Synthesis and pH-Responsive “Schizophrenic” Aggregation of a Linear-Dendron-Like Polyampholyte Based on Oppositely Charged Polypeptides

Abstract

A novel linear-dendron-like polyampholyte, poly(L-lysine)-b-D2-poly(L-glutamic acid) [PLL-b-D2-(PLGA)4], where D2 is the second generation of poly(amido amine), was prepared by hydrolyzing poly(ε-benzyloxycarbonyl-L-lysine)-b-D2-poly(γ-benzyl-L-glutamate) copolymer which was synthesized via a combination of ring-opening polymerization and click chemistry. The pH-responsive self-assembly behaviors of PLL-b-D2-(PLGA)4 were investigated in detail. It is found that PLL-b-D2-(PLGA)4 can self-assemble into PLGA-core aggregates at acidic pH and PLL-core aggregates at alkaline pH, which was accompanied with the coil-to-helix conformational transition of PLGA and PLL segments, respectively. The self-assembled aggregates with various morphologies, such as large compound micelles, worm-like micelles, large compound vesicles, simple vesicles, and rigid tubular structures have been obtained in "schizophrenic" aggregation process with simply increasing the solution pH. The hierarchical assembled fractal structures of PLL-b-D2-(PLGA)4 were observed during the solvent evaporation at high pH value.

Functional aqueous assemblies of linear‐dendron hybrids

“…These materials are particularly attractive due to the monodispersity of the dendron component, its multivalent periphery, and the unique architecture imparted by the coupling of the globular architecture of the dendron component with rod or coil‐shaped linear oligomers and polymers. The approach has even been extended to other structures that couple linear and dendritic fragments including dendronized linear polymers, dendronized star polymers, and LD hybrids with linear polymers attached to the dendron periphery …”

Covalent Defects Restrict Supramolecular Self-Assembly of Homopolypeptides: Case Study of β2-Fibrils of Poly-L-Glutamic Acid

“…[11]–[12]), components of tumor targeting gene carriers (e.g. [13]), pH-switchable multi-topology vesicles [14], and multilayer films (in complexes with polylysine) for enhancement of cell adhesion (e.g. [15]).…”

Physicochemical Properties of Hydrophobically Modified Polymeric Betaines and of Their Langmuir‐Blodgett Films

“…[24,25] In aqueous KOH solution the carboxylic groups are in ionized state and responsible for polyelectrolyte behavior. According to commonly accepted approach, the hydrophobic groups in aqueous solution will tend to form intramacromolecular micelle or inter-macromolecular vesicular structures stabilized by hydrophobic interactions of long alkyl groups as shown in Figure 3.…”