Most of reported polymeric light-responsive nanocarriers make use of UV light to trigger morphological changes and the subsequent release of encapsulated cargoes. Moving from UV- to visible-responsive units is interesting for the potential biomedical applications of these materials. Herein we report the synthesis by ring opening polymerization (ROP) of a series of amphiphilic diblock copolymers, into which either UV or visible responsive azobenzenes have been introduced via copper(I) catalyzed azide-alkyne cycloaddition (CuAAC). These copolymers are able to self-assemble into spherical micelles or vesicles when dispersed in water. The study of the response of the self-assemblies upon UV (365 nm) or visible (530 or 625 nm) light irradiation has been studied by Transmission Electron Microscopy (TEM), Cryogenic Transmission Electron Microscopy (Cryo-TEM), and Dynamic Light Scattering (DLS) studies. Encapsulation of Nile Red, in micelles and vesicles, and Rhodamine B, in vesicles, and its light-stimulated release has been studied by fluorescence spectroscopy and confocal microscopy. Appreciable morphological changes have been induced with green light, and the subsequent release of encapsulated cargoes upon green light irradiation has been confirmed.

The work assesses the performance of nanocarriers from amphiphilic block copolymers with functional azobenzene or coumarin moieties for delivery of paclitaxel. Placlitaxel was encapsulated by the nanoprecipitation method. Characterisations were performed by DLS, TEM, Zeta potential and HPLC. Cell viability was investigated in HeLa and Huh-5-2-cell lines. Coumarin-containing polymeric micelles (D_h = 26 ± 2 nm, PDI = 0.28, ζ = ‒22.9 ± 3.6 mV) with 11.2 ± 0.5%w/w drug loading showed enhanced cytotoxicity in HeLa cells (IC50 < 0.02 nM) compared to free paclitaxel (IC50 = 0.17 ± 0.02 nM). Azobenzene-containing polymeric vesicles (D_h = 390 ± 20 nm, PDI = 0.24, ζ = ‒33.2 ± 5.0 mV) with a 6.8 ± 0.4%w/w drug loading showed increased cytotoxicity under 530 nm light (IC50 = 0.0114 ± 0.00033 nM) in HeLa cells due to a stimulated delivery of paclitaxel. Effectivity of these block copolymers as paclitaxel nanovectors and light stimulated release has been demonstrated.