Dynamic actuation of glassy polymersomes through isomerization of a single azobenzene unit at the block copolymer interface

Abstract

Nature has engineered exquisitely responsive systems where molecular-scale information is transferred across an interface and propagated over long length scales. Such systems rely on multiple interacting, signalling and adaptable molecular and supramolecular networks that are built on dynamic, non-equilibrium structures. Comparable synthetic systems are still in their infancy. Here, we demonstrate that the light-induced actuation of a molecularly thin interfacial layer, assembled from a hydrophilic- azobenzene -hydrophobic diblock copolymer, can result in a reversible, long-lived perturbation of a robust glassy membrane across a range of over 500 chemical bonds. We show that the out-of-equilibrium actuation is caused by the photochemical trans-cis isomerization of the azo group, a single chemical functionality, in the middle of the interfacial layer. The principles proposed here are implemented in water-dispersed nanocapsules, and have implications for on-demand release of embedded cargo molecules.

Design of Colloidally Stable and Non‐Toxic Petox‐Based Polymersomes for Cargo Molecule Encapsulation

“…The ratio of R g / R h is a morphologic assessment which is used to distinguish the shape of the polymeric assemblies . When the R g / R h ratios of PEtOx‐ b ‐PLA self‐assemblies evaluated, it is found to be between 0.91–0.93 which are in accordance with previous findings and fits to the theoretical value (1.0) for vesicles…”

Programmed supramolecular nanoassemblies: enhanced serum stability and cell specific triggered release of anti-cancer drugs

“…[21][22][23][24][25][26][27][28][29][30] In dendrimers, the major problems are insolubility and non-degradability, whereas in small moleculebased assemblies, the major drawbacks are high critical aggregation concentrations (CAC) and low inherent stabilities. Although polymer and dendrimer-based assemblies have low CAC, it is very challenging to maintain the stability of the nanoassemblies like micelles, 23,[31][32][33][34][35] vesicles 24,[36][37][38][39] and liposomes [40][41][42][43] made of polymers, dendrimers or small molecules in the vascular system. Due to the dilution effect in a large volume of blood serum, nanoassemblies disassemble and eventually release guest molecules in undesired locations.…”

Modular Design of Stimuli‐Responsive Supramolecular Nanocarriers Based on Pro‐Guest Strategy

“…or external stimuli (photo‐irradiation, etc.) . It is desired to develop a modular design strategy to introduce variable stimuli‐responsive types with similar nanocarrier size, morphology and cargo loading capability.…”