Scheme 1.

Synthesis of nanostars and chain extension cycle: a) Tris‐hydroxy terminated octagol‐nanostar 1 is converted to Wang‐type, 4, and Rink, 6, nanostar; the Wang anchor is loaded by slow esterification with the first AA before entering the synthesizer. b) Using the Fmoc strategy, peptide‐nanostars are grown in a three‐step cycle of coupling, Fmoc removal, and diafiltration, then removed from the synthesizer for global deprotection.