24 publications

24 publications

A Clamp-Like Biohybrid Catalyst for DNA Oxidation

Nolte, R. J. M.

Nat. Chem., 2013, 10.1038/NCHEM.1752

In processive catalysis, a catalyst binds to a substrate and remains bound as it performs several consecutive reactions, as exemplified by DNA polymerases. Processivity is essential in nature and is often mediated by a clamp-like structure that physically tethers the catalyst to its (polymeric) template. In the case of the bacteriophage T4 replisome, a dedicated clamp protein acts as a processivity mediator by encircling DNA and subsequently recruiting its polymerase. Here we use this DNA-binding protein to construct a biohybrid catalyst. Conjugation of the clamp protein to a chemical catalyst with sequence-specific oxidation behaviour formed a catalytic clamp that can be loaded onto a DNA plasmid. The catalytic activity of the biohybrid catalyst was visualized using a procedure based on an atomic force microscopy method that detects and spatially locates oxidized sites in DNA. Varying the experimental conditions enabled switching between processive and distributive catalysis and influencing the sliding direction of this rotaxane-like catalyst.


Metal: Mn
Ligand type: Porphyrin
Host protein: gp45
Anchoring strategy: Covalent
Optimization: ---
Max TON: ---
ee: ---
PDB: 1CZD
Notes: ---

Albumin-Conjugated Corrole Metal Complexes: Extremely Simple Yet Very Efficient Biomimetic Oxidation Systems

Gross, Z.

J. Am. Chem. Soc., 2005, 10.1021/ja045372c

An extremely simple biomimetic oxidation system, consisting of mixing metal complexes of amphiphilic corroles with serum albumins, utilizes hydrogen peroxide for asymmetric sulfoxidation in up to 74% ee. The albumin-conjugated manganese corroles also display catalase-like activity, and mechanistic evidence points toward oxidant-coordinated manganese(III) as the prime reaction intermediate.


Metal: Mn
Ligand type: Corrole
Anchoring strategy: Supramolecular
Optimization: Chemical & genetic
Reaction: Sulfoxidation
Max TON: 8
ee: 74
PDB: ---
Notes: ---

Metal: Mn
Ligand type: Corrole
Anchoring strategy: Supramolecular
Optimization: Chemical & genetic
Reaction: Sulfoxidation
Max TON: 42
ee: 52
PDB: ---
Notes: ---

A Site-Selective Dual Anchoring Strategy for Artificial Metalloprotein Design

Lu, Y.

J. Am. Chem. Soc., 2004, 10.1021/ja046908x

Introducing nonnative metal ions or metal-containing prosthetic groups into a protein can dramatically expand the repertoire of its functionalities and thus its range of applications. Particularly challenging is the control of substrate-binding and thus reaction selectivity such as enantioselectivity. To meet this challenge, both non-covalent and single-point attachments of metal complexes have been demonstrated previously. Since the protein template did not evolve to bind artificial metal complexes tightly in a single conformation, efforts to restrict conformational freedom by modifying the metal complexes and/or the protein are required to achieve high enantioselectivity using the above two strategies. Here we report a novel site-selective dual anchoring (two-point covalent attachment) strategy to introduce an achiral manganese salen complex (Mn(salen)), into apo sperm whale myoglobin (Mb) with bioconjugation yield close to 100%. The enantioselective excess increases from 0.3% for non-covalent, to 12.3% for single point, and to 51.3% for dual anchoring attachments. The dual anchoring method has the advantage of restricting the conformational freedom of the metal complex in the protein and can be generally applied to protein incorporation of other metal complexes with minimal structural modification to either the metal complex or the protein.


Metal: Mn
Ligand type: Salen
Host protein: Myoglobin (Mb)
Anchoring strategy: Covalent
Optimization: Genetic
Reaction: Sulfoxidation
Max TON: 3.9
ee: 51
PDB: 1MBO
Notes: Sperm whale myoglobin

Coordinated Design of Cofactor and Active Site Structures in Development of New Protein Catalysts

Watanabe, Y.

