Visible light-driven oxidation of non-native substrate by laccase attached on Ru-based metal-organic frameworks

Light-induced electron transfer can broaden the substrate range of metalloenzyme. However, the efficiency of photo-enzyme coupling is limited by the poor combination of photosensitizer or photocatalyst with enzyme. Herein, we prepared the nano-photocatalyst MIL-125-NH2@Ru(bpy) by in site embedding ruthenium pyridine-diimine complex [Ru(bpy)3]2+ into metal organic frameworks MIL-125-NH2 and associated it with multicopper oxidase (MCO) laccase. Compared to [Ru(bpy)3]2+, the coupling efficiency of MIL-125-NH2@Ru(bpy)3 for enzymatic oxygen reduction increased by 35.7%. A series of characterizations confirmed that the amino group of laccase formed chemical bonds with the surface defects or hydrophobic groups of MIL-125-NH2@Ru(bpy)3. Consequently, the tight binding accelerated the quenching process and electron transfer between laccase and the immobilized ruthenium pyridine-diimine complex. This work would open an avenue for the synthesis of MOFs photocatalyst towards photo-enzyme coupling.