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Carbon‐Nanotube‐Appended PAMAM Dendrimers Bearing Iron(II) α‐Keto Acid Complexes: Catalytic Non‐Heme Oxygenase Models
Author(s) -
Sheet Debobrata,
Bera Abhijit,
Fu Yang,
Desmecht Antonin,
Riant Olivier,
Hermans Sophie
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901735
Subject(s) - dendrimer , chemistry , catalysis , amide , heme oxygenase , turnover number , carbon nanotube , electrophile , combinatorial chemistry , amine gas treating , ligand (biochemistry) , heme , polymer chemistry , organic chemistry , enzyme , materials science , nanotechnology , biochemistry , receptor
Poly(amidoamine) dendrimers grafted on carbon nanotubes have been appended with iron(II)‐α‐keto acid (benzoylformate) complex of polypyridyl ligand to design artificial non‐heme oxygenase model. This nano‐enzyme was applied for selective catalytic oxidation of organic molecules. Although the carbon nanotubes serve as a robust heterogeneous platform, the amine terminals of dendrimers provide catalysts binding sites and the amide bonds provide a necessary second coordination sphere similar to the enzymatic polypeptide chains. Such a hybrid design prevented the deactivation of the primary active sites leading to 8 times faster oxidative decarboxylation rates than those of its homogeneous analogue. An electrophilic iron(IV)‐oxo intermediate has been intercepted, which catalyzes the selective oxidation of alcohols to aldehydes and incorporates single oxygen atoms into sulfides and olefins by using aerial oxygen with multiple turnover numbers. The catalyst was consecutively regenerated three times by mild chemical treatment and showed negligible loss of activity.