Self-assembly of photoresponsive azo-containing phospholipids with a polar group as the tail

Abstract

Vesicles or micelles prepared from amphiphiles with azobenzene (Az) moieties and long alkyl chains have attracted much attention in drug delivery systems. To induce release behavior from smart carriersvia trans-cisphotoisomerization of theAzgroups, UV light exposure is typically used, but it can damage DNA and hardly penetrates cells. In this paper,Az-containing phospholipids without long alkyl tails were designed and synthesized; in these compounds, the end group of theAzmoiety was substituted with a -NO2and -OCH3group (abbreviatedN6andM6, respectively).N6self-assembled into H-aggregates with an interdigitated bilayered structure in water through the antiparallel orientation due to π-π interactions of theAzgroup, the attractive van der Waals forces, and the interactions and bending behavior of the phosphocholine groups. Vesicles showing visible light stimuli-responsive behavior were obtained by mixingN6andM6, and the release of encapsulated calcein was triggered by visible light.