title: Galactodendritic porphyrinic conjugates as new biomimetic catalysts for oxidation reactions.
abstract: This work employed [5,10,15,20-tetrakis(pentafluorophenyl)porphyrin] ([H2(TPPF20)], H2P1) as the platform to prepare a tetrasubstituted galactodendritic conjugate porphyrin (H2P3). After metalation with excess copper(II) acetate, H2P3 afforded a new solid porphyrin material, Cu4CuP3S. This work also assessed the ability of the copper(II) complex (CuP3) of H2P3 to coordinate with zinc(II) acetate, to yield the new material Zn4CuP3S. UV-visible, Fourier transform infrared, and electron paramagnetic resonance spectroscopies aided full characterization of the synthesized solids. (Z)-Cyclooctene epoxidation under heterogeneous conditions helped to evaluate the catalytic activity of Cu4CuP3S and Zn4CuP3S. The efficiency of Cu4CuP3S in the oxidation of another organic substrate, catechol, was also investigated. According to the results obtained in the heterogeneous process, Cu4CuP3S mimicked the activity of cytochrome P-450 and catecholase. In addition, Cu4CuP3S was reusable after recovery and reactivation. The data obtained herein were compared with the results achieved for the copper complex (CuP1) of [H2(TPPF20)] and for CuP3 under homogeneous conditions.
authors.affiliation: †Laboratório de Química Bioinorgânica e Catálise, Universidade Federal do Paraná (UFPR), CP 19081, CEP 81531-990, Curitiba, Paraná Brazil.
authors.forename: Kelly A D F
authors.initials: KA
authors.lastname: Castro
authors.affiliation: ‡Department of Chemistry and QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal.
authors.forename: Sandrina
authors.initials: S
authors.lastname: Silva
authors.affiliation: ‡Department of Chemistry and QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal.
authors.forename: Patrícia M R
authors.initials: PM
authors.lastname: Pereira
authors.affiliation: ‡Department of Chemistry and QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal.
authors.forename: Mário M Q
authors.initials: MM
authors.lastname: Simões
authors.affiliation: ‡Department of Chemistry and QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal.
authors.forename: Maria da Graça P M S
authors.initials: Mda G
authors.lastname: Neves
authors.affiliation: ‡Department of Chemistry and QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal.
authors.forename: José A S
authors.initials: JA
authors.lastname: Cavaleiro
authors.affiliation: †Laboratório de Química Bioinorgânica e Catálise, Universidade Federal do Paraná (UFPR), CP 19081, CEP 81531-990, Curitiba, Paraná Brazil.
authors.forename: Fernando
authors.initials: F
authors.lastname: Wypych
authors.affiliation: ‡Department of Chemistry and QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal.|§Department of Organic and Macromolecular Chemistry, Ghent University, B-9000 Gent, Belgium.
authors.forename: João P C
authors.initials: JP
authors.lastname: Tomé
authors.affiliation: †Laboratório de Química Bioinorgânica e Catálise, Universidade Federal do Paraná (UFPR), CP 19081, CEP 81531-990, Curitiba, Paraná Brazil.
authors.forename: Shirley
authors.initials: S
authors.lastname: Nakagaki
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry*; D002384:Catalysis; D004156:Catechol Oxidase / Q000737:chemistry; D002396:Catechols / Q000737:chemistry*; D003577:Cytochrome P-450 Enzyme System / Q000737:chemistry; D004578:Electron Spin Resonance Spectroscopy; D008665:Metalloporphyrins / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D019345:Zinc Acetate / Q000737:chemistry*
chemical_list: D002396:Catechols; D008665:Metalloporphyrins; D009942:Organometallic Compounds; C015092:cupric acetate; D003577:Cytochrome P-450 Enzyme System; D004156:Catechol Oxidase; D019345:Zinc Acetate; C034221:catechol