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.

Routine and reliable syntheses of self-assembled hybrid materials with tuneable functionalities are urgently required if novel functional nanostructures are to be developed for real-life applications and economic commercialization. This Highlight presents an overview of recent progress in the synthesis and use of a new class of mesolamellar magnesium organophyllosilicate clays containing covalently linked organic functionalities. We focus in particular on strategies of template-directed synthesis, exfoliation, fractionation and re-assembly involving aminopropyl-functionalized organoclays, and illustrate how combinations of these approaches can be used for the fabrication of novel functional hybrid materials with complex morphological form and structure. Examples of mesolamellar intercalation of functional biomolecules such as enzymes, DNA and drugs, nanoscale wrapping of isolated proteins, enzymes and polynucleotides, and engineering of photoactive cell membrane/organoclay superstructures are presented.

Acoustic standing waves offer an excellent opportunity to trap and spatially manipulate colloidal objects. This noncontact technique is used for the in situ formation and patterning in aqueous solution of 1D or 2D arrays of pH‐responsive coacervate microdroplets comprising poly(diallyldimethylammonium) chloride and the dipeptide N‐fluorenyl‐9‐methoxy‐carbonyl‐D‐alanine‐D‐alanine. Decreasing the pH of the preformed droplet arrays results in dipeptide nanofilament self‐assembly and subsequent formation of a micropatterned supramolecular hydrogel that can be removed as a self‐supporting monolith. Guest molecules such as molecular dyes, proteins, and oligonucleotides are sequestered specifically within the coacervate droplets during acoustic processing to produce micropatterned hydrogels containing spatially organized functional components. Using this strategy, the site‐specific isolation of multiple enzymes to drive a catalytic cascade within the micropatterned hydrogel films is exploited.

Higher-ordered 3D macroporous TiO₂-functionalized chitosan scaffolds were prepared by ice segregation induced self-assembly (ISISA), in which homogenous dispersions of 6, 27 or 200 nm sized TiO₂nanoparticles and chitosan cross-linked with glycidoxypropyltrimethoxysilane were unidirectionally frozen at −196 °C. Scanning electron microscopy showed that under established optimum conditions the monoliths comprised well-aligned 30–50 µm sized micro-channels running parallel to the direction of ice growth. The surface morphology of the internal wall structure was influenced by the size of the titania nanoparticles. Scaffolds prepared in the presence of 6 nm sized anatase particles showed featureless walls with concealed/embedded nanoparticles, whereas larger TiO₂ particles remained exposed at the surface of the channel walls. Mechanical properties of the composite scaffolds were studied under compressive loads and stress–strain measurements obtained, and the effect of particle size on the elastic properties of the macroporous constructs determined. The hybrid scaffolds were shown to be reusable substrates for the photocatalytic degradation of methylene blue and Orange II dye molecules.