Conjugates of enzymes and poly(2-methyloxazoline) were used as organosoluble amphiphilic polymer nanocontainers for dissolving osmate, thereby converting the enzymes into organosoluble artificial metalloenzymes. These were shown to catalyze the dihydroxylation of different alkenes with high enantioselectivity. The highest selectivities, found for osmate complexed with laccase polymer-enzyme con...

A Rh(NHC) phosphonate complex reacts with the lipases cutinase and Candida antarctica lipase B resulting in the first (soluble) artificial metalloenzymes formed by covalent active site-directed hybridization. When compared to unsupported complexes, these new robust hybrids show enhanced chemoselectivity in the (competitive) hydrogenation of olefins over ketones.

A novel idea for biochemical microanalysis of heavy metal ions in combination with flow-injection techniques is proposed. The microdetermination of the cofactors based on an apoenzyme reactivation method is reviewed exemplifying the assays for heavy metal ions with use of several kinds of immobilized metalloenzymes as the recognition elements for each metal ion.

Many metalloenzymes exhibit distinctive spectral features that are now becoming well understood. These reflect active site electronic structures that can make significant contributions to catalysis. Copper proteins provide well-characterized examples in which the unusual electronic structures of their active sites contribute to rapid, long-range electron transfer reactivity, oxygen binding and ...

Current research is reshaping basic theories regarding the roles of metal ions in ribozyme function. No longer viewed as strict metalloenzymes, some ribozymes can access alternative catalytic mechanisms depending on the identity and availability of metal ions. Similarly, reaction conditions can allow different folding pathways to predominate, with divalent cations sometimes playing opposing roles.

Metalloenzymes that activate molecular oxygen possess great potential as catalyst for specific oxidation reactions and as guides for the development of efficient small molecule catalysts. These lowmolecular metal complexes serves as functional model and catalyze the same (or a closely related) reaction as does the metalloenzyme to be mimicked. In combination with the structural models which mim...