Near-Infrared-Triggered Reversible Transformations of Gold Nanorod-Laden Lipid Assemblies: Implications for Cellular Delivery

Robust drug and gene delivery systems require innovative methods to control payload release and tune delivery efficiency. The most promising delivery materials are lipid-based and their efficiency often hinges on structural transformations activated by endogenous pH changes. Exogenously driving phase transitions in lipid assemblies is a tantalizing idea that could lead to better control of cargo release dynamics. Multiple reports have demonstrated phase transitions induced in lipid systems, achieved via plasmonic heating of entrained gold nanorods. However, undesirable nonlocalized heating is common due to the size mismatch between the nanorods and the lipid architecture in these systems. Lipid assemblies often exhibit lattice dimensions of just a few nanometers, rendering gold particles challenging to integrate due to their incommensurate sizes, especially in lipid nanoparticle or colloidal forms. We investigate these processes using a judiciously chosen ternary lipid system with entrained small gold nanorods that undergoes transitions between bicontinuous cubic and inverse hexagonal phases on exposure to near-infrared light. Utilizing small-angle X-ray scattering alongside electron reconstruction, we show that gold nanorods integrate into the lipid assembly core lattice by colocalizing in the water nanochannels. We also found that plasmonically activated transformations occur in a couple of minutes and are reversible.