The
design and construction of higher-order structure and function
in proteinosome microcompartments enclosed by a cross-linked membrane
of amphiphilic bovine serum albumin/poly(N-isopropylacrylamide)
(BSA-NH2/PNIPAAm) nanoconjugates is described. Three structure/function
relationships are investigated: (i) differential chemical cross-linking
for the control of membrane disassembly and regulated release of encapsulated
genetic polymers; (ii) enzyme-mediated hydrogel structuring of the
internal microenvironment to increase mechanical robustness and generate
a molecularly crowded reaction environment; and (iii) self-production
of a membrane-enclosing outer hydrogel wall for generating protease-resistant
forms of the protein–polymer protocells. Our results highlight
the potential of integrating aspects of supramolecular and polymer
chemistry into the design and construction of novel bioinspired microcompartments
as a step toward small-scale materials systems based on synthetic
cellularity