Enzyme-triggered cascade reactions and assembly of abiotic block copolymers into micellar nanostructures.
Catalytic action of an enzyme is shown to transform a non-assembling block copolymer, composed of a completely non-natural repeat unit structure, into a self-assembling polymer building block. To achieve this, poly(styrene) is combined with an enzyme-sensitive methacrylate-based polymer segment carrying carefully designed azobenzene side chains. Once exposed to the enzyme azoreductase, in the presence of coenzyme NADPH, the azobenzene linkages undergo a bond scission reaction. This triggers a spontaneous 1,6-self-elimination cascade process and transforms the initially hydrophobic methacrylate polymer segment into a hydrophilic hydroxyethyl methacrylate structure. This change in chemical polarity of one of the polymer blocks confers an amphiphilic character to the diblock copolymer and permits it to self-assemble into a micellar nanostructure in water.
Department of Materials, ETH-Zürich , CH-8093 Zürich, Switzerland.
Jingyi
J
Rao
Christine
C
Hottinger
Anzar
A
Khan
D006801:Humans; D008823:Micelles; D009247:NADH, NADPH Oxidoreductases / Q000378:metabolism*; D009249:NADP / Q000378:metabolism; D049329:Nanostructures / Q000737:chemistry*; D009601:Nitroreductases; D011137:Polystyrenes / Q000737:chemistry*
D008823:Micelles; D011137:Polystyrenes; D009249:NADP; D009247:NADH, NADPH Oxidoreductases; D009601:Nitroreductases; C021106:azoreductase