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Reconciling structure prediction of alloyed, ultrathin nanowires with spectroscopy.

ABSTRACT: A number of complementary, synergistic advances are reported herein. First, we describe the 'first-time' synthesis of ultrathin Ru₂Co₁ nanowires (NWs) possessing average diameters of 2.3 ± 0.5 nm using a modified surfactant-mediated protocol. Second, we utilize a combination of quantitative EDS, EDS mapping (along with accompanying line-scan profiles), and EXAFS spectroscopy results to probe the local atomic structure of not only novel Ru₂Co₁ NWs but also 'control' samples of analogous ultrathin Ru₁Pt₁, Au₁Ag₁, Pd₁Pt₁, and Pd₁Pt₉ NWs. We demonstrate that ultrathin NWs possess an atomic-level geometry that is fundamentally dependent upon their intrinsic chemical composition. In the case of the PdPt NW series, EDS mapping data are consistent with the formation of a homogeneous alloy, a finding further corroborated by EXAFS analysis. By contrast, EXAFS analysis results for both Ru₁Pt₁ and Ru₂Co₁ imply the generation of homophilic structures in which there is a strong tendency for the clustering of 'like' atoms; associated EDS results for Ru₁Pt₁ convey the same conclusion, namely the production of a heterogeneous structure. Conversely, EDS mapping data for Ru₂Co₁ suggests a uniform distribution of both elements. In the singular case of Au₁Ag₁, EDS mapping results are suggestive of a homogeneous alloy, whereas EXAFS analysis pointed to Ag segregation at the surface and an Au-rich core, within the context of a core-shell structure. These cumulative outcomes indicate that only a combined consideration of both EDS and EXAFS results can provide for an accurate representation of the local atomic structure of ultrathin NW motifs.

SUBMITTER: McGuire SC

PROVIDER: S-EPMC8153242 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:BackgroundRadiation therapy is a main treatment option for cancer. Due to normal tissue toxicity, radiosensitizers are commonly used to enhance RT. In particular, heavy metal or high-Z materials, such as gold nanoparticles, have been investigated as radiosensitizers. So far, however, the related studies have been focused on spherical gold nanoparticles. In this study, we assessed the potential of ultra-thin gold nanowires as a radiosensitizer, which is the first time.MethodsGold nanowires were synthesized by the reduction of HAuCl4 in hexane. The as-synthesized gold nanowires were then coated with a layer of PEGylated phospholipid to be rendered soluble in water. Spherical gold nanoparticles coated with the same phospholipid were also synthesized as a comparison. Gold nanowires and gold nanospheres were first tested in solutions for their ability to enhance radical production under irradiation. They were then incubated with 4T1 cells to assess whether they could elevate cell oxidative stress under irradiation. Lastly, gold nanowires and gold nanoparticles were intratumorally injected into a 4T1 xenograft model, followed by irradiation applied to tumors (3 Gy/per day for three days). Tumor growth was monitored and compared.ResultsOur studies showed that gold nanowires are superior to gold nanospheres in enhancing radical production under X-ray radiation. In vitro analysis found that the presence of gold nanowires caused elevated lipid peroxidation and intracellular oxidative stress under radiation. When tested in vivo, gold nanowires plus irradiation led to better tumor suppression than gold nanospheres plus radiation. Moreover, gold nanowires were found to be gradually reduced to shorter nanowires by glutathione, which may benefit fractionated radiation.ConclusionOur studies suggest that gold nanowires are a promising type of radiosensitizer that can be safely injected into tumors to enhance radiotherapy. While the current study was conducted in a breast cancer model, the approach can be extended to the treatment of other cancer types.

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Reconciling structure prediction of alloyed, ultrathin nanowires with spectroscopy.

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