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Host protein

6-Phospho-gluconolactonase (6-PGLac) A2A adenosine receptor Adipocyte lipid binding protein (ALBP) Antibody Antibody 03-1 Antibody 12E11G Antibody 13G10 Antibody 13G10 / 14H7 Antibody 14H7 Antibody 1G8 Antibody 28F11 Antibody 38C2 Antibody 3A3 Antibody 7A3 Antibody7G12-A10-G1-A12 Antibody L-chain from Mab13-1 hybridoma cells Antibody SN37.4 Apo-[Fe]-hydrogenase from M. jannaschii Apo-ferritin Apo-HydA1 ([FeFe]-hydrogenase) from C. reinhardtii Apo-HydA enzymes from C. reinhardtii, M. elsdenii, C. pasteurianum Artificial construct Avidin (Av) Azurin Binding domain of Rabenosyn (Rab4) Bovine carbonic anhydrase (CA) Bovine carbonic anhydrase II (CA) Bovine serum albumin (BSA) Bovine β-lactoglobulin (βLG) Bromelain Burkavidin C45 (c-type cytochrome maquette) Carbonic anhydrase (CA) Carboxypeptidase A Catabolite activator protein (CAP) CeuE C-terminal domain of calmodulin Cutinase Cytochrome b562 Cytochrome BM3h Cytochrome c Cytochrome c552 Cytochrome cb562 Cytochrome c peroxidase Cytochrome P450 (CYP119) Domain of Hin recombinase Due Ferro 1 E. coli catabolite gene activator protein (CAP) [FeFe]-hydrogenase from C. pasteurianum (CpI) Ferredoxin (Fd) Ferritin FhuA FhuA ΔCVFtev Flavodoxin (Fld) Glyoxalase II (Human) (gp27-gp5)3 gp45 [(gp5βf)3]2 Heme oxygenase (HO) Hemoglobin Horse heart cytochrome c Horseradish peroxidase (HRP) Human carbonic anhydrase Human carbonic anhydrase II (hCAII) Human retinoid-X-receptor (hRXRa) Human serum albumin (HSA) HydA1 ([FeFe]-hydrogenase) from C. reinhardtii IgG 84A3 Laccase Lipase B from C. antarctica (CALB) Lipase from G. thermocatenulatus (GTL) LmrR Lysozyme Lysozyme (crystal) Mimochrome Fe(III)-S6G(D)-MC6 (De novo designed peptide) Mouse adenosine deaminase Myoglobin (Mb) Neocarzinostatin (variant 3.24) NikA Nitrobindin (Nb) Nitrobindin variant NB4 Nuclease from S. aureus Papain (PAP) Photoactive Yellow Protein (PYP) Photosystem I (PSI) Phytase Prolyl oligopeptidase (POP) Prolyl oligopeptidase (POP) from P. furiosus Rabbit serum albumin (RSA) Ribonuclease S RNase A Rubredoxin (Rd) Silk fibroin fibre Small heat shock protein from M. jannaschii ß-lactoglobulin Staphylococcal nuclease Steroid Carrier Protein 2L (SCP 2L) Sterol Carrier Protein (SCP) Streptavidin (monmeric) Streptavidin (Sav) Thermolysin Thermosome (THS) tHisF TM1459 cupin TRI peptide Trypsin Tryptophan gene repressor (trp) Xylanase A (XynA) Zn8:AB54 Zn8:AB54 (mutant C96T) α3D peptide α-chymotrypsin β-lactamase β-lactoglobulin (βLG)