J. Am. Chem. Soc., 2005, 10.1021/ja045995q


Metal: Mn
Ligand type: Salophen
Host protein: Myoglobin (Mb)
Anchoring strategy: Reconstitution
Optimization: Chemical & genetic
Max TON: ---
ee: ---
PDB: 1V9Q
Notes: ---

Metal: Cr
Ligand type: Salophen
Host protein: Myoglobin (Mb)
Anchoring strategy: Reconstitution
Optimization: Chemical & genetic
Max TON: ---
ee: ---
PDB: 1J3F
Notes: ---

Metal: Mn
Ligand type: Salen
Host protein: Myoglobin (Mb)
Anchoring strategy: Reconstitution
Optimization: Chemical & genetic
Max TON: ---
ee: ---
PDB: ---
Notes: ---

Metal: Cr
Ligand type: Salen
Host protein: Myoglobin (Mb)
Anchoring strategy: Reconstitution
Optimization: Chemical & genetic
Max TON: ---
ee: ---
PDB: ---
Notes: ---

Covalent Versus Non-covalent (Biocatalytic) Approaches for Enantioselective Sulfoxidation Catalyzed by Corrole Metal Complexes

Gross, Z.

Cat. Sci. Technol., 2011, 10.1039/c1cy00046b


Metal: Mn
Ligand type: Corrole
Anchoring strategy: Supramolecular
Optimization: Chemical & genetic
Reaction: Sulfoxidation
Max TON: 45
ee: 70
PDB: ---
Notes: ---

C(sp3)–H Bond Hydroxylation Catalyzed by Myoglobin Reconstituted with Manganese Porphycene

Hayashi, T

J. Am. Chem. Soc., 2013, 10.1021/ja409404k


Metal: Mn
Ligand type: Porphycene
Host protein: Myoglobin (Mb)
Anchoring strategy: Reconstitution
Optimization: ---
Reaction: Hydroxylation
Max TON: ---
ee: ---
PDB: 2WI8
Notes: ---

Incorporation of Biotinylated Manganese-Salen Complexes into Streptavidin: New Artificial Metalloenzymes for Enantioselective Sulfoxidation

Ward, T. R.

J. Organomet. Chem., 2009, 10.1016/j.jorganchem.2008.11.023


Metal: Mn
Ligand type: Oxide; Salen
Host protein: Streptavidin (Sav)
Anchoring strategy: Supramolecular
Optimization: Chemical & genetic
Reaction: Sulfoxidation
Max TON: 28
ee: 13
PDB: ---
Notes: ---

Incorporation of Manganese Complexes into Xylanase: New Artificial Metalloenzymes for Enantioselective Epoxidation

Mahy, J.-P.; Ricoux, R.

ChemBioChem, 2012, 10.1002/cbic.201100659


Metal: Mn
Ligand type: Porphyrin
Host protein: Xylanase A (XynA)
Anchoring strategy: Supramolecular
Optimization: ---
Reaction: Epoxidation
Max TON: 21
ee: 80
PDB: ---
Notes: ---

Intramolecular C(sp3)-H Amination of Arylsulfonyl Azides with Engineered and Artificial Myoglobin-Based Catalysts

Fasan, R.

Bioorg. Med. Chem., 2014, 10.1016/j.bmc.2014.05.015


Metal: Mn
Ligand type: Amino acid; Porphyrin
Host protein: Myoglobin (Mb)
Anchoring strategy: Metal substitution
Optimization: Chemical & genetic
Reaction: C-H activation
Max TON: 142
ee: ---
PDB: ---
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

Manganese Terpyridine Artificial Metalloenzymes for Benzylic Oxygenation and Olefin Epoxidation

Lewis, J. C.

Tetrahedron, 2014, 10.1016/j.tet.2014.03.008


Metal: Mn
Ligand type: Poly-pyridine
Host protein: Nitrobindin (Nb)
Anchoring strategy: Covalent
Optimization: Chemical
Max TON: 19.2
ee: ---
PDB: 3EMM
Notes: ---

Metal: Mn
Ligand type: Poly-pyridine
Host protein: Nitrobindin (Nb)
Anchoring strategy: Covalent
Optimization: Chemical
Reaction: Epoxidation
Max TON: 19.8
ee: ---
PDB: 3EMM
Notes: ---

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: ---

Metal Incorporated Horseradish Peroxidase (HRP) Catalyzed Oxidation of Resveratrol: Selective Dimerization or Decomposition

Pan, Y.

RSC Adv., 2013, 10.1039/c3ra43784a


Metal: Ca; Co; Mn; Ni; Zn
Ligand type: Undefined
Anchoring strategy: Undefined
Optimization: Chemical
Reaction: Oxidation
Max TON: ---
ee: ---
PDB: ---
Notes: Oxidation of resveratrol. Dimerisation product obtained.

Multifunctional Nanoenzymes from Carbonic Anhydrase Skeleton

Yilmaz, F.

