Controlled ring-opening polymerization of N-(3-tert-butoxy-3-oxopropyl) glycine derived N-carboxyanhydrides towards well-defined peptoid-based polyacids

Abstract

Polypeptoids bearing carboxylic acid groups on the N-substituent are useful building blocks for the construction of peptidomimetic supramolecular assemblies with stimuli-responsive properties.

Polypeptoids and Peptoid–Peptide Hybrids by Transition Metal Catalysis

“…For NMOE NNCA at an [M]:[I] of 200:1 in THF at 50 °C, all the monomer was consumed within 48 h. However, polymerization of NBnGlu NNCA took nearly 5 days to complete under the same conditions. Interestingly, Zhang et al 37 found NMOE NNCA polymerized more slowly than N-(3-tertbutoxy-3-oxopropyl) NNCA; however, their system was in low dielectric toluene with primary amines. We attempted polymerization in toluene; however, solubility of these materials was poor and bimodal SEC traces were observed.…”

“…Glutamic acid analogues have been incorporated into short peptoids by the submonomer synthesis method, but to our knowledge, only one example of a high-MW polypeptoid bearing acid groups has been demonstrated. This study used primary amine initiation to polymerize N -(3-tert-butoxy-3-oxopropyl) NNCA . Excellent control over chain length in homopolymers prepared in toluene was demonstrated.…”

“…This study used primary amine initiation to polymerize N-(3-tertbutoxy-3-oxopropyl) NNCA. 37 Excellent control over chain length in homopolymers prepared in toluene was demonstrated. However, the authors note the method is limited due to a transamidation termination pathway with certain monomers.…”

Self‐assembled free‐floating nanomaterials from sequence‐defined polymers

“…Notably, Zhang et al have made significant progress toward modified N‐carboxyanhydride ring opening polymerization reactions, allowing for the rapid polymerization of polypeptoids with narrow molecular weight distributions 70 . Using N‐substituted N‐carboxyanhydrides and a benzyl amine initiator, Zhang et al have synthesized both linear and cyclic 71 amphiphilic block copolypeptoids, which self‐assemble into rigid nanorods and nanosheets 72,73 …”

“…Notably, Zhang et al have made significant progress toward modified N-carboxyanhydride ring opening polymerization reactions, allowing for the rapid polymerization of polypeptoids with narrow molecular weight distributions. 70 Using N-substituted N-carboxyanhydrides and a benzyl amine initiator, Zhang et al have synthesized both linear and cyclic 71 amphiphilic block copolypeptoids, which self-assemble into rigid nanorods and nanosheets. 72,73 Further studying the interactions determining polymer structure in solution, Li et al analyzed the combined effects of hydrophobicity, π-π stacking and chain mobility by varying poly(N-(2-phenylethyl)glycine (Npe) chain length from 4 to 24 units in PEG-b-Npe diblock copolymers.…”