25 publications

25 publications

A Metal Ion Regulated Artificial Metalloenzyme

Roelfes, G.

Dalton Trans., 2017, 10.1039/C7DT00533D

Regulation of enzyme activity is essential in living cells. The rapidly increasing number of designer enzymes with new-to-nature activities makes it necessary to develop novel strategies for controlling their catalytic activity. Here we present the development of a metal ion regulated artificial metalloenzyme created by combining two anchoring strategies, covalent and supramolecular, for introducing a regulatory and a catalytic site, respectively. This artificial metalloenzyme is activated in the presence of Fe2+ ions, but only marginally in the presence of Zn2+.


Metal: Fe
Ligand type: Bypyridine
Host protein: LmrR
Anchoring strategy: Covalent
Optimization: Genetic
Max TON: 14
ee: 75
PDB: ---
Notes: ---

Metal: Zn
Ligand type: Bypyridine
Host protein: LmrR
Anchoring strategy: Covalent
Optimization: Genetic
Max TON: 6
ee: 80
PDB: ---
Notes: ---

Artificial Metalloenzymes

Review

Ward, T. R.

Effects of Nanoconfinement on Catalysis, 2017, 10.1007/978-3-319-50207-6_3


Notes: Book chapter

A Well-Defined Osmium–Cupin Complex: Hyperstable Artificial Osmium Peroxygenase

Fujieda, N.; Itoh, S.

J. Am. Chem. Soc., 2017, 10.1021/jacs.7b00675


Metal: Os
Ligand type: Amino acid
Host protein: TM1459 cupin
Anchoring strategy: Metal substitution
Optimization: Genetic
Reaction: Dihydroxylation
Max TON: 45
ee: ---
PDB: 5WSE
Notes: Exclusively cis dihydroxylation product obtained

Metal: Os
Ligand type: Amino acid
Host protein: TM1459 cupin
Anchoring strategy: Metal substitution
Optimization: Genetic
Reaction: Dihydroxylation
Max TON: 45
ee: ---
PDB: 5WSF
Notes: Exclusively cis dihydroxylation product obtained

Beyond Iron: Iridium-Containing P450 Enzymes for Selective Cyclopropanations of Structurally Diverse Alkenes

Hartwig, J. F.

ACS Cent. Sci., 2017, 10.1021/acscentsci.6b00391


Metal: Ir
Ligand type: Methyl; Porphyrin
Host protein: Cytochrome P450 (CYP119)
Anchoring strategy: Metal substitution
Optimization: Chemical & genetic
Reaction: Cyclopropanation
Max TON: 10181
ee: 98
PDB: ---
Notes: Selectivity for cis product (cis/trans = 90:1)

Catalytic Cyclopropanation by Myoglobin Reconstituted with Iron Porphycene: Acceleration of Catalysis due to Rapid Formation of the Carbene Species

Hasegawa, J.-Y.; Lehnert, N.

J. Am. Chem. Soc., 2017, 10.1021/jacs.7b10154


Metal: Fe
Ligand type: Amino acid; Porphycene
Host protein: Myoglobin (Mb)
Anchoring strategy: Reconstitution
Optimization: ---
Reaction: Cyclopropanation
Max TON: ---
ee: ---
PDB: ---
Notes: Cyclopropanation of styrene with ethyl diazoacetate: kcat/KM = 1.3 mM-1 * s-1, trans/cis = 99:1

Catalytic Water Oxidation by Iridium-Modified Carbonic Anhydrase

Lee, S.-Y.

Chem. - Asian J., 2017, 10.1002/asia.201701543


Metal: Ir
Ligand type: Amino acid
Anchoring strategy: Metal substitution
Optimization: Chemical
Reaction: Water oxidation
Max TON: ---
ee: ---
PDB: ---
Notes: Sodium periodate as sacrificial oxidant. TOF at pH 7 and 30°C is 39.8 min-1.

Chalcogenide Substitution in the [2Fe] Cluster of [FeFe]-Hydrogenases Conserves High Enzymatic Activity

Apfel, U.-P.; Happe, T.

Dalton Trans., 2017, 10.1039/C7DT03785F


Metal: Fe
Ligand type: CN; CO; Diselenolate
Anchoring strategy: Dative
Optimization: Chemical
Reaction: H2 evolution
Max TON: ---
ee: ---
PDB: 5OEF
Notes: ---

Chemoselective, Enzymatic C−H Bond Amination Catalyzed by a Cytochrome P450 Containing an Ir(Me)-PIX Cofactor

Hartwig, J. F.