Corresponding author

Akabori, S. Alberto, R. Albrecht, M. Anderson, J. L. R. Apfel, U.-P. Arnold, F. H. Artero, V. Bäckvall, J. E. Baker, D. Ball, Z. T. Banse, F. Berggren, G. Bian, H.-D. Birnbaum, E. R. Borovik, A. S. Bren, K. L. Bruns, N. Brustad, E. M. Cardona, F. Case, M. A. Cavazza, C. Chan, A. S. C. Coleman, J. E. Craik, C. S. Creus, M. Cuatrecasas, P. Darnall, D. W. DeGrado, W. F. Dervan, P. B. de Vries, J. Diéguez, M. Distefano, M. D. Don Tilley, T. Duhme-Klair, A. K. Ebright, R. H. Emerson, J. P. Eppinger, J. Fasan, R. Filice, M. Fontecave, M. Fontecilla-Camps, J. C. Fruk, L. Fujieda, N. Fussenegger, M. Gademann, K. Gaggero, N. Germanas, J. P. Ghattas, W. Ghirlanda, G. Golinelli-Pimpaneau, B. Goti, A. Gras, E. Gray, H. B. Green, A. P. Gross, Z. Gunasekeram, A. Happe, T. Harada, A. Hartwig, J. F. Hasegawa, J.-Y. Hayashi, T Hemschemeier, A. Herrick, R. S. Hilvert, D. Hirota, S. Huang, F.-P. Hureau, C. Hu, X. Hyster, T. K. Imanaka, T. Imperiali, B. Itoh, S. Janda, K. D. Jarvis, A. G. Jaussi, R. Jeschek, M. Kaiser, E. T. Kamer, P. C. J. Kazlauskas, R. J. Keinan, E. Khare, S. D. Kim, H. S. Kitagawa, S. Klein Gebbink, R. J. M. Kokubo, T. Korendovych, I. V. Kuhlman, B. Kurisu, G. Laan, W. Lee, S.-Y. Lehnert, N. Leow, T. C. Lerner, R. A. Lewis, J. C. Liang, H. Lindblad, P. Lin, Y.-W. Liu, J. Lombardi, A. Lubitz, W. Lu, Y. Maglio, O. Mahy, J.-P. Mangiatordi, G. F. Marchetti, M. Maréchal, J.-D. Marino, T. Marshall, N. M. Matile, S. Matsuo, T. McNaughton, B. R. Ménage, S. Messori, L. Mulfort, K. L. Nastri, F. Nicholas, K. M. Niemeyer, C. M. Nolte, R. J. M. Novič, M. Okamoto, Y. Okano, M. Okuda, J. Onoda, A. Oohora, K. Palomo, J. M. Pàmies, O. Panke, S. Pan, Y. Paradisi, F. Pecoraro, V. L. Pordea, A. Reetz, M. T. Reijerse, E. Renaud, J.-L. Ricoux, R. Rimoldi, I. Roelfes, G. Rovis, T. Sakurai, S. Salmain, M. Sasaki, T. Sauer, D. F. Schultz, P. G. Schwaneberg, U. Seelig, B. Shafaat, H. S. Shahgaldian, P. Sheldon, R. A. Shima, S. Sigman, D. S. Song, W. J. Soumillion, P. Strater, N. Sugiura, Y. Szostak, J. W. Tezcan, F. A. Thorimbert, S. Tiede, D. M. Tiller, J. C. Turner, N. J. Ueno, T. Utschig, L. M. van Koten, G. Wang, J. Ward, T. R. Watanabe, Y. Whitesides, G. M. Wilson, K. S. Woolfson, D. N. Yilmaz, F. Zhang, J.-L.

