2 publications
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Artificial Diels–Alderase based on the Transmembrane Protein FhuA
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Beilstein J. Org. Chem. 2016, 12, 1314-1321, 10.3762/bjoc.12.124
Copper(I) and copper(II) complexes were covalently linked to an engineered variant of the transmembrane protein Ferric hydroxamate uptake protein component A (FhuA ΔCVFtev). Copper(I) was incorporated using an N-heterocyclic carbene (NHC) ligand equipped with a maleimide group on the side arm at the imidazole nitrogen. Copper(II) was attached by coordination to a terpyridyl ligand. The spacer length was varied in the back of the ligand framework. These biohybrid catalysts were shown to be active in the Diels–Alder reaction of a chalcone derivative with cyclopentadiene to preferentially give the endo product.
Metal: CuLigand type: TerpyridineHost protein: Ferric hydroxamate uptake protein component: A (FhuA)Anchoring strategy: Cystein-maleimideOptimization: ChemicalNotes: ---
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Carbene in Cupredoxin Protein Scaffolds: Replacement of a Histidine Ligand in the Active Site Substantially Alters Copper Redox Properties
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Angew. Chem. Int. Ed. 2018, 130, 10837-10842, 10.1002/ange.201807168
Im Tausch gegen NHC: Die Einfügung eines N‐heterocyclischen Carbenliganden (grün/blau) als Ersatz für His in das aktive Zentrum des Redoxenzyms Azurin rekonstituiert das T1‐Kupferzentrum. Der resultierende Komplex ist spektroskopisch kaum unterscheidbar von der N‐Bindung von His oder N‐Methylimidazol, senkt aber signifikant das Reduktionspotential des Kupferzentrums und erleichtert dadurch Elektronentransferprozesse.
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