group [26] who prepared an O 2 -"breathing" vesicle upon alternately purging with O 2 and Ar. Noteworthy, SRPVs with dual or multiresponsiveness have attracted enormous attention because multiresponsive systems can greatly improve their versatility in a variety of applications. [31][32][33][34] In contrast to lots of contact-triggered stimuli responses, light is a contact-free and environment-friendly stimulus. [35] Therefore, light is one of the most common triggers to realize remote controlled release. [36,37] So far, to the best of our knowledge, combining light responsiveness with CO 2 and O 2 -responsiveness to prepare triple-responsive vesicles has not yet been explored. A further challenge of such a vesicular system, besides the synthetic challenge, is how to maintain its "breathing"-responsive behavior instead of causing a sharp disassembly or a vesicle-tomicelle transition upon external stimuli (CO 2 , O 2 , and light). Usually, apart from cross-linked vesicles, a suitable polymer structure is an efficient strategy to endow SRPVs with a swelling responsive behavior to achieve a tunable membrane permeability. [15,38] In the present work, we report on the first CO 2 -, O 2 -, and lightresponsive vesicles from an amphiphilic triblock copolymer. To fabricate "breathable" vesicles, the work from Feng's group was referred to for the design of suitable chemical structures of triblock copolymers. [38] In this case, poly(N,N-dimethylamino ethyl methacrylate-co-2,2,2-trifluoroethyl methacrylate) (P(DMAEMAco-TFEMA)) with CO 2 and O 2 -responsiveness was chosen as the middle block, and poly(4-(4-methoxy-phenylazo)phenoxy methacrylate) (PMEPPMA) with light responsiveness was chosen as the end block. Due to the rigid structure of PMEPPMA, selfassembled vesicles can exhibit only swollen transitions upon CO 2 and O 2 stimulation, rather than switching to micelles or dissociating into unimers. Based on this suitable chemical structure and stimuli responsiveness, such vesicles present a "breathing" behavior under external stimulation (see Scheme 1), indicating the membrane permeability of such vesicles can be controlled via a single stimulus or various stimuli combinations. Furthermore, using Calcein as a model, it is demonstrated that the vesicles with their altering membrane permeability could serve as potential nanocarriers for an efficient rate-tunable controlled drug release.
Results and DiscussionHerein, a CO 2 -, O 2 -, and light-responsive amphiphilic triblock copolymer, poly[(ethylene glycol)methyl ether]-block-poly(N,Ndimethylamino ethyl methacrylate-co-2,2,2-trifluoroethyl