Photo- and pH-responsive giant vesicles: harnessing the properties of surface-active ionic liquids in designing dual-responsive catanionic vesicles

Abstract

Considerable interest in designing multi-responsive soft materials for diverse applications is leading to the development of systems that are embedded with functional groups with stimuli-responsive characters. Surface-active ionic liquids (SAILs) with an ability to form various structural aggregates represent an interesting candidate for designing soft materials with stimuli-responsive characters. Embedding photo-responsive moieties into SAILs with existing pH-responsive properties can unlock a broader range of potential uses. Herein, we prepared photo- and pH-responsive catanionic giant vesicles (GVs) through a synergetic interaction between the pH-responsive choline oleate ([Ch][Ol]) and photo-responsive (4-methyl-4-(2-(octyloxy)-2-oxoethyl)) morpholin-4-ium(E)-4-((4-(dimethylamino) phenyl) diazinyl) benzenesulfonate ([C₈EMorph][MO]). The photo-responsiveness in the GVs was introduced through [C₈EMorph][MO], which shows E–Z isomerisation under 460 nm light irradiation, whereas the pH-responsive character was obtained through [Ch][Ol]. We used absorbance measurements complimented with a computational study to characterize the photo-responsive behaviour. Irradiating the GVs with light of suitable wavelength and changing the pH of the system altered the behaviour of the aggregates. Small-angle neutron scattering (SANS) analysis showed that, before irradiation, the size of the bilayer thickness of the GVs was 28 Å and after irradiation it was increased to 31 Å, leading to an increment in the overall size of the GVs. This was due to the formation of Z-[C₈EMorph][MO] after irradiation, which leads to a slight alteration in the interactions between both SAILs. Moreover, the change in pH of the vesicles caused alterations in the size and shape of the vesicles, as confirmed through the SANS analysis. The stability of the GVs in terms of temperature, dilution, and time was analysed to characterise the GVs for practical applications. The insights gained from this study could be valuable for developing materials for these applications such as probes, cargo carriers, and microreactors in future.