Journal

3 Biotech Acc. Chem. Res. ACS Catal. ACS Cent. Sci. ACS Sustainable Chem. Eng. Adv. Synth. Catal. Angew. Chem., Int. Ed. Appl. Biochem. Biotechnol. Appl. Organomet. Chem. Artificial Metalloenzymes and MetalloDNAzymes in Catalysis: From Design to Applications Beilstein J. Org. Chem. Biochemistry Biochim. Biophys. Acta, Bioenerg. Biochimie Bioconjug. Chem. Bioorg. Med. Chem. Bioorg. Med. Chem. Lett. Bioorganometallic Chemistry: Applications in Drug Discovery, Biocatalysis, and Imaging Biopolymers Biotechnol. Adv. Biotechnol. Bioeng. Can. J. Chem. Catal. Lett. Catal. Sci. Technol. Cat. Sci. Technol. ChemBioChem ChemCatChem Chem. Commun. Chem. Rev. Chem. Sci. Chem. Soc. Rev. Chem. - Eur. J. Chem. - Asian J. Chem. Lett. ChemistryOpen ChemPlusChem Chimia Commun. Chem. Comprehensive Inorganic Chemistry II Comprehensive Supramolecular Chemistry II C. R. Chim. Coordination Chemistry in Protein Cages: Principles, Design, and Applications Coord. Chem. Rev. Croat. Chem. Acta Curr. Opin. Biotechnol. Curr. Opin. Chem. Biol. Curr. Opin. Struct. Biol. Dalton Trans. Effects of Nanoconfinement on Catalysis Energy Environ. Sci. Eur. J. Biochem. Eur. J. Inorg. Chem. FEBS Lett. Helv. Chim. Acta Inorg. Chim. Acta Inorg. Chem. Int. J. Mol. Sci. Isr. J. Chem. J. Biol. Chem. J. Biol. Inorg. Chem. J. Immunol. Methods J. Inorg. Biochem. J. Mol. Catal. A: Chem. J. Mol. Catal. B: Enzym. J. Organomet. Chem. J. Phys. Chem. Lett. J. Porphyr. Phthalocyanines J. Protein Chem. J. Am. Chem. Soc. J. Chem. Soc. J. Chem. Soc., Chem. Commun. Methods Enzymol. Mol. Divers. Molecular Encapsulation: Organic Reactions in Constrained Systems Nature Nat. Catal. Nat. Chem. Biol. Nat. Chem. Nat. Commun. Nat. Protoc. Nat. Rev. Chem. New J. Chem. Org. Biomol. Chem. Plos ONE Proc. Natl. Acad. Sci. U. S. A. Process Biochem. Prog. Inorg. Chem. Prot. Eng. Protein Engineering Handbook Protein Expression Purif. Pure Appl. Chem. RSC Adv. Science Small Synlett Tetrahedron Tetrahedron: Asymmetry Tetrahedron Lett. Chem. Rec. Top. Catal. Top. Organomet. Chem. Trends Biotechnol.

(η6-Arene) Ruthenium(II) Complexes and Metallo-Papain Hybrid as Lewis Acid Catalysts of Diels–Alder Reaction in Water

Covalent embedding of a (η6-arene) ruthenium(II) complex into the protein papain gives rise to a metalloenzyme displaying a catalytic efficiency for a Lewis acid-mediated catalysed Diels–Alder reaction enhanced by two orders of magnitude in water.

Metal:

Ru

Ligand type:

Benzene; Phenanthroline

Host protein:

Papain (PAP)

Anchoring strategy:

Covalent

Optimization:

Chemical

Max TON:

440

ee:

---

PDB:

---

Notes:

TOF = 220 h-1

X-Ray Structure and Designed Evolution of an Artificial Transfer Hydrogenase

Metal:

Ru

Ligand type:

Amino-sulfonamide; Benzene

Host protein:

Streptavidin (Sav)

Anchoring strategy:

Supramolecular

Optimization:

Chemical & genetic

Max TON:

100

ee:

92

PDB:

2QCB

Notes:

---

Metal:

Ru

Ligand type:

Amino-sulfonamide; P-cymene

Host protein:

Streptavidin (Sav)

Anchoring strategy:

Supramolecular

Optimization:

Chemical & genetic

Max TON:

97

ee:

96

PDB:

2QCB

Notes:

---

Various Strategies for Obtaining Oxidative Artificial Hemoproteins with a Catalytic Oxidative Activity: From "Hemoabzymes" to "Hemozymes"?

