Gold nanorods with phase-changing polymer corona for remotely near-infrared-triggered drug release

Herein, we report a new drug-delivery system (DDS) that is comprised of a near-infrared (NIR)- light-sensitive gold-nanorod (GNR) core and a phase-changing poly(e-caprolactone)- b-poly(ethylene glycol) polymer corona (GNR@PCL-b-PEG). The underlying mechanism of the drugloading and triggered-release behaviors involves the entrapment of drug payloads among the PCL crystallites and a heat-induced phase change, respectively. A low premature release of the pre-loaded doxorubicin was observed in PBS buffer (pH 7.4) at 37 °C (<10% of the entire payload after 48 h). However, release could be activated within 30 min by conventional heating at 50 °C, above the Tm of the crystalline PCL domain (43.5 °C), with about 60% release over the subsequent 42 h at 37 °C. The NIR-induced heating of an aqueous suspension of GNR@PCL-b- PEG under NIR irradiation (802 nm) was investigated in terms of the irradiation period, power, and concentrationdependent heating behavior, as well as the NIR-induced shape-transformation of the GNR cores. Remotely NIR-triggered release was also explored upon NIR irradiation for 30 min and about 70% release was achieved in the following 42 h at 37°C, with a mild warming (<4 °C) of the surroundings. The cytotoxicity of GNR@PCL-b-PEG against the mouse fibroblastic-like L929 cell-line was assessed by MTS assay and good compatibility was confirmed with a cell viability of over 90% after incubation for 72 h. The cellular uptake of GNR@PCL-b-PEG by melanoma MEL-5 cells was also confirmed, with an averaged uptake of 1250 ( ± 110) particles cell-1 after incubation for 12 h (50 mg mL-1). This GNR@PCL-b-PEG DDS is aimed at addressing the different requirements for therapeutic treatments and is envisaged to provide new insights into DDS targeting for remotely triggered release by NIR activation.