New gold nanorod (Au NR)-in-shell nanostructures were developed to be more efficacious than Au NRs in near-IR (NIR) hyperthermia and nonlinear optical imaging contrast. Au NR-in-shell nanostructures are composed of an intact Au NR in a Au/Ag nanoshell. These nanostructures have a broad, intense absorption band that extends from 400 nm to 900 nm in the NIR. They are more efficient and efficacious than Au NRs with respect to in vitro hypothermia performance. Au NR-in-shell-labeled cancer cells were destroyed using continuous-wave NIR radiation with 50% less laser power than needed for Au NRs. Noticeably, the area of the destroyed cells was significantly larger than the size of the laser irradiation beam; in contrast, the destroyed area was usually restricted to the size of the laser beam spot when Au NRs were used. With their extraordinarily broad and strong surface plasmon resonance band, Au NR-in-shell nanostructures efficiently augmented several multiphoton nonlinear processes as well. The multiphoton emission spectrum covered almost the entire visible wavelength. The yield of the multiphoton signals of Au NR-in-shell nanostructures was on average 55 times larger than that of Au NRs. In vitro images of cancer cells targeted by Au NR-in-shell nanostructures revealed a stronger multiphoton contrast than those targeted by Au NRs.
A new class of Au(x)Ag(1-x) nanostructures with dendrite morphology and a hollow interior were synthesized by using a replacement reaction between Ag dendrites and an aqueous solution of HAuCl(4). The Ag nanostructured dendrites were generated by the reaction of AgNO(3) with ascorbic acid in a methanol/water system. The dendrites resemble a coral shape and are built up of many stems with an asymmetric arrangement. Each stem is approximately 400 nm in length and 65 nm in diameter. The bimetallic composition of Au(x)Ag(1-x) can be tuned by the addition of different amounts of HAuCl(4) to the Ag dendritic solution. The hollowing process resulted in tubular structures with a wall thickness of 10.5 nm in Au(0.3)Ag(0.7) dendrites. The UV/Vis spectra indicate that the strongest NIR absorption among the resulting hollow Au(x)Ag(1-x) dendrites was in Au(0.3)Ag(0.7). The MTT assay was conducted to evaluate the cytotoxicity of Ag dendrites, hollow Au(0.06)Ag(0.94) and Au(0.3)Ag(0.7) dendrites, and Au nanorods. It was found that hollow Au(0.06)Ag(0.94) and Au(0.3)Ag(0.7) dendrites exhibited good biocompatibility, while both Ag dendrites and Au nanorods showed dose-dependent toxicity. Because of absorption in the NIR region, hollow Au(0.3)Ag(0.7) dendrites were used as photothermal absorbers for destroying A549 lung cancer cells. Their photothermal performance was compared to that of Au nanorod photothermal therapeutic agents. As a result, the particle concentration and laser power required for efficient cancer cell damage were significantly reduced for hollow Au(0.3)Ag(0.7) dendrites relative to those used for Au nanorods. The hollow Au(0.3)Ag(0.7) nanostructured dendrites show potential in photothermolysis for killing cancer cells.
Two-dimensional Ag nanoprisms readily formed Ag triangular nanoframes upon electron beam irradiation. Following meso-2, 3-dimercaptosuccinicacid (DMSA) ripening behavior, continuous electron beam exposure transformed a solid nanoplate into a core/void/shell morphology, which then evolved into a hollow nanoframe structure. TEM was used to observe the ripening and etching processes of Ag nanoprisms as a function of DMSA concentration and electron irradiation time. X-ray diffraction (XRD) and FT-IR analysis were conducted to characterize the Ag nanoprism structure and surface before and after treatment with DMSA. X-ray photoelectron spectroscopy (XPS) was used to determine surface chemical compositions and indicated DMSA was adsorbed on the Ag nanoprisms in the form of Ag(+)-S(-). Raman measurements provided evidence of a disulfide group on Ag nanoprisms. Similar organosulfur structures such as mercaptosuccinic acid and 2-mercaptoacetic acid were also studied with results suggesting that the two S-H groups of dithiol DMSA played the crucial role in nanoframe fabrication. Using the same strategy with DMSA, the nano-architecture can be extended to 2D nanodiscs yielding nanorings.
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