Polymer‐assisted biocatalysis: Unprecedented enzymatic oxidation of fullerene in aqueous medium

Enzymatic complexes, constructed by linear‐dendritic copolymers and laccase, are used for the unprecedented one‐pot biotransformation of fullerene (C60) into epoxide‐ and hydroxyl‐derivatives under mild and environmentally friendly reaction conditions (45 °C and aqueous medium). The reaction is catalyzed by mediator pairs ‐ N‐hydroxy‐5‐norbornene‐2,3‐dicarboxylic acid imide/1‐Hydroxybenzotriazole or 2,2′‐Azino‐bis(3‐ethylbenzothiazoline‐6‐sulfonic acid)/1‐Hydroxybenzotriazole used in equimolar amounts. After 24 and 48 h, the biotransformation products C60On, C60(OH)n, C60(H)n(OH)n, and/or C60On(H)m(OH)m range between 50 and 78%, respectively. Their structure is revealed by FTIR, NMR, and mass‐spectrometry. The mechanism of the process is discussed and elucidated. The reaction procedure allows the repeated usage of the enzyme/linear‐dendritic complex, which retains its catalytic activity after several cycles.