Macromolecular self-assembly is attracting increasing scientific interest in polymer science. One of the most studied assemblies are stimuli-responsive polymersomes that can convert specific environmental changes to functional outputs based on a physicochemical adjustment of their chain structures and membrane properties. These unique features have made it possible to design and construct smart self-assembled architectures for various emerging applications such as polymeric nanocapsules for tunable delivery vehicles. Moreover, stimuli-responsive polymersomes possess the ability to encapsulate active enzymatic species which makes them well suited as nanoreactors capable of performing enzymatic reactions. In this regard, this class of smart polymersomes provides an avenue to apply synthetic polymer systems as biomimetic materials. Here, in this review, we will highlight recent progress with regard to stimuli-responsive polymer vesicles/nanocapsules and their development towards intelligent nanocarriers and nanoreactors or artificial organelles.

Here we present the development of self-regulated “breathing” polymersome nanoreactors that show temporally programmable biocatalysis induced by a chemical fuel. pH-sensitive polymersomes loaded with horseradish peroxidase (HRP) and urease were developed. Addition of an acidic urea solution (“fuel”) endowed the polymersomes with a transient size increase and permeability enhancement, driving a temporal “ON” state of the HRP enzymatic catalysis; subsequent depletion of fuel led to shrinking of the polymersomes, resulting in the catalytic “OFF” state. Moreover, the nonequilibrium nanoreactors could be reinitiated several cycles as long as fuel was supplied. This feedback-induced temporal control of catalytic activity in polymersome nanoreactors provides a platform for functional nonequilibrium systems as well as for artificial organelles with precisely controlled adaptivity.

Responsive polymer interfacial materials are ideal candidates for controlling surface wetting behavior. Here we developed smart nanostructured electrospun polymer membranes which are capable of switching oil/water wettability using CO2 as the trigger. In particular, the combination of CO2 -responsiveness and porous nanostructure enables the as-prepared membranes to be used as a novel oil/water on-off switch. We anticipate that the promising versatility and simplicity of this system would not only open up a new way of surface wettability change regulation by gas, but also have obvious advantages in terms of highly controlled oil/water separation and CO2 applications.

Adaptive polymersome systems have gained much interest in a wide variety of research fields, ranging from cell mimics to nanomedicine, because of their high stability, tunable shape and size. Furthermore, polymersomes can be effectively transformed into nanoreactors via the incorporation of catalytic species. By employing polymersomes which are adaptive in structure and function the features of polymersome nanoreactors can be even further extended. In this review, we focus on recent impressive developments of smart polymersomes as functional nanoreactors with an emphasis on the type of adaptivity that is installed, which includes intrinsic permeability, stimuli‐responsiveness and self‐adaptivity. Moreover, particular attention is given to the utility of polymersome nanoreactors in vitro and in vivo, which paves the next step forward towards the engineering of artificial organelles as therapeutic materials.

Photodynamic therapy (PDT) is an effective noninvasive therapeutic method that employs photosensitizers (PSs) converting oxygen to highly cytotoxic singlet oxygen ( 1 O 2 ) under light irradiation. The conventional PDT efficacy is, however, compromised by the nonspecific delivery of PSs to tumor tissue, the hypoxic tumor microenvironment, and the reduction of generated 1 O 2 by the intracellular antioxidant glutathione (GSH). Herein, an intelligent multifunctional synergistic nanoplatform (CMGCC) for T 1 -weighted magnetic resonance (MR) imaging-guided enhanced PDT is presented, which consists of nanoparticles composed of catalase (CAT) and manganese dioxide (MnO 2 ) that are integrated within chlorin-e6-modified glycol chitosan (GC) polymeric micelles. In this system, (1) GC polymers with pH-sensitive surface charge switchability from neutral to positive could improve the PS accumulation within the tumor region, (2) CAT could effectively reoxygenate the hypoxic tumor via catalyzing endogenous hydrogen peroxide to O 2 , and (3) MnO 2 could consume the intracellular GSH while simultaneously producing Mn 2+ as a contrast agent for T 1 -weighted MR imaging. The CMGCC particles possess uniform size distribution, well-defined structure, favorable enzyme activity, and superior 1 O 2 generation ability. Both in vitro and in vivo experiments demonstrate that the CMGCC exhibit significantly enhanced PDT efficacy toward HeLa cells and subcutaneous HeLa tumors. Our study thereby demonstrates this to be a promising synergistic theranostic nanoplatform with highly efficient PDT performance for cancer therapy.