Glycopolypeptide conformations in bioactive block copolymer assemblies influence their nanoscale morphologyElectronic supplementary information (ESI) available: Spectral data for all new compounds. See DOI: 10.1039/c3sm27559k

We describe the preparation and assembly of glycosylated amphiphilic diblock copolypeptides, where the hydrophilic glycosylated segments adopt either α-helical or disordered conformations. In this study, glycosylated amphiphilic diblock copolypeptides were prepared using poly( l -leucine), poly(L), as the hydrophobic segment, and poly(α- d -galactopyranosyl- l -lysine), poly(α-gal-K), or poly(α- d -galactopyranosyl- l -cysteine sulfone), poly(α-gal-C O2 ), as the hydrophilic segment. The poly(α-gal-K) and poly(α-gal-C O2 ) segments are known to be fully α-helical (>90% at 20 °C) and fully disordered in water, respectively. We found that block copolypeptides containing galactosylated hydrophilic segments of either α-helical or disordered conformation give different assembly morphologies, where the disordered glycopolypeptide segments favor vesicle formation and also present sugar residues that can bind to biological targets. Polypeptide chain conformations were used to direct assembly of nanocarriers into desired morphologies and simultaneously introduce bioactive functionality.