Biosensing with nanoholes is one of the most promising applications of nanoplasmonic devices. The sensor properties, however, are complex due to coupled resonances through propagating and localized surface plasmons. This Full Paper demonstrates experimental and simulation studies on different plasmonic hole systems, namely various patterns of circular holes in gold films. In contrast to most previous work, here, the challenging situation of optically thin films is considered. The refractive-index-sensing properties, such as sensitive locations in the nanostructure and sensitive spectral features, are investigated. The multiple multipole program provides the complete field distribution in the nanostructure for different wavelengths. It is shown that the spectral feature most sensitive to refractive-index changes is the extinction minimum, rather than the maximum. The results are consistent with theory for perfect electrical conductors. The spectral response is investigated for molecular adsorption at different positions inside or outside a hole. Furthermore, the optical properties of nanohole arrays with long-range and short-range order are compared and found to demonstrate remarkable similarities. Our results help to predict the resonance wavelengths of nanoholes with arbitrary patterns, including short-range order. The results presented here are highly important since they extend and challenge several aspects of the current understanding of plasmon resonances in nanohole arrays. These theoretical models, simulation results, and experimental data together help provide the understanding necessary for the development of efficient biomolecular analysis tools based on metallic nanoholes.
We demonstrate a reliable fabrication method to produce plasmonic dipole nanoantennas with gap values in the range of 3.5-20 nm. The method combines electron beam lithography to create gold nanorods and helium focused ion beam milling to cut the gaps. Results show a reproducibility within 1 nm. Scattering spectra of antennas show a red shift of resonance wavelengths and an increase of the intensity of resonance peaks with a decrease of the gap size, which is in agreement with finite element simulations. The measured refractive index sensitivity was about 250 nm per refractive index unit for antennas with gap values below 5 nm.
Metal oxide nanoparticles have emerged as exceptionally potent biomedical sensors and actuators due to their unique physicochemical features. Despite fascinating achievements, the current limited understanding of the molecular interplay between nanoparticles and the surrounding tissue remains a major obstacle in the rationalized development of nanomedicines, which is reflected in their poor clinical approval rate. This work reports on the nanoscopic characterization of inorganic nanoparticles in tissue by the example of complex metal oxide nanoparticle hybrids consisting of crystalline cerium oxide and the biodegradable ceramic bioglass. A validated analytical method based on semiquantitative X‐ray fluorescence and inductively coupled plasma spectrometry is used to assess nanoparticle biodistribution following intravenous and topical application. Then, a correlative multiscale analytical cascade based on a combination of microscopy and spectroscopy techniques shows that the topically applied hybrid nanoparticles remain at the initial site and are preferentially taken up into macrophages, form apatite on their surface, and lead to increased accumulation of lipids in their surroundings. Taken together, this work displays how modern analytical techniques can be harnessed to gain unprecedented insights into the biodistribution and biotransformation of complex inorganic nanoparticles. Such nanoscopic characterization is imperative for the rationalized engineering of safe and efficacious nanoparticle‐based systems.
For several decades, food-grade synthetic amorphous silica (SAS) have been used as a technological additive to reduce caking of food powders. Human exposure is thus inevitable and safety concerns are taken seriously. The toxicity of silica in general and SAS in particular has been studied extensively. Overall, there is little evidence that food-grade SAS pose any health risks to humans. However, from the available data it was often not clear which type of silica was used. Accordingly, the latest report of the European food safety authority requested additional toxicity data for well-characterised "real food-grade SAS". To close this gap, we screened a panel of ten well-defined, food-grade SAS for potential adverse effects on differentiated Caco-2 cells. Precipitated and fumed SAS with low, intermediate and high specific surface area were included to determine structure-activity relationships. In a physiological dose-range up to 50 µg/ml and 48 hours of incubation, none of the materials induced adverse effects on differentiated Caco-2 cells. This held true for endpoints of acute cytotoxicity as well as epithelial specific measures of barrier integrity. These results showed that despite considerable differences in production routes and material characteristics, food-relevant SAS did not elicit acute toxicity responses in intestinal epithelial cells. strongly indicate that independent of the production process and the specific surface area, SAS materials do not induce acute toxicity after oral exposure.
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