Accelerated Preparation of Polypeptides and Related Hybrid Materials from a Disintegrable Initiator Array with Masked Carbenium Precursors

We report a disintegrable initiator array for the synthesis of well-defined polypeptides using raw N-carboxyanhydride monomers that are purified in situ. Free polypeptides can be obtained through the superfast disintegration of the initiation system after polymerization, simultaneously revealing unmasked, highly active benzhydrylium (BHD) ends for efficient conjugation. The polypeptide synthesis and conjugation combined can be accomplished in 3.5 h starting from amino acids. The high activity of BHD on the polypeptides can be utilized to construct complex hybrid materials with ease, shown in two proof-of-concept examples. The BHD-capped polypeptide presents the first reported case of the polymer being used as a dopant, which grafts onto and dopes poly(3-hexylthiophene) directly to give biocompatible, conductive polypeptide brushes. In addition, such polypeptides can directly decorate two-dimensional MoS2 nanosheets for significantly improved dispersibility and activity as a heterogeneous catalyst.

Automated summary

In this study, a disintegrable initiator array was developed for the synthesis of well-defined polypeptides using purified N-carboxyanhydride monomers. The fast disintegration of the initiation system after polymerization allowed for the efficient conjugation of polypeptides. The high activity of the benzhydrylium ends on the polypeptides enabled the construction of complex hybrid materials.