J. Am. Chem. Soc., 2017, 10.1021/jacs.6b11410


Metal: Ir
Ligand type: Methyl; Porphyrin
Host protein: Cytochrome P450 (CYP119)
Anchoring strategy: Metal substitution
Optimization: Chemical & genetic
Reaction: C-H activation
Max TON: 294
ee: 26
PDB: ---
Notes: ---

Metal: Ir
Ligand type: Methyl; Porphyrin
Host protein: Cytochrome P450 (CYP119)
Anchoring strategy: Metal substitution
Optimization: Chemical & genetic
Reaction: C-H activation
Max TON: 192
ee: 95
PDB: ---
Notes: ---

Construction and In Vivo Assembly of a Catalytically Proficient and Hyperthermostable De Novo Enzyme

Anderson, J. L. R.

Nat. Commun., 2017, 10.1038/s41467-017-00541-4


Metal: Fe
Ligand type: Porphyrin
Anchoring strategy: Supramolecular
Optimization: Genetic
Reaction: Oxidation
Max TON: ---
ee: ---
PDB: ---
Notes: Oxidation of 2,2′-azino-bis(3-ethylbenzothiazo-line-6-sulfonic acid (ABTS)

Cross-Linked Artificial Enzyme Crystals as Heterogeneous Catalysts for Oxidation Reactions

Cavazza, C.; Ménage, S.

J. Am. Chem. Soc., 2017, 10.1021/jacs.7b09343


Metal: Fe
Ligand type: ---
Host protein: NikA
Anchoring strategy: Supramolecular
Optimization: Chemical
Max TON: 28000
ee: ---
PDB: 5ON0
Notes: Cross-Linked Enzyme Crystals (CLEC) as catalysts.

Metal: Fe
Ligand type: ---
Host protein: NikA
Anchoring strategy: Supramolecular
Optimization: Chemical
Max TON: 5900
ee: ---
PDB: 5ON0
Notes: Cross-Linked Enzyme Crystals (CLEC) as catalysts.

Cross-Regulation of an Artificial Metalloenzyme

Ward, T. R.

Angew. Chem., Int. Ed., 2017, 10.1002/anie.201702181


Metal: Ir
Ligand type: Cp*; Phenanthroline
Host protein: Streptavidin (Sav)
Anchoring strategy: Supramolecular
Optimization: Chemical & genetic
Max TON: 96
ee: ---
PDB: ---
Notes: Cross-regulated reduction of the antibiotic enrofloxacin by an ArM.

Design of an Enantioselective Artificial Metallo-Hydratase Enzyme Containing an Unnatural Metal-Binding Amino Acid

Maréchal, J.-D.; Roelfes, G.

Chem. Sci., 2017, 10.1039/C7SC03477F


Metal: Cu
Ligand type: Bipyridine
Host protein: LmrR
Anchoring strategy: ---
Optimization: Genetic
Reaction: Hydration
Max TON: 9
ee: 64
PDB: ---
Notes: ---

Design of Artificial Metalloproteins/Metalloenzymes by Tuning Noncovalent Interactions

Review

Hirota, S.; Lin, Y.-W.

J. Biol. Inorg. Chem., 2017, 10.1007/s00775-017-1506-8


Notes: ---

Diruthenium Diacetate-Catalyzed Aerobic Oxidation of Hydroxylamines and Improved Chemoselectivity by Immobilization to Lysozyme

Cardona, F.; Goti, A.; Messori, L.

ChemCatChem, 2017, 10.1002/cctc.201701083


Metal: Ru
Ligand type: Amino acid; OAc
Host protein: Lysozyme
Anchoring strategy: Dative
Optimization: Chemical
Max TON: 1000
ee: ---
PDB: ---
Notes: ---

Enzyme Activity by Design: An Artificial Rhodium Hydroformylase for Linear Aldehydes

Jarvis, A. G.; Kamer, P. C. J.

Angew. Chem., Int. Ed., 2017, 10.1002/ange.201705753


Metal: Rh
Ligand type: Acac; Diphenylphosphine
Anchoring strategy: Cystein-maleimide
Optimization: Chemical & genetic
Reaction: Hydroformylation
Max TON: 409
ee: ---
PDB: ---
Notes: Selectivity for the linear product over the branched product

Enzyme stabilization via computationally guided protein stapling

Fasan, R.; Khare, S. D.

