6 publications

6 publications

A Hydrogenase Model System Based on the Sequence of Cytochrome c: Photochemical Hydrogen Evolution in Aqueous Media

Hayashi, T

Chem. Commun. 2011, 47, 8229, 10.1039/c1cc11157d

The diiron carbonyl cluster is held by a native CXXC motif, which includes Cys14 and Cys17, in the cytochrome c sequence. It is found that the diiron carbonyl complex works well as a catalyst for H2 evolution. It has a TON of ∼80 over 2 h at pH 4.7 in the presence of a Ru-photosensitizer and ascorbate as a sacrificial reagent in aqueous media.


Metal: Fe
Ligand type: Carbonyl
Host protein: Cytochrome c
Anchoring strategy: Dative
Optimization: ---
Reaction: H2 evolution
Max TON: 82
ee: ---
PDB: ---
Notes: Horse heart cytochrome C

An Artificial Metalloenzyme for Olefin Metathesis

Hilvert, D.; Ward, T.R.

Chem. Commun. 2011, 47, 12068, 10.1039/c1cc15005g

A Grubbs–Hoveyda type olefin metathesis catalyst, equipped with an electrophilic bromoacetamide group, was used to modify a cysteine-containing variant of a small heat shock protein from Methanocaldococcus jannaschii. The resulting artificial metalloenzyme was found to be active under acidic conditions in a benchmark ring closing metathesis reaction.


Metal: Ru
Ligand type: Carbene
Anchoring strategy: Covalent
Optimization: ---
Reaction: Olefin metathesis
Max TON: 25
ee: ---
PDB: ---
Notes: RCM

Artificial Metalloenzymes for Olefin Metathesis Based on the Biotin-(Strept)Avidin Technology

Ward, T.R.

Chem. Commun. 2011, 47, 12065, 10.1039/c1cc15004a

Incorporation of a biotinylated Hoveyda-Grubbs catalyst within (strept)avidin affords artificial metalloenzymes for the ring-closing metathesis of N-tosyl diallylamine in aqueous solution. Optimization of the performance can be achieved either by chemical or genetic means.


Metal: Ru
Ligand type: Carbene
Host protein: Streptavidin (Sav)
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Olefin metathesis
Max TON: 14
ee: ---
PDB: ---
Notes: RCM

Metal: Ru
Ligand type: Carbene
Host protein: Avidin (Av)
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Olefin metathesis
Max TON: 19
ee: ---
PDB: ---
Notes: RCM

Definite Coordination Arrangement of Organometallic Palladium Complexes Accumulated on the Designed Interior Surface of Apo-Ferritin

Ueno, T.

Chem. Commun. 2011, 47, 170-172, 10.1039/C0CC02221G

Apo-ferritin (apo-Fr) mutants are used as scaffolds to accommodate palladium (allyl) complexes. Various coordination arrangements of the Pd complexes are achieved by adjusting the positions of cysteine and histidine residues on the interior surface of the apo-Fr cage.


Metal: Pd
Ligand type: Allyl
Host protein: Ferritin
Anchoring strategy: Dative
Optimization: Genetic
Reaction: Suzuki coupling
Max TON: ---
ee: ---
PDB: ---
Notes: ---

Dual Modification of a Triple-Stranded β-Helix Nanotube with Ru and Re Metal Complexes to Promote Photocatalytic Reduction of CO2

Ueno, T.

Chem. Commun. 2011, 47, 2074, 10.1039/C0CC03015E

We have constructed a robust β-helical nanotube from the component proteins of bacteriophage T4 and modified this nanotube with RuII(bpy)3 and ReI(bpy)(CO)3Cl complexes. The photocatalytic system arranged on the tube catalyzes the reduction of CO2 with higher reactivity than that of the mixture of the monomeric forms.


Metal: Re
Ligand type: Bipyridine; CO
Host protein: [(gp5βf)3]2
Anchoring strategy: Cystein-maleimide
Optimization: ---
Reaction: CO2 reduction
Max TON: ---
ee: ---
PDB: ---
Notes: ---

Metal: Ru
Ligand type: Bipyridine
Host protein: [(gp5βf)3]2
Anchoring strategy: Lysine-succinimide
Optimization: Genetic
Reaction: CO2 reduction
Max TON: ---
ee: ---
PDB: ---
Notes: ---

Merging the Best of Two Worlds: Artificial Metalloenzymes for Enantioselective Catalysis

Review

Ward, T.R.

Chem. Commun. 2011, 47, 8470, 10.1039/c1cc11592h

Artificial metalloenzymes result from combining a catalytically active organometallic moiety with a macromolecular host. The resulting hybrid catalysts combine attractive features of both homogeneous and enzymatic systems. Herein we summarize the recent progress in this emerging field and outline the challenges ahead.


Notes: ---