Oxidant dependent oxidation of copper bound catecholate: Catecholase versus catechol dioxygenase activity

Dóra Lakk-Bogáth, Róbert Csonka, Noémi Lorencz, Michel Giorgi, G. Speier, J. Kaizer

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

A series of new mixed ligand copper complexes CuII(PBI)(O2Ncat) (1) (PBI = 2-(2-pyridyl)-benzimidazole), CuII(DMPBI)(O2Ncat) (2) (DMPBI = 5,6-dimethyl-2-(2-pyridyl)-benzimidazole), CuII(PBO)(O2Ncat) (3) (PBO = 2-(2-pyridyl)-benzoxazole), CuII(PBT)(O2Ncat) (4) (PBT = 2-(2-pyridyl)-benzothiazole), and Cu(TBA)(O2Ncat) (5) (TBA = 4-(1H-1,3-benzodiazol-2-yl)-1,3-thiazole) have been synthesized by classic organic, bioinorganic methods. The complexes have been found to mimic catechol oxidase and catechol dioxygenase activity depending on the oxidant used. Triplet state dioxygen activates the complex leading to intradiol cleavage product, 2-nitromuconic acid while sterically more demanding tert-butyl hydroperoxide (TBHP) oxidizes the 4-nitrocatechol (4-O2NcatH2) ligand into 4-nitrobenzoquinone. We have also found that the electron density on the copper center significantly increase the reactivity toward the oxidant used.

Original languageEnglish
Pages (from-to)185-192
Number of pages8
JournalPolyhedron
Volume102
DOIs
Publication statusPublished - Dec 14 2015

Fingerprint

Dioxygenases
Oxidants
Copper
Benzoxazoles
Ligands
tert-Butylhydroperoxide
Catechol Oxidase
Thiazoles
copper
Oxidation
ligands
oxidation
oxidase
atomic energy levels
Carrier concentration
cleavage
reactivity
Oxygen
acids
Acids

Keywords

  • Catechol dioxygenase
  • Catecholase
  • Copper complex
  • Enzyme mimics
  • Intradiol cleavage

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Materials Chemistry
  • Physical and Theoretical Chemistry

Cite this

Oxidant dependent oxidation of copper bound catecholate : Catecholase versus catechol dioxygenase activity. / Lakk-Bogáth, Dóra; Csonka, Róbert; Lorencz, Noémi; Giorgi, Michel; Speier, G.; Kaizer, J.

In: Polyhedron, Vol. 102, 14.12.2015, p. 185-192.

Research output: Contribution to journalArticle

Lakk-Bogáth, Dóra ; Csonka, Róbert ; Lorencz, Noémi ; Giorgi, Michel ; Speier, G. ; Kaizer, J. / Oxidant dependent oxidation of copper bound catecholate : Catecholase versus catechol dioxygenase activity. In: Polyhedron. 2015 ; Vol. 102. pp. 185-192.
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abstract = "A series of new mixed ligand copper complexes CuII(PBI)(O2Ncat) (1) (PBI = 2-(2-pyridyl)-benzimidazole), CuII(DMPBI)(O2Ncat) (2) (DMPBI = 5,6-dimethyl-2-(2-pyridyl)-benzimidazole), CuII(PBO)(O2Ncat) (3) (PBO = 2-(2-pyridyl)-benzoxazole), CuII(PBT)(O2Ncat) (4) (PBT = 2-(2-pyridyl)-benzothiazole), and Cu(TBA)(O2Ncat) (5) (TBA = 4-(1H-1,3-benzodiazol-2-yl)-1,3-thiazole) have been synthesized by classic organic, bioinorganic methods. The complexes have been found to mimic catechol oxidase and catechol dioxygenase activity depending on the oxidant used. Triplet state dioxygen activates the complex leading to intradiol cleavage product, 2-nitromuconic acid while sterically more demanding tert-butyl hydroperoxide (TBHP) oxidizes the 4-nitrocatechol (4-O2NcatH2) ligand into 4-nitrobenzoquinone. We have also found that the electron density on the copper center significantly increase the reactivity toward the oxidant used.",
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AB - A series of new mixed ligand copper complexes CuII(PBI)(O2Ncat) (1) (PBI = 2-(2-pyridyl)-benzimidazole), CuII(DMPBI)(O2Ncat) (2) (DMPBI = 5,6-dimethyl-2-(2-pyridyl)-benzimidazole), CuII(PBO)(O2Ncat) (3) (PBO = 2-(2-pyridyl)-benzoxazole), CuII(PBT)(O2Ncat) (4) (PBT = 2-(2-pyridyl)-benzothiazole), and Cu(TBA)(O2Ncat) (5) (TBA = 4-(1H-1,3-benzodiazol-2-yl)-1,3-thiazole) have been synthesized by classic organic, bioinorganic methods. The complexes have been found to mimic catechol oxidase and catechol dioxygenase activity depending on the oxidant used. Triplet state dioxygen activates the complex leading to intradiol cleavage product, 2-nitromuconic acid while sterically more demanding tert-butyl hydroperoxide (TBHP) oxidizes the 4-nitrocatechol (4-O2NcatH2) ligand into 4-nitrobenzoquinone. We have also found that the electron density on the copper center significantly increase the reactivity toward the oxidant used.

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