Process Biochem., 2018, 10.1016/j.procbio.2018.06.005


Metal: Zn
Ligand type: Amino acid
Host protein: Carbonic anhydrase (CA)
Anchoring strategy: Metal substitution
Optimization: Chemical
Reaction: Hydrolysis
Max TON: ---
ee: ---
PDB: ---
Notes: Cross-linked carbonic anhydrase nano-enzyme particles (93 nm in diameter). Hydrolysis of 4-nitrophenyl acetate.

Metal: Rh
Ligand type: Amino acid
Host protein: Carbonic anhydrase (CA)
Anchoring strategy: Metal substitution
Optimization: Chemical
Reaction: Hydration
Max TON: ---
ee: ---
PDB: ---
Notes: Cross-linked carbonic anhydrase nano-enzyme particles (93 nm in diameter). Hydration of styrene.

Metal: Mn
Ligand type: Amino acid
Host protein: Carbonic anhydrase (CA)
Anchoring strategy: Metal substitution
Optimization: Chemical
Reaction: Oxidation
Max TON: ---
ee: ---
PDB: ---
Notes: Cross-linked carbonic anhydrase nano-enzyme particles (93 nm in diameter). Oxidation of styrene.

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

Oxidation Catalysis via Visible-Light Water Activation of a [Ru(bpy)3]2+ Chromophore BSA–Metallocorrole Couple

Gross, Z.; Mahy, J.-P.

Dalton Trans., 2016, 10.1039/c5dt04158a


Metal: Mn
Ligand type: Corrole
Anchoring strategy: Supramolecular
Optimization: ---
Reaction: Sulfoxidation
Max TON: 21
ee: 16
PDB: ---
Notes: Water as oxygen source

Oxidation of Organic Molecules in Homogeneous Aqueous Solution Catalyzed by Hybrid Biocatalysts (Based on the Trojan Horse Strategy)

Mahy, J.-P.

Tetrahedron: Asymmetry, 2010, 10.1016/j.tetasy.2010.03.050


Metal: Fe
Ligand type: Porphyrin
Host protein: Antibody 7A3
Anchoring strategy: Supramolecular
Optimization: ---
Reaction: Sulfoxidation
Max TON: 9
ee: 10
PDB: ---
Notes: ---

Metal: Mn
Ligand type: Porphyrin
Host protein: Antibody 7A3
Anchoring strategy: Supramolecular
Optimization: ---
Reaction: Epoxidation
Max TON: 105
ee: ---
PDB: ---
Notes: Imidazole as co-catalyst

Peroxidation of Pyrogallol by Antibody−Metalloporphyrin Complexes

Harada, A.

Inorg. Chem., 1997, 10.1021/ic9610849


Metal: Mn
Ligand type: Porphyrin
Host protein: Antibody 03-1
Anchoring strategy: Antibody
Optimization: ---
Max TON: 200
ee: ---
PDB: ---
Notes: ---

Metal: Fe
Ligand type: Porphyrin
Host protein: Antibody 03-1
Anchoring strategy: Antibody
Optimization: ---
Max TON: 300
ee: ---
PDB: ---
Notes: ---

Protein Scaffold of a Designed Metalloenzyme Enhances the Chemoselectivity in Sulfoxidation of Thioanisole

Lu, Y.

Chem. Commun., 2008, 10.1039/b718915j


Metal: Mn
Ligand type: Salen
Host protein: Myoglobin (Mb)
Anchoring strategy: Supramolecular
Optimization: Chemical & genetic
Reaction: Sulfoxidation
Max TON: 5.2
ee: 60
PDB: ---
Notes: Sperm whale myoglobin

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

Lu, Y.; Zhang, J.-L.

ACS Catal., 2011, 10.1021/cs200258e


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 Protein Environment Drives Selectivity for Sulfide Oxidation by an Artificial Metalloenzyme

Cavazza, C.; Ménage, S.

ChemBioChem, 2009, 10.1002/cbic.200800595


Metal: Mn
Ligand type: Salen
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Sulfoxidation
Max TON: 97
ee: ---
PDB: ---
Notes: ---

Towards Antibody-Mediated Metallo-Porphyrin Chemistry

Keinan, E.

Pure Appl. Chem., 1990, 10.1351/pac199062102013


Metal: Mn
Ligand type: Porphyrin
Host protein: Antibody
Anchoring strategy: Supramolecular
Optimization: ---
Max TON: 549
ee: ---
PDB: ---
Notes: ---

Towards the Directed Evolution of Hybrid Catalysts

Reetz, M. T.

Chimia, 2002, 10.2533/000942902777679920


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: ---

Transforming Carbonic Anhydrase into Epoxide Synthase by Metal Exchange

Soumillion, P.

ChemBioChem, 2006, 10.1002/cbic.200600127


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: ---