Synthesis of Polymeric Enzyme-like Catalysts

Abstract

This account summarizes our recent achievements in synthesis of enzyme-like catalysts on the backbones of synthetic polymers. To synthesize effective artificial enzymes, it is desirable to design artificial active sites comprising binding unit and convergent catalytic groups. We developed several novel methodologies to position several catalytic elements in proximity on highly branched polymers. The resulting polymers manifested high catalytic effects in peptide hydrolysis. Some of the artificial peptidases we prepared achieved faster rates compared with catalytic antibodies with peptidase activity, approaching the level of catalytic rates achieved by natural peptidases. We have also achieved stereoselective hydrolysis of unactivated amides and effective hydrolysis of DNA molecules.

Combining Medium Effects and Cofactor Catalysis: Metal‐Coordinated Synzymes Accelerate Phosphate Transfer by 108

“…Following earlier work by Klotz and others, [18][19][20][21][22][23][24][25][26] we have demonstrated in previous studies that environmental effects can also be exploited in water by using synthetic polymeric enzyme models ('synzymes'). Synzymes are based on a polyethylene imine (PEI) backbone that is functionalised combinatorially to create a microenvironment in which desolvation, dispersion interactions and specific medium effects support catalysis.…”

Peptide‐ or Protein‐Cleaving Agents Based on Metal Complexes

“…Catalytic antibodies are examples of semisynthetic artificial enzymes (11)(12)(13)(14). Fully synthetic molecules also have been designed as enzyme mimics by using either peptidic (15,16) or nonpeptidic (17)(18)(19)(20)(21)(22)(23)(24) molecules.…”

Nature: A Model System for Chemists

“…Klotz and Suh used a large polyaziridine with extensive cross-links, and in some cases they added alkyl chains to form a hydrophobic region. In his independent research, Suh pursued this area, examining other polymers as well such as polystyrene (25). Also, Hollfelder et al examined this system quantitatively and concluded that there was a medium effect in the polyamines with added hydrocarbon chains (26).…”