New macromolecular self-assembling building blocks star polypeptide-b-polyhedral oligomeric silsesquioxane (POSS) copolymers were synthesized from octa-azido functionalized POSS (OVBN3-POSS) with alkyne-poly(gamma-benzyl-L-glutamate) (alkyne-PBLG) via a click reaction The incorporation of PUSS units at the core of PBLG moieties plays an important role allowing intramolecular hydrogen bonding between the POSS and PBLG units to enhance the alpha-helical conformations in the solid state based on Fourier Transform Infrared spectroscopy (FTIR) solid state nuclear magnetic resonance (NMR) and wide-angle X-ray diffraction (WAXD) analyses (C) 2010 Elsevier Ltd All rights reserved