Photo-induced reversible uniform to Janus shape change of vesicles composed of PNIPAM-b-PAzPy2

In this work, three kinds of vesicles are fabricated by the self-assembly of amphiphilic block copolymers (BCPs), in which the hydrophobic chains are side chain azobenzene polymers with spacers of 0, 2 and 6 methylene units, respectively. It has been found that vesicles formed by BCPs with a spacer of 0 methylene units have no photo-responsive behavior and vesicles with a spacer of 6 have a photoinduced swelling behavior under the irradiation of light at 365 nm. Unexpectedly, the vesicle formed by BCPs with a spacer of 2 shows a photo-induced reversible uniform to Janus shape change under the same irradiation. This reversible process means that a bistable shape change of the vesicle can be controlled by the switching of UV light. A UV-visible absorption spectrum and a laser-trapped Raman spectrum (LTRS) are used to investigate differences in the morphology and photo-induced behavior of these vesicles. Results have confirmed that the photo-induced Janus shape of vesicles formed by BCPs with a spacer of 2 is a metastable shape, different from the stable Janus shape of vesicles formed by BCPs with a spacer of 0. This is also testified by a two-photon confocal laser scanning microscope (CLSM). From the results it is realized that the spacer length in the hydrophobic chains of BCPs can affect the photo-induced behavior of vesicles formed by BCPs, which will be a key point in designing functional vesicles with special morphologies.