Assembly-Line Biosynthesis in Living-Cell Emulsions via Tunable Supramolecular Surface Chemistry

Nature organizes enzymes in micro-compartments to enable efficient biosynthesis, inspiring multienzyme cascades for producing complex molecules. However, practical implementation is often limited by enzyme incompatibility, poor substrate transfer, and inefficient catalyst recycling. Here, we report a living biocatalytic platform that operates as a factory-like assembly line within Pickering emulsions. Tunable supramolecular chemistry is used to graft an oil-derived photocatalyst onto enzyme-overexpressing Escherichia coli (E. coli) cells, generating amphiphilic "suprabacteria" that self-assemble at water-oil interfaces and stabilize emulsions. These interfacial suprabacteria accelerate chemoenzymatic and multienzyme cascades, achieving reaction rates up to 45-fold higher than conventional biphasic systems. The platform supports single-step, sequential, and one-pot cascade reactions, including gram-scale benzoin synthesis. Importantly, the dynamic supramolecular linkage enables on-demand dual recycling: either the living-cell conjugate is reused, or the synthetic catalyst is selectively recovered and reattached to fresh cells. This strategy integrates chemical and biological catalysis in a sustainable, scalable platform for future greener industrial biosynthesis.