Proc. Natl. Acad. Sci. U. S. A., 2017, 10.1073/pnas.1708907114


Metal: Fe
Ligand type: Porphyrin
Host protein: Myoglobin (Mb)
Anchoring strategy: Supramolecular
Optimization: Chemical & genetic
Reaction: Cyclopropanation
Max TON: 4740
ee: 99.2
PDB: ---
Notes: Stapling of protein via thioether bond formation between the noncanonical amino acid O-2-bromoethyl tyrosine and cysteine

Exploiting and Engineering Hemoproteins for Abiological Carbene and Nitrene Transfer Reactions

Review

Arnold, F. H.; Fasan, R.

Curr. Opin. Biotechnol., 2017, 10.1016/j.copbio.2017.06.005


Notes: ---

Importance of Scaffold Flexibility/Rigidity in the Design and Directed Evolution of Artificial Metallo-β-Lactamases

Song, W. J.; Tezcan, F. A.

J. Am. Chem. Soc., 2017, 10.1021/jacs.7b08981


Metal: Zn
Ligand type: Amino acid
Host protein: Zn8:AB54
Anchoring strategy: Dative
Optimization: Genetic
Reaction: Hydrolysis
Max TON: ---
ee: ---
PDB: 5XZI
Notes: Supramolecular protein scaffold constructed from cytochrome cb562 building blocks, Ampicillin hydrolysis: kcat/KM = 130 min-1 * M-1

Metal: Zn
Ligand type: Amino acid
Host protein: Zn8:AB54 (mutant C96T)
Anchoring strategy: Dative
Optimization: Genetic
Reaction: Hydrolysis
Max TON: ---
ee: ---
PDB: 5XZJ
Notes: Supramolecular protein scaffold constructed from cytochrome cb562 building blocks, Ampicillin hydrolysis: kcat/KM = 210 min-1 * M-1

Manganese(V) Porphycene Complex Responsible for Inert C–H Bond Hydroxylation in a Myoglobin Matrix

Oohora, K.

J. Am. Chem. Soc., 2017, 10.1021/jacs.7b11288


Metal: Mn
Ligand type: Amino acid; Porphycene
Host protein: Myoglobin (Mb)
Anchoring strategy: Reconstitution
Optimization: ---
Reaction: Hydroxylation
Max TON: 13
ee: ---
PDB: 5YL3
Notes: ---

Orthogonal Expression of an Artificial Metalloenzyme for Abiotic Catalysis

Brustad, E. M.

ChemBioChem, 2017, 10.1002/cbic.201700397


Metal: Ir
Ligand type: Methyl; Porphyrin
Host protein: Cytochrome BM3h
Anchoring strategy: Reconstitution
Optimization: Chemical & genetic
Reaction: Cyclopropanation
Max TON: 339
ee: 97
PDB: ---
Notes: Reaction of styrene with ethyl diazoacetate, cis:trans = 29:71

Peroxide Activation Regulated by Hydrogen Bonds within Artificial Cu Proteins

Borovik, A. S.

J. Am. Chem. Soc., 2017, 10.1021/jacs.7b10452


Metal: Cu
Host protein: Streptavidin (Sav)
Anchoring strategy: Supramolecular
Optimization: Chemical & genetic
Reaction: Oxidation
Max TON: ---
ee: ---
PDB: 6ANX
Notes: ---

Selective C–H Bond Functionalization Using Repurposed or Artificial Metalloenzymes

Review

Lewis, J. C.

Curr. Opin. Chem. Biol., 2017, 10.1016/j.cbpa.2016.12.027


Notes: ---

Stereoselective Sulfoxidation Catalyzed by Achiral Schiff Base Complexes in the Presence of Serum Albumin in Aqueous Media

Bian, H.-D.; Huang, F.-P.

Tetrahedron: Asymmetry, 2017, 10.1016/j.tetasy.2017.10.021


Metal: Co
Anchoring strategy: Undefined
Optimization: ---
Reaction: Sulfoxidation
Max TON: ~60
ee: 59
PDB: ---
Notes: ---

Supramolecular Anchoring of NCN-Pincer Palladium Complexes into a β-Barrel Protein Host: Molecular-Docking and Reactivity Insights

Salmain, M.; Thorimbert, S.

Eur. J. Inorg. Chem., 2017, 10.1002/ejic.201700365


Metal: Pd
Ligand type: NCN-Pincer (amines)
Host protein: β-lactoglobulin (βLG)
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Aldol condensation
Max TON: 4.9
ee: 0
PDB: ---
Notes: Aldol condensation of methyl isocyanoacetate and benzaldehyde (trans/cis = 38:62)

Supramolecular Enzyme Mimics

Review

Okamoto, Y.; Ward, T. R.

Comprehensive Supramolecular Chemistry II, 2017, 10.1016/B978-0-12-409547-2.12551-X


Notes: Book chapter