An aqueous‐based microcompartmentalized model involving the integration of partially hydrophobic Fe(III)‐rich montmorillonite (FeM) clay particles as structural and catalytic building blocks for colloidosome membrane assembly, self‐directed membrane remodeling, and signal‐induced protocell communication is described. The clay colloidosomes exhibit size‐ and charge‐selective permeability, and show dual catalytic functions involving spatially confined enzyme‐mediated dephosphorylation and peroxidase‐like membrane activity. The latter is used for the colloidosome‐mediated synthesis and assembly of a temperature‐responsive poly(N‐isopropylacrylamide)(PNIPAM)/clay‐integrated hybrid membrane. In situ PNIPAM elaboration of the membrane is coupled to a glucose oxidase (GOx)‐mediated signaling pathway to establish a primitive model of chemical communication and functional activation within a synthetic “protocell community” comprising a mixed population of GOx‐containing silica colloidosomes and alkaline phosphatase (ALP)‐containing FeM‐clay colloidosomes. Triggering the enzyme reaction in the silica colloidosomes gives a hydrogen peroxide signal that induces polymer wall formation in a coexistent population of the FeM‐clay colloidosomes, which in turn generates self‐regulated membrane‐gated ALP‐activity within the clay microcompartments. The emergence of new functionalities in inorganic colloidosomes via chemical communication between different protocell populations provides a first step toward the realization of interacting communities of synthetic functional microcompartments.

We present a new strategy for the design and construction of artificial photoresponsive protocells based on the encapsulation and activation of metallized peptide/porphyrin self-assembled nanofilaments within silica nanoparticle-stabilized colloidosomes. The protocells exhibit high light sensitivity and can utilise day light (700 lux) for the production of nicotinamide adenine dinucleotide (NADH) by photo-mediated reduction of NAD⁺ within the colloidosomes. The results provide a promising step towards artificial photosynthetic micro-compartmentalized devices with integrated functional structures and photoresponsive behaviour.

The bioinspired design and construction of enzyme@capsule microreactors with specific cell-like functionality has generated tremendous interest in recent years. Inspired by their fascinating complexity, scientists have endeavored to understand the essential aspects of a natural cell and create biomimicking microreactors so as to immobilize enzymes within the hierarchical structure of a microcapsule. In this study, simultaneous encapsulation of alcohol dehydrogenase (ADH) was achieved during the preparation of microcapsules by the Pickering emulsion method using amphiphilic modified TiO₂ nanoparticles (NPs) as building blocks for assembling the photocatalytic microcapsule membrane. The ADH@TiO₂ NP microreactors exhibited dual catalytic functions, i.e., spatially confined enzymatic catalysis and the membrane-associated photocatalytic oxidation under visible light. The sustainable cycling of nicotinamide adenine dinucleotide (NAD) coenzyme between NADH and NAD⁺ was realized by enzymatic regeneration of NADH from NAD⁺ reduction, and was provided in a form that enabled further photocatalytic oxidation to NAD⁺ under visible light. This bioinspired ADH@TiO₂ NP microreactor allowed the linking of a semiconductor mineral-based inorganic photosystem to enzymatic reactions. This is a first step toward the realization of sustainable biological cycling of NAD⁺/NADH coenzyme in synthetic functional microsystems operating under visible light irradiation.