Polyphosphoramidates That Undergo Acid-Triggered Backbone Degradation

The direct and facile synthesis of polyphosphoramidates (PPAs) with acid-labile phosphoramidate backbone linkages are reported, together with demonstration of their hydrolytic degradability, evaluated under acidic conditions. The introduction of acid-labile linkages along the polymer backbone led to rapid degradation of the polymer backbone dependent upon the environmental stimuli. An oxazaphospholidine monomer bearing a phosphoramidate linkage was designed and synthesized to afford the PPAs via organobase-catalyzed ring-opening polymerization in a controlled manner. The hydrolytic degradation of the PPAs was studied, revealing breakdown of the polymer backbone through cleavage of the phosphoramidate linkages under acidic conditions

Two-Dimensional Controlled Syntheses of Polypeptide Molecular Brushes via <i>N</i>‑Carboxyanhydride Ring-Opening Polymerization and Ring-Opening Metathesis Polymerization

Well-defined molecular brushes bearing polypeptides as side chains were prepared by a “grafting through” synthetic strategy with two-dimensional control over the brush molecular architectures. By integrating <i>N</i>-carboxyanhydride ring-opening polymerizations (NCA ROPs) and ring-opening metathesis polymerizations (ROMPs), desirable segment lengths of polypeptide side chains and polynorbornene brush backbones were independently constructed in controlled manners. The N₂ flow accelerated NCA ROP was utilized to prepare polypeptide macromonomers with different lengths initiated from a norbornene-based primary amine, and those macromonomers were then polymerized via ROMP. It was found that a mixture of dichloromethane and an ionic liquid were required as the solvent system to allow for construction of molecular brush polymers having densely-grafted peptide chains emanating from a polynorbornene backbone, poly­(norbornene-<i>graft</i>-poly­(β-benzyl-l-aspartate)) (P­(NB-<i>g</i>-PBLA)). Highly efficient postpolymerization modification was achieved by aminolysis of PBLA side chains for facile installment of functional moieties onto the molecular brushes