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Creators/Authors contains: "Smith, John W"

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  1. Voids—the nothingness—broadly exist within nanomaterials and impact properties ranging from catalysis to mechanical response. However, understanding nanovoids is challenging due to lack of imaging methods with the needed penetration depth and spatial resolution. Here, we integrate electron tomography, morphometry, graph theory and coarse-grained molecular dynamics simulation to study the formation of interconnected nanovoids in polymer films and their impacts on permeance and nanomechanical behaviour. Using polyamide membranes for molecular separation as a representative system, three-dimensional electron tomography at nanometre resolution reveals nanovoid formation from coalescence of oligomers, supported by coarse-grained molecular dynamics simulations. Void analysis provides otherwise inaccessible inputs for accurate fittings of methanol permeance for polyamide membranes. Three-dimensional structural graphs accounting for the tortuous nanovoids within, measure higher apparent moduli with polyamide membranes of higher graph rigidity. Our study elucidates the significance of nanovoids beyond the nothingness, impacting the synthesis‒morphology‒function relationships of complex nanomaterials. 
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  2. Abstract Near‐term iterative forecasting is a powerful tool for ecological decision support and has the potential to transform our understanding of ecological predictability. However, to this point, there has been no cross‐ecosystem analysis of near‐term ecological forecasts, making it difficult to synthesize diverse research efforts and prioritize future developments for this emerging field. In this study, we analyzed 178 near‐term (≤10‐yr forecast horizon) ecological forecasting papers to understand the development and current state of near‐term ecological forecasting literature and to compare forecast accuracy across scales and variables. Our results indicated that near‐term ecological forecasting is widespread and growing: forecasts have been produced for sites on all seven continents and the rate of forecast publication is increasing over time. As forecast production has accelerated, some best practices have been proposed and application of these best practices is increasing. In particular, data publication, forecast archiving, and workflow automation have all increased significantly over time. However, adoption of proposed best practices remains low overall: for example, despite the fact that uncertainty is often cited as an essential component of an ecological forecast, only 45% of papers included uncertainty in their forecast outputs. As the use of these proposed best practices increases, near‐term ecological forecasting has the potential to make significant contributions to our understanding of forecastability across scales and variables. In this study, we found that forecastability (defined here as realized forecast accuracy) decreased in predictable patterns over 1–7 d forecast horizons. Variables that were closely related (i.e., chlorophyll and phytoplankton) displayed very similar trends in forecastability, while more distantly related variables (i.e., pollen and evapotranspiration) exhibited significantly different patterns. Increasing use of proposed best practices in ecological forecasting will allow us to examine the forecastability of additional variables and timescales in the future, providing a robust analysis of the fundamental predictability of ecological variables. 
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  3. Abstract Reconfigurable hybrid nanoparticles made by decorating flexible polymer shells on rigid inorganic nanoparticle cores can provide a unique means to build stimuli‐responsive functional materials. The polymer shell reconfiguration has been expected to depend on the local core shape details, but limited systematic investigations have been undertaken. Here, two literature methods are adapted to coat either thiol‐terminated polystyrene (PS) or polystyrene‐poly(acrylic acid) (PS‐b‐PAA) shells onto a series of anisotropic gold nanoparticles of shapes not studied previously, including octahedron, concave cube, and bipyramid. These core shapes are complex, rendering shell contours with nanoscale details (e.g., local surface curvature, shell thickness) that are imaged and analyzed quantitatively using the authors' customized analysis codes. It is found that the hybrid nanoparticles based on the chosen core shapes, when coated with the above two polymer shells, exhibit distinct shell segregations upon a variation in solvent polarity or temperature. It is demonstrated for the PS‐b‐PAA‐coated hybrid nanoparticles, the shell segregation is maintained even after a further decoration of the shell periphery with gold seeds; these seeds can potentially facilitate subsequent deposition of other nanostructures to enrich structural and functional diversity. These synthesis, imaging, and analysis methods for the hybrid nanoparticles of anisotropically shaped cores can potentially aid in their predictive design for materials reconfigurable from the bottom up. 
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