Hayakawa Yutaro, Furuya Masato, Tahara Hironobu, Kosuge Yasuhiro, Kimura Tsuyoshi, Sugawa Kosuke, Otsuki Joe
Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, Chiyoda, Tokyo, 101-8308, Japan.
Graduate School of Engineering, Nagasaki University, Bunkyo, Nagasaki, 852-8521, Japan.
Nanoscale Res Lett. 2022 Jun 23;17(1):60. doi: 10.1186/s11671-022-03697-1.
Although plasmonic palladium (Pd) nanospheres are thermodynamically stable and have high photothermal conversion due to the free and bound electron coupling associated with the intrinsic high interband transition, they have not attracted attention as a photothermal conversion material for next-generation photothermal cancer therapy. This is because the Pd nanospheres generate the localized surface plasmon resonance (LSPR) intrinsically in the ultraviolet region, which is far away from the biological transparent window (750-900 nm). In this study, we controlled the LSP wavelength of Pd nanospheres by coating with high refractive index TiO shells taking advantage of the Pd LSPR which is highly sensitive to changes in the local refractive index around the nanospheres. Our calculations indicated that the absorption cross section at 808 nm (corresponding to the wavelength used for photothermal treatment) was increased by 4.5 times by redshifting the LSPR and increasing the extinction intensity associated with the coating with TiO shell. Experiments confirmed the theoretical prediction in that the LSPR of the synthesized Pd nanospheres with a diameter of 81 nm was significantly redshifted by coating with amorphous TiO shell, resulting in significant large extinction intensity at 808 nm. The photothermal conversion efficiency was estimated to be 50%. In vitro cell tests, HeLa cells incubated with 100-300 μg/mL TiO-coated Pd nanospheres were efficiently killed by irradiating 808 nm laser (1.8 W) even though the nanospheres with the same concentrations showed little cytotoxicity. These results indicate that the Pd nanospheres coated with high refractive index shells can be promising as a photothermal therapy agent.
尽管等离子体钯(Pd)纳米球在热力学上是稳定的,并且由于与本征高带间跃迁相关的自由电子和束缚电子耦合而具有高光热转换性能,但它们尚未作为下一代光热癌症治疗的光热转换材料受到关注。这是因为Pd纳米球在紫外区域固有地产生局域表面等离子体共振(LSPR),该区域远离生物透明窗口(750 - 900 nm)。在本研究中,我们利用对纳米球周围局部折射率变化高度敏感的Pd LSPR,通过涂覆高折射率TiO壳来控制Pd纳米球的LSP波长。我们的计算表明,通过使LSPR红移并增加与TiO壳涂层相关的消光强度,808 nm(对应于光热处理所用波长)处的吸收截面增加了4.5倍。实验证实了理论预测,即通过用非晶TiO壳涂层,合成的直径为81 nm的Pd纳米球的LSPR显著红移,导致在808 nm处有显著大的消光强度。光热转换效率估计为50%。在体外细胞测试中,用100 - 300μg/mL TiO包覆的Pd纳米球孵育的HeLa细胞,即使相同浓度的纳米球显示出很小的细胞毒性,但通过照射808 nm激光(1.8 W)也能被有效杀死。这些结果表明,涂覆有高折射率壳的Pd纳米球有望成为一种光热治疗剂。
ACS Appl Bio Mater. 2018-10-15
Nanomaterials (Basel). 2024-2-7