Chitosan-Modified Stable Colloidal Gold Nanostars for the Photothermolysis of Cancer Cells

The preparation and properties of plasmonic gold nanostars (Au NSs) modified with a biopolymer chitosan are reported. The colloidal stability of Au NSs at the physiological pH of 7.5 and their performance in the photothermolysis of cancer cells in vitro were compared with those of gold nanorods (Au NRs). The optical characteristics of chitosan-modified Au NSs dispersed in a medium with pH = 7.5 had higher stability than those of chitosan-capped NRs because of the slower aggregation of NSs. At pH = 7.5, the chitosan-modified Au NRs formed aggregates with highly nonuniform sizes. On the other hand, Au NSs formed small chain-like clusters, in which individual NSs were connected to one another, preferably via association of branches with central cores. It is possible that the difference in areal charge density at these parts of NSs is responsible for their preferred association. Flow cytometry analysis showed the relatively nonequivalent distribution of the chitosan-capped Au NRs across the cell line compared with that of Au NSs because of the fast and nonuniform aggregation of NRs. An in-vitro photothermolysis experiment on J5 cancer cells showed that energy fluences of 23 and 33 mJ/cm2 are necessary to cause complete death of J5 cells incubated with 4 μg/mL chitosan-capped Au NSs and NRs, respectively. When chitosan was used as a surface-capping agent, the Au NSs exhibited higher colloidal stability at the physiological pH than the NRs and lower energy fluence necessary for cell photothermolysis because of more uniform cellular uptake.