Controlled Hierarchical Assembly of Spider Silk-DNA Chimeras into Ribbons and Raft-Like Morphologies

Spider silk-DNA conjugates comprising the recombinant spider silk protein eADF4(C16) and short oligonucleotides were arranged in a linear antiparallel and parallel as well as in a branched manner via designed complementarity of the DNA moieties. After cross-beta fibril self-assembly, temperature-induced annealing of the DNA moieties triggered fibril association into ribbons, composed of aligned nanofibrils, and rafts composed of ribbons ordered into sharply bordered, squared fibrous microstructures. The formation of the superstructures was clearly dependent on the individual silk-DNA conjugate. A combination of 5'-conjugated silk moieties via complementary nucleic acids enhanced fibril association, whereas mixing complementary 5'- and 3'-silk conjugates inhibited the formation of higher-order structures.