring of the alkyne group of the complex to azide functionalized mesoporous silica through “click” chemistry resulted in the retention of the SOD activity and improved stability. A dicationic Cu(II)-N4-Schiff base complex encapsulated in mesoporous silica was also tested as an SOD mimic, displaying higher activity than the free complex, although lower than [Cu(pypapn)(solv)2]2+. The robustness of covalently attached or encapsulated doubly charged Cu(II) complexes in a mesoporous matrix appears as a suitable approach for the design of copper-based hybrid catalysts for O2•− dismutation under physiological conditions.

Funder

National University of Rosario

Consejo Nacional de Investigaciones Científicas y Técnicas

Centre National de la Recherche Scientifique

Agencia Nacional de Promoción Científica y Tecnológica

Publisher

MDPI AG

Subject

Inorganic Chemistry

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