Food and Beverage Ingredients Induce the Formation of Silver Nanoparticles in Products Stored within Nanotechnology-Enabled Packaging.

Nanotechnology-based packaging may improve food quality and safety, but packages manufactured with polymer nanocomposites (PNCs) could be a source of human dietary exposure to engineered nanomaterials (ENMs). Previous studies showed that PNCs release ENMs to foods predominantly in a dissolved state, but most of this work used food simulants like dilute acetic acid and water, leaving questions about how substances in real foods may influence exposure. Here, we demonstrate that food and beverage ingredients with reducing properties, like sweeteners, may alter exposure by inducing nanoparticle formation in foods contacting silver nanotechnology-enabled packaging. We incorporated 12.8 ± 1.4 nm silver nanoparticles (AgNPs) into polyethylene and stored media containing reducing ingredients in packages manufactured from this material under accelerated room-temperature and refrigerated conditions. Analysis of the leachates revealed that reducing ingredients increased the total silver transferred to foods contacting PNC packaging (by as much as 7-fold) and also induced the (re)formation of AgNPs from this dissolved silver during storage. AgNP formation was also observed when Ag+ was introduced to solutions of natural and artificial sweeteners (glucose, sucrose, aspartame), commercial beverages (soft drinks, juices, milk), and liquid foods (yogurt, starch slurry), and the amount and morphology of reformed AgNPs depended on the ingredient formulation, silver concentration, storage conditions, and light exposure. These results imply that food and beverage ingredients may influence dietary exposure to nanoparticles when PNCs are used in packaging applications, and the practice of using food simulants may in certain cases underpredict the amount of ENMs likely to be found in foods stored in these materials.

Dynamics of Transformation from Platinum Icosahedral Nanoparticles to Larger FCC Crystal at Millisecond Time Resolution.

Atomic motion at grain boundaries is essential to microstructure development, growth and stability of catalysts and other nanostructured materials. However, boundary atomic motion is often too fast to observe in a conventional transmission electron microscope (TEM) and too slow for ultrafast electron microscopy. Here, we report on the entire transformation process of strained Pt icosahedral nanoparticles (ICNPs) into larger FCC crystals, captured at 2.5 ms time resolution using a fast electron camera. Results show slow diffusive dislocation motion at nm/s inside ICNPs and fast surface transformation at µm/s. By characterizing nanoparticle strain, we show that the fast transformation is driven by inhomogeneous surface stress. And interaction with pre-existing defects led to the slowdown of the transformation front inside the nanoparticles. Particle coalescence, assisted by oxygen-induced surface migration at T ≥ 300 °C, also played a critical role. Thus by studying transformation in the Pt ICNPs at high time and spatial resolution, we obtain critical insights into the transformation mechanisms in strained Pt nanoparticles.

Large-deformation and high-strength amorphous porous carbon nanospheres.

Carbon is one of the most important materials extensively used in industry and our daily life. Crystalline carbon materials such as carbon nanotubes and graphene possess ultrahigh strength and toughness. In contrast, amorphous carbon is known to be very brittle and can sustain little compressive deformation. Inspired by biological shells and honeycomb-like cellular structures in nature, we introduce a class of hybrid structural designs and demonstrate that amorphous porous carbon nanospheres with a thin outer shell can simultaneously achieve high strength and sustain large deformation. The amorphous carbon nanospheres were synthesized via a low-cost, scalable and structure-controllable ultrasonic spray pyrolysis approach using energetic carbon precursors. In situ compression experiments on individual nanospheres show that the amorphous carbon nanospheres with an optimized structure can sustain beyond 50% compressive strain. Both experiments and finite element analyses reveal that the buckling deformation of the outer spherical shell dominates the improvement of strength while the collapse of inner nanoscale pores driven by twisting, rotation, buckling and bending of pore walls contributes to the large deformation.

Large area and depth-profiling dislocation imaging and strain analysis in Si/SiGe/Si heterostructures.

We demonstrate the combined use of large area depth-profiling dislocation imaging and quantitative composition and strain measurement for a strained Si/SiGe/Si sample based on nondestructive techniques of electron beam-induced current (EBIC) and X-ray diffraction reciprocal space mapping (XRD RSM). Depth and improved spatial resolution is achieved for dislocation imaging in EBIC by using different electron beam energies at a low temperature of ~7 K. Images recorded clearly show dislocations distributed in three regions of the sample: deep dislocation networks concentrated in the "strained" SiGe region, shallow misfit dislocations at the top Si/SiGe interface, and threading dislocations connecting the two regions. Dislocation densities at the top of the sample can be measured directly from the EBIC results. XRD RSM reveals separated peaks, allowing a quantitative measurement of composition and strain corresponding to different layers of different composition ratios. High-resolution scanning transmission electron microscopy cross-section analysis clearly shows the individual composition layers and the dislocation lines in the layers, which supports the EBIC and XRD RSM results.

The formation and utility of sub-angstrom to nanometer-sized electron probes in the aberration-corrected transmission electron microscope at the University of Illinois.

We evaluate the probe forming capability of a JEOL 2200FS transmission electron microscope equipped with a spherical aberration (Cs) probe corrector. The achievement of a real space sub-Angstrom (0.1 nm) probe for scanning transmission electron microscopy (STEM) imaging is demonstrated by acquisition and modeling of high-angle annular dark-field STEM images. We show that by optimizing the illumination system, large probe currents and large collection angles for electron energy loss spectroscopy (EELS) can be combined to yield EELS fine structure data spatially resolved to the atomic scale. We demonstrate the probe forming flexibility provided by the additional lenses in the probe corrector in several ways, including the formation of nanometer-sized parallel beams for nanoarea electron diffraction, and the formation of focused probes for convergent beam electron diffraction with a range of convergence angles. The different probes that can be formed using the probe corrected STEM opens up new applications for electron microscopy and diffraction.

Imaging of plasmonic modes of silver nanoparticles using high-resolution cathodoluminescence spectroscopy.

Cathodoluminescence spectroscopy has been performed on silver nanoparticles in a scanning electron microscopy setup. Peaks appearing in the visible range for particles fabricated on silicon substrate are shown to arrive from excitation of out-of-plane eigenmodes by the electron beam. Monochromatic emission maps have been shown to resolve spatial field variation of resonant plasmon mode on length scale smaller than 25 nm. Finite-difference time-domain numerical simulations are performed for both the cases of light excitation and electron excitation. The results of radiative emission under electron excitation show an excellent agreement with experiments. A complete vectorial description of induced field is given, which complements the information obtained from experiments.