Catalytic processing in ruthenium-based polyoxometalate coacervate protocells.

The development of programmable microscale materials with cell-like functions, dynamics and collective behaviour is an important milestone in systems chemistry, soft matter bioengineering and synthetic protobiology. Here, polymer/nucleotide coacervate micro-droplets are reconfigured into membrane-bounded polyoxometalate coacervate vesicles (PCVs) in the presence of a bio-inspired Ru-based polyoxometalate catalyst to produce synzyme protocells (Ru4PCVs) with catalase-like activity. We exploit the synthetic protocells for the implementation of multi-compartmentalized cell-like models capable of collective synzyme-mediated buoyancy, parallel catalytic processing in individual horseradish peroxidase-containing Ru4PCVs, and chemical signalling in distributed or encapsulated multi-catalytic protocell communities. Our results highlight a new type of catalytic micro-compartment with multi-functional activity and provide a step towards the development of protocell reaction networks.

A Lewis acid catalytic core sandwiched by inorganic polyoxoanion caps: selective H2O2-based oxidations with [Al(III)4(H2O)10(ß-XW9O33H)2](6-) (X = As(III), Sb(III)).

The Al(III)-containing polyanions [Al(III)4(H2O)10(ß-XW9O33H)2](4-) with X = As(III) (1) and Sb(III) (2) feature four aluminum(III) centers sandwiched by two trivacant (ß-XW9O33) Keggin units, and trigger peroxide catalysis as well as substrate coordination via multiple Lewis acid site interactions.