Review

Notes:

---

Various Strategies for Obtaining Artificial Hemoproteins: From "Hemoabzymes" to "Hemozymes"

Metal:

Fe

Ligand type:

Porphyrin

Host protein:

Xylanase A (XynA)

Anchoring strategy:

Supramolecular

Optimization:

Chemical

Reaction:

Sulfoxidation

Max TON:

---

ee:

36

PDB:

---

Notes:

---

Vanadium-Catalysed Enantioselective Sulfoxidations: Rational Design of Biocatalytic and Biomimetic Systems

Metal:

V

Ligand type:

Oxide

Host protein:

Phytase

Anchoring strategy:

Undefined

Optimization:

Chemical

Reaction:

Sulfoxidation

Max TON:

---

ee:

68

PDB:

---

Notes:

---

Use of the Confined Spaces of Apo-Ferritin and Virus Capsids as Nanoreactors for Catalytic Reactions

Review

Notes:

---

Upregulation of an Artificial Zymogen by Proteolysis

Metal:

Ir

Ligand type:

Cp*; Tripeptide

Host protein:

Streptavidin (Sav)

Anchoring strategy:

Supramolecular

Optimization:

Chemical & genetic

Max TON:

2000

ee:

73

PDB:

---

Notes:

---

Transforming Carbonic Anhydrase into Epoxide Synthase by Metal Exchange

Metal:

Mn

Ligand type:

Amino acid

Anchoring strategy:

Metal substitution

Optimization:

Chemical & genetic

Reaction:

Epoxidation

Max TON:

4.1

ee:

52

PDB:

---

Notes:

---

Metal:

Mn

Ligand type:

Amino acid

Anchoring strategy:

Metal substitution

Optimization:

Chemical & genetic

Reaction:

Epoxidation

Max TON:

10.3

ee:

40

PDB:

---

Notes:

---

Toward the Computational Design of Artificial Metalloenzymes: From Protein–Ligand Docking to Multiscale Approaches

Review

Notes:

---

Towards the Directed Evolution of Hybrid Catalysts

Metal:

Mn

Ligand type:

Salen

Host protein:

Papain (PAP)

Anchoring strategy:

Covalent

Optimization:

---

Reaction:

Epoxidation

Max TON:

---

ee:

< 10

PDB:

---

Notes:

---

Metal:

Rh

Ligand type:

Dipyridin-2-ylmethane

Host protein:

Papain (PAP)

Anchoring strategy:

Covalent

Optimization:

---

Reaction:

Hydrogenation

Max TON:

---

ee:

< 10

PDB:

---

Notes:

---

Towards Evolution of Artificial Metalloenzymes - A Protein Engineer’s Perspective

Review

Notes:

---

Towards Antibody-Mediated Metallo-Porphyrin Chemistry

Metal:

Mn

Ligand type:

Porphyrin

Host protein:

Antibody

Anchoring strategy:

Supramolecular

Optimization:

---

Max TON:

549

ee:

---

PDB:

---

Notes:

---

Thermostable Peroxidase-Activity with a Recombinant Antibody L-Chain-Porphyrin Fe(III) Complex

Metal:

Fe

Ligand type:

Porphyrin

Anchoring strategy:

Antibody

Optimization:

---

Reaction:

Peroxidation

Max TON:

---

ee:

---

PDB:

---

Notes:

---

The Rational Design of Semisynthetic Peroxidases

Metal:

V

Ligand type:

Oxide

Host protein:

Phytase

Anchoring strategy:

Undefined

Optimization:

Chemical

Reaction:

Sulfoxidation

Max TON:

---

ee:

66

PDB:

---

Notes:

Reaction performed in 30% organic co-solvent.

The Protein Environment Drives Selectivity for Sulfide Oxidation by an Artificial Metalloenzyme

Metal:

Mn

Ligand type:

Salen

Anchoring strategy:

Supramolecular

Optimization:

Chemical

Reaction:

Sulfoxidation

Max TON:

97

ee:

---

PDB:

---

Notes:

---

The Plasticity of Redox Cofactors: From Metalloenzymes to Redox-Active DNA

Review

Notes:

---

The Important Role of Covalent Anchor Positions in Tuning Catalytic Properties of a Rationally Designed MnSalen-Containing Metalloenzyme

Metal:

Mn

Ligand type:

Salen

Host protein:

Myoglobin (Mb)

Anchoring strategy:

Covalent

Optimization:

Genetic

Reaction:

Sulfoxidation

Max TON:

---

ee:

83

PDB:

---

Notes:

Reaction rate: 2.3 min-1

The Bovine Serum Albumin-2-Phenylpropane-1,2-diolatodioxoosmium(VI) Complex as an Enantioselective Catalyst for cis-Hydroxylation of Alkenes

