10 publications

10 publications

A Hybrid Ring- Opening Metathesis Polymerization Catalyst Based on an Engineered Variant of the Beta-Barrel Protein FhuA

Okuda, J.; Schwaneberg, U.

Chem. - Eur. J., 2013, 10.1002/chem.201301515

A β‐barrel protein hybrid catalyst was prepared by covalently anchoring a Grubbs–Hoveyda type olefin metathesis catalyst at a single accessible cysteine amino acid in the barrel interior of a variant of β‐barrel transmembrane protein ferric hydroxamate uptake protein component A (FhuA). Activity of this hybrid catalyst type was demonstrated by ring‐opening metathesis polymerization of a 7‐oxanorbornene derivative in aqueous solution.


Metal: Ru
Ligand type: Carbene
Host protein: FhuA ΔCVFtev
Anchoring strategy: Covalent
Optimization: Chemical
Reaction: Olefin metathesis
Max TON: 955
ee: ---
PDB: ---
Notes: ROMP

An Artificial Enzyme Made by Covalent Grafting of an FeII Complex into β-Lactoglobulin: Molecular Chemistry, Oxidation Catalysis, and Reaction-Intermediate Monitoring in a Protein

Banse, F.; Mahy, J.-P.

Chem. - Eur. J., 2015, 10.1002/chem.201501755

An artificial metalloenzyme based on the covalent grafting of a nonheme FeII polyazadentate complex into bovine β‐lactoglobulin has been prepared and characterized by using various spectroscopic techniques. Attachment of the FeII catalyst to the protein scaffold is shown to occur specifically at Cys121. In addition, spectrophotometric titration with cyanide ions based on the spin‐state conversion of the initial high spin (S=2) FeII complex into a low spin (S=0) one allows qualitative and quantitative characterization of the metal center’s first coordination sphere. This biohybrid catalyst activates hydrogen peroxide to oxidize thioanisole into phenylmethylsulfoxide as the sole product with an enantiomeric excess of up to 20 %. Investigation of the reaction between the biohybrid system and H2O2 reveals the generation of a high spin (S=5/2) FeIII(η2‐O2) intermediate, which is proposed to be responsible for the catalytic sulfoxidation of the substrate.


Metal: Fe
Ligand type: Poly-pyridine
Host protein: ß-lactoglobulin
Anchoring strategy: Covalent
Optimization: ---
Reaction: Sulfoxidation
Max TON: 5.6
ee: 20
PDB: ---
Notes: ---

Artificial Metalloenzymes for Enantioselective Catalysis Based on the Noncovalent Incorporation of Organometallic Moieties in a Host Protein

Review

Ward, T. R.

Chem. - Eur. J., 2005, 10.1002/chem.200401232


Notes: ---

Bioinspired Catalyst Design and Artificial Metalloenzymes

Review

Kamer, P. C. J.; Laan, W.

Chem. - Eur. J., 2011, 10.1002/chem.201003646


Notes: ---

Engineered Metalloenzymes with Non-Canonical Coordination Environments

Review

Green, A. P.; Hilvert, D.

Chem. - Eur. J., 2018, 10.1002/chem.201800975


Notes: ---

Manganese-Substituted Carbonic Anhydrase as a New Peroxidase

Kazlauskas, R. J.

Chem. - Eur. J., 2006, 10.1002/chem.200501413


Metal: Mn
Ligand type: Amino acid
Anchoring strategy: Metal substitution
Optimization: Chemical & genetic
Reaction: Epoxidation
Max TON: 22
ee: 67
PDB: ---
Notes: ---

Metal: Mn
Ligand type: Amino acid
Anchoring strategy: Metal substitution
Optimization: Chemical & genetic
Reaction: Epoxidation
Max TON: 9.5
ee: 55
PDB: 4CAC
Notes: PDB ID 4CAC = Structure of Zn containing hCAII

Noncovalent Modulation of pH-Dependent Reactivity of a Mn–Salen Cofactor in Myoglobin with Hydrogen Peroxide

Lu, Y.

Chem. - Eur. J., 2009, 10.1002/chem.200802449


Metal: Mn
Ligand type: Salen
Host protein: Myoglobin (Mb)
Anchoring strategy: Covalent
Optimization: Chemical & genetic
Reaction: Sulfoxidation
Max TON: 4.1
ee: 50
PDB: ---
Notes: Sperm whale myoglobin

Peroxidase Activity of Cationic Metalloporphyrin-Antibody Complexes

Harada, A.

Chem. - Eur. J., 2004, 10.1002/chem.200305692


Metal: Fe
Ligand type: Porphyrin
Host protein: Antibody 12E11G
Anchoring strategy: Antibody
Optimization: ---
Max TON: ---
ee: ---
PDB: ---
Notes: ---

Ring-Closing and Cross-Metathesis with Artificial Metalloenzymes Created by Covalent Active Site- Directed Hybridization of a Lipase

Klein Gebbink, R. J. M.

Chem. - Eur. J., 2015, 10.1002/chem.201502381


Metal: Ru
Ligand type: Carbene
Host protein: Cutinase
Anchoring strategy: Covalent
Optimization: Chemical
Reaction: Olefin metathesis
Max TON: 17
ee: ---
PDB: ---
Notes: RCM

Metal: Ru
Ligand type: Carbene
Host protein: Cutinase
Anchoring strategy: Covalent
Optimization: Chemical
Reaction: Olefin metathesis
Max TON: 20
ee: ---
PDB: ---
Notes: Cross metathesis

Stereoselective Hydrogenation of Olefins Using Rhodium-Substituted Carbonic Anhydrase—A New Reductase

Kazlauskas, R. J.

Chem. - Eur. J., 2008, 10.1002/chem.200801673


Metal: Rh
Ligand type: COD
Anchoring strategy: Metal substitution
Optimization: Genetic
Reaction: Hydrogenation
Max TON: 15.8
ee: ---
PDB: ---
Notes: ---

Metal: Rh
Ligand type: COD
Anchoring strategy: Metal substitution
Optimization: Genetic
Reaction: Hydrogenation
Max TON: 80.5
ee: ---
PDB: 4CAC
Notes: PDB ID 4CAC = Structure of Zn containing hCAII