Dynamic Docking and Undocking Processes Addressing Selectively the Outside and Inside of Polymersomes

Abstract

Increasing complexity and diversity of polymersomes and their compartments is a key issue for mimicking cellular functions and protocells. Thus, new challenges arise in terms of achieving tunable membrane permeability and combining it with control over the membrane diffusion process, and thus enabling a localized and dynamic control of functionality and docking possibilities within or on the surface of polymeric compartments. This study reports the concept of polymersomes with pH-tunable membrane permeability for controlling sequential docking and undocking processes of small molecules and nanometer-sized protein mimics selectively on the inside and outside of the polymersome membrane as a further step toward the design of intelligent multifunctional compartments for use in synthetic biology and as protocells. Host-guest interactions between adamantane and β-cyclodextrin as well as noncovalent interactions between poly(ethylene glycol) tails and β-cyclodextrin are used to achieve selective and dynamic functionalization of the inner and outer spheres of the polymersome membrane.

Avidin Localizations in pH-Responsive Polymersomes for Probing the Docking of Biotinylated (Macro)molecules in the Membrane and Lumen

“…42,60,63 Once the Psomes are obtained, they are crosslinked for 3 min of UV irradiation, if not otherwise mentioned, to obtain robust and pH-stable polymeric vesicles (Figure 1 and Table 1). 42,43,60,63,64 In situ and post loading method was used to fabricate Avidin-Psomes. In situ loading describes the encapsulation of cargo during the formation of Psomes, while post loading implies the encapsulation and/or interaction of cargo by/with Psomes after their formation (Figure 1).…”

“…Known from a previous study that glycodendrimer b7 is suited to cross the membrane. 43 Generally, the post loading approach for Avidin-Psomes leads to a successful loading of all kinds of biotinylated (macro)molecules. Thus, this study emphasizes an alternative to the in situ loading process of Psomes.…”

The chemistry of cross-linked polymeric vesicles and their functionalization towards biocatalytic nanoreactors

“…One of the cross-linked polymersomes, which have been studied very intensively over the last 10 years, are the photo-cross-linked and pH sensitive ones from Voit et al first reported in 2011 [59]. We will now focus on this polymer and the application of the corresponding polymersomes as functional nanoreactors as single compartment and novel contribution in the field of multicompartments [9,17,[60][61][62][63][64][65][66][67].…”

Modular Approach for the Design of Smart Polymeric Nanocapsules

“…Common linker groups for covalent binding approaches are amine moieties, carboxyl groups, azido, or alkyne groups to utilize esterification and click chemistries on the nanocapsule surface. In addition, non‐covalent attachments such as biotin‐streptaviding binding, adamantane‐cyclodextrin inclusion and nitrilotiriacetic acid (NTA) metal complexations are also useful functionalization tools for producing smart nanocapsules.…”

“…Adamantane functional polymersomes with PDIEM crosslinker units were also reported. Since the corresponding functionalities placed at both inner and outer region of the bilayer membrane as proposed by self‐assembly principles, the post‐conjugation with cyclodextrin modified glycodendrimers was shown by tuning the membrane permeability as open and closed states through the trigger of pH‐stimulus …”