Metal:

Os

Ligand type:

Undefined

Anchoring strategy:

Undefined

Optimization:

---

Reaction:

Dihydroxylation

Max TON:

40

ee:

68

PDB:

---

Notes:

---

The Ascent of Man(Made Oxidoreductases)

Review

Notes:

---

Tailoring the Active Site of Chemzymes by Using a Chemogenetic-Optimization Procedure: Towards Substrate-Specific Artificial Hydrogenases Based on the Biotin–Avidin Technology

Metal:

Rh

Ligand type:

Phosphine

Host protein:

Streptavidin (Sav)

Anchoring strategy:

Supramolecular

Optimization:

Chemical & genetic

Reaction:

Hydrogenation

Max TON:

---

ee:

94

PDB:

---

Notes:

---

Systematic Tuning of Heme Redox Potentials and Its Effects on O2 Reduction Rates in a Designed Oxidase in Myoglobin

Metal:

Cu

Ligand type:

Amino acid

Host protein:

Myoglobin (Mb)

Anchoring strategy:

Dative

Optimization:

Chemical & genetic

Max TON:

1600

ee:

---

PDB:

4FWX

Notes:

Sperm whale myoglobin

Synthetic Cascades are Enabled by Combining Biocatalysts with Artificial Metalloenzymes

Metal:

Ir

Ligand type:

Amino-sulfonamide; Cp*

Host protein:

Streptavidin (Sav)

Anchoring strategy:

Supramolecular

Optimization:

Genetic

Max TON:

100

ee:

> 99

PDB:

---

Notes:

Cascade

Synthesis of Hybrid Transition-Metalloproteins via Thiol-Selective Covalent Anchoring of Rh-Phosphine and Ru-Phenanthroline Complexes

Metal:

Rh

Ligand type:

COD; Phosphine

Anchoring strategy:

Covalent

Optimization:

---

Reaction:

Hydrogenation

Max TON:

---

ee:

---

PDB:

2PHY

Notes:

---

Synthesis of a Sequence-Specific DNA-Cleaving Peptide

Metal:

Fe

Ligand type:

EDTA

Anchoring strategy:

Covalent

Optimization:

---

Reaction:

DNA cleavage

Max TON:

<1

ee:

---

PDB:

---

Notes:

Engineered sequence specificity

Synthesis of a New Estradiol–Iron Metalloporphyrin Conjugate Used to Build up a New Hybrid Biocatalyst for Selective Oxidations by the ‘Trojan Horse’ Strategy

Metal:

Fe

Ligand type:

Porphyrin

Host protein:

Antibody 7A3

Anchoring strategy:

Supramolecular

Optimization:

---

Reaction:

Sulfoxidation

Max TON:

12

ee:

8

PDB:

---

Notes:

---

Synthesis of a Heterogeneous Artificial Metallolipase with Chimeric Catalytic Activity

Metal:

Cu

Ligand type:

Phenanthroline

Anchoring strategy:

Covalent

Optimization:

Genetic

Max TON:

411

ee:

92

PDB:

---

Notes:

ArM is immobilized on Sepabeads. Endo/exo = 93.5%

Metal:

Cu

Ligand type:

Phenanthroline

Anchoring strategy:

Covalent

Optimization:

Genetic

Reaction:

Reduction

Max TON:

---

ee:

---

PDB:

---

Notes:

Cascade reaction: Ester hydrolysis (natural function of the host protein) followed by reduction (function of the designed ArM).

Supramolecular Interactions Between Functional Metal Complexes and Proteins

Review

Notes:

---

Supramolecular Enzyme Mimics

Review

Notes:

Book chapter

Supramolecular Assembly of Artificial Metalloenzymes Based on the Dimeric Protein LmrR as Promiscuous Scaffold

Metal:

Cu

Ligand type:

Phenanthroline

Host protein:

LmrR

Anchoring strategy:

Supramolecular

Optimization:

Genetic

Max TON:

11.1

ee:

94

PDB:

3F8B

Notes:

---

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

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)