RESUMO
Current environmental challenges and the shrinking fossil-fuel feedstock are important criteria for the next generation of polymer materials. In this context, we present a fully bio-based material, which shows promise as a thermoplastic elastomer (TPE). Due to the use of ß-farnesene and L-lactide as monomers, bio-based feedstocks, namely sugar cane and corn, can be used. A bifunctional initiator for the carbanionic polymerization was employed, to permit an efficient synthesis of ABA-type block structures. In addition, the "green" solvent MTBE (methyl tert-butyl ether) was used for the anionic polymerisation, enabling excellent solubility of the bifunctional anionic initiator. This afforded low dispersity (D=1.07 to 1.10) and telechelic polyfarnesene macroinitiators. These were employed for lactide polymerization to obtain H-shaped triblock copolymers. TEM and SAXS revealed clearly phase-separated morphologies, and tensile tests demonstrated elastic mechanical properties. The materials featured two glass transition temperatures, at - 66 °C and 51 °C as well as gyroid or cylindrical morphologies, resulting in soft elastic materials at room temperature.
RESUMO
Secondary structure formation differentiates polypeptides from most of the other synthetic polymers, and the transitions from random coils to rod-like α-helices or ß-sheets represent an additional parameter to direct self-assembly and the morphology of nanostructures. We investigated the influence of distinct secondary structures on the self-assembly of reactive amphiphilic polypept(o)ides. The individual morphologies can be preserved by core cross-linking via chemoselective disulfide bond formation. A series of thiol-responsive copolymers of racemic polysarcosine-block-poly(S-ethylsulfonyl-dl-cysteine) (pSar-b-p(dl)Cys), enantiopure polysarcosine-block-poly(S-ethylsulfonyl-l-cysteine) (pSar-b-p(l)Cys), and polysarcosine-block-poly(S-ethylsulfonyl-l-homocysteine) (pSar-b-p(l)Hcy) was prepared by N-carboxyanhydride polymerization. The secondary structure of the peptide segment varies from α-helices (pSar-b-p(l)Hcy) to antiparallel ß-sheets (pSar-b-p(l)Cys) and disrupted ß-sheets (pSar-b-p(dl)Cys). When subjected to nanoprecipitation, copolymers with antiparallel ß-sheets display the strongest tendency to self-assemble, whereas disrupted ß-sheets hardly induce aggregation. This translates to worm-like micelles, solely spherical micelles, or ellipsoidal structures, as analyzed by atomic force microscopy and cryogenic transmission electron microscopy, which underlines the potential of secondary structure-driven self-assembly of synthetic polypeptides.