Biomembrane curvature formation has long been observed to be essential in the change of membrane morphology and intracellular processes. The significant importance of curvature formation has attracted scientists from different backgrounds to study it. Although magnificent progress has been achieved using liposome models, the instability of these models restrict further exploration. Here, we report a new approach to mimic biomembrane curvature formation using polymersomes as a model, and poly(N-isopropylacrylamide) to induce the local curvature based on its co-nonsolvency phenomenon. Curvatures form when poly(N-isopropylacrylamide) becomes hydrophobic and inserts into the membrane through solvent addition. The insertion area can be fine-tuned by adjusting the poly(N-isopropylacrylamide) concentration, accompanied by the formation of new polymersome-based non-axisymmetric shapes. Moreover, a systematic view of curvature formation is provided through investigation of the segregation, local distribution and dissociation of inserted poly(N-isopropylacrylamide). This strategy successfully mimicks biomembrane curvature formation in polymersomes and a detailed observation of the insertion can be beneficial for a further understanding of the curvature formation process. Furthermore, polymer insertion induced shape changing could open up new routes for the design of non-axisymmetric nanocarriers and nanomachines to enrich the boundless possibilities of nanotechnology.

Covalent and non-covalent molecular binding are two strategies to tailor surface properties and functions. However, the lack of responsiveness and requirement for specific binding groups makes spatiotemporal control challenging. Here, we report the adaptive insertion of a hydrophobic anchor into a poly(ethylene glycol) (PEG) host as a non-covalent binding strategy for surface functionalization. By using polycyclic aromatic hydrocarbons as the hydrophobic anchor, hydrophilic charged and non-charged functional modules were spontaneously loaded onto PEG corona in 2 min without the assistance of any catalysts and binding groups. The thermodynamically favourable insertion of the hydrophobic anchor can be reversed by pulling the functional module, enabling programmable surface functionalization. We anticipate that the adaptive molecular recognition between the hydrophobic anchor and the PEG host will challenge the hydrophilic understanding of PEG and enhance the progress in nanomedicine, advanced materials and nanotechnology.

Functionalizing polymersomes remains a challenge due to the limitation in reaction conditions applicable to the chemistry on the surface, hindering their application for selective targeting. In order to overcome this limitation, functionalization can be introduced right before the self-assembly. Here, we have synthesized a library (32 examples) of PEG-b-PS and PEG-b-PDLLA with various functional groups derived from the amine-functionalized polymers, leading to functionally active polymersomes. We show that polymersome formation is possible via the general method with all functionalized groups and that these handles are present on the surface and are able to undergo reactions. Additionally, this methodology provides a general synthetic tool to tailor the functional group of the polymersome right before self-assembly, without limitation on the reaction conditions.

Organophosphorus-catalyzed Staudinger ligation between carboxylic acids and azides in the presence of phenylsilane reductant produces amides. NMR-based mechanistic investigations revealed that the catalytic Staudinger ligation does not proceed via reduction of phosphine oxide but rather via reduction of iminophosphorane, which can subsequently undergo several transformations to produce the amide product.

The design of stable, inert, and permeable nanoreactors remains a challenge due to the additives required to create a cross-linked network, limiting their potential for catalysis. Polymersomes are nanovesicles self-assembled from amphiphilic block copolymers that can act as nanoreactors by encapsulating catalysts. A major restriction toward their use is their stability and reduced permeability. In order to overcome this, polymersome membranes can be cross-linked to retain their shape and function. Here, we report the synthesis of a PEG- b -P(S- co -4-VBA) polymer, which can self-assemble into polymersomes and subsequently be cross-linked using UV light. We demonstrate that these polymersomes are stable over a long period of time in various organic solvents, that incorporation of functional handles on their surface is possible, and that they are able to undergo reactions. Additionally, we show that co-assembly with up to 40% PEG- b -PS present results in the formation of pores in the membrane structure, which allows for the structure to be used as a nanoreactor. By encapsulating a platinum nanocatalyst, we are able to catalyze the depropargylation of a small coumarin substrate, which was able to enter and leave the porous nanoreactor.

In recent years various polymeric vesicles have been reported that show promising results for drug delivery applications, nanomotors and/or nanoreactors. These polymeric vesicles can be assembled from many different materials and various coupling reactions have been applied for functionalization of the vesicles. However, the designs reported are still rather simple, as it is challenging to mimic biological complex systems. In this review we focus on the properties of widely used hydrophobic polymers to better understand polymersome properties for various applications. Examples are shown of how researchers have used and modulated block‐copolymers and their properties to their advantage. Furthermore, an overview of possible end group functionalizations of nanoparticles is reported, giving insight in recent developments of smart nanoparticles for biomedical applications.

An adaptive surface that can sense and respond to environmental stimuli is integral to smart functional materials. Here, we report pH-responsive anchoring systems onto the poly(ethylene glycol) (PEG) corona of polymer vesicles. The hydrophobic anchor, pyrene, is reversibly inserted into the PEG corona through the reversible protonation of its covalently linked pH-sensing group. Depending on the pK a of the sensor, the pH-responsive region is engineered from acidic to neutral and basic conditions. The switchable electrostatic repulsion between the sensors contributes to the responsive anchoring behavior. Our findings provide a new responsive binding chemistry for the creation of smart nanomedicine and a nanoreactor.

The surface area of anisotropic polymeric assemblies is a critical parameter concerning their properties. However, it is still a grand challenge for traditional techniques to determine the surface area. Here, a molecular probe loading (MPL) method is developed to measure the surface area of anisotropic polymersomes in the shape of tube, disc, and stomatocyte. This method uses an amphiphilic molecular probe, comprising hydrophobic pyrene as the anchor and hydrophilic tetraethylene glycol (EG4) as the float. The surface area of spherical polymersomes determined by dynamic light scattering is quantitatively correlated with the loading amount of probes, allowing the calculation of the average separation distance between the loaded probes. With the separation distance, we successfully determine the surface area of anisotropic polymersomes by measuring the loading amount. We envision that the MPL method will assist in the real‐time surface area characterization, enabling the customization of functions.