The synthesis of anisotropic branched gold nanoparticles remines to be challenging as their arm number and arm length could hardly be controlled, greatly limited their biomedical application. We report the large-scale high-yield synthesis of PdCu@Au tripods, and, for the first time, their two-photon luminescence properties with quantitative characterization of the two-photon action cross section as well as quantum yield. By introducing nitrogen protection to the synthesis of the PdCu bimetallic cores, this approach eliminates the oxidative etching caused by oxygen in the air, providing a 2.5 times higher synthetic yield of 70.4 %, which enables the large-scale preparation of PdCu@Au at ca. 380 mg per batch. By the conformal coating of PdCu bimetallic cores, the PdCu@Au tripods are prepared with a purity of >90 % with average arm length 45.3 ± 5.6 nm that is ideal for biomedical applications. The PdCu@Au tripods demonstrate a much brighter two-photon luminescence than that from Au nanorods, with a 3.6 ± 0.9 times larger two-photon action cross section and comparable quantum yield. Our result also shows the two-photon luminescence property of PdCu@Au tripods could be tuned by their distinct localized surface plasmon resonance property and, in turn, the different amount of Au coating. This tunability could be explained by the recently-proposed two-step excitation mechanism of two-photon luminescence in Au nanoparticle. The folate-targeted in vitro two-photon luminescence imaging of MDA-MB-435 breast cancer cells were also demonstrated to show the great potential using PdCu@Au tripods as novel multi-functional platforms for cancer theranostics.
Two-photon luminescence properties of gold nanorods
