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  1. Free, publicly-accessible full text available August 22, 2024
  2. Nanocomposites integrate functional nanofillers into viscoelastic matrices for electronics, lightweight structural materials, and tissue engineering. Herein, the effect of methacrylate-functionalized (MA-SiO 2 ) and vinyl-functionalized (V-SiO 2 ) silica nanoparticles on the thermal, mechanical, physical, and morphological characteristics of poly(ethylene glycol) (PEG) nanocomposites was investigated. The gel fraction of V-SiO 2 composites decreases upon addition of 3.8 wt% but increases with further addition (>7.4 wt%) until it reaches a plateau at 10.7 wt%. The MA-SiO 2 induced no significant changes in gel fraction and both V-SiO 2 and MA-SiO 2 nanoparticles had a negligible impact on the nanocomposite glass transition temperature and water absorption. The Young's modulus and ultimate compressive stress increased with increasing nanoparticle concentration for both nanoparticles. Due to the higher crosslink density, MA-SiO 2 composites reached a maximum mechanical stress at a concentration of 7.4 wt%, while V-SiO 2 composites reached a maximum at a concentration of 10.7 wt%. Scanning electron microscopy, transmission electron microscopy, and small-angle X-ray scattering revealed a bimodal size distribution for V-SiO 2 and a monomodal size distribution for MA-SiO 2 . Although aggregates were observed for both nanoparticle surface treatments, V-SiO 2 dispersion was poor while MA-SiO 2 were generally well-dispersed. These findings lay the framework for silica nanofillers in PEG-based nanocomposites for advanced manufacturing applications. 
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  3. Abstract

    Advancements in electronics and energy storage and conversion technologies brings with it myriads of exciting material design challenges. Charge‐containing block polymers (BPs) offer unique features which can overcome some of these challenges and have thus aroused substantial interest within the field of designer soft materials. The properties of BPs are intricately coupled to the dynamic and rich nature of the nanostructured assemblies, which result from the phase separation between blocks. The introduction of strong secondary forces, such as electrostatics and hydrogen bonding (H‐bonding), into BPs greatly influences their self‐assembly behavior, and therefore affects their physical and electrochemical properties often in nontrivial ways. In this review, some of the prevailing research, which has expanded the understanding of structure–property relationships to include several design strategies for improving ionic conductivity and modulus in charged block polymers, is presented. The profound extent to which electrostatics and hydrogen bonding impact block polymer thermodynamics, an extent which is demonstrated by recent theoretical and experimental work, is also highlight. Insights gained from the research presented here help to lay the groundwork for a long and bright future in the field of advanced soft materials.

     
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  5. Aryl chlorides (ArCl) or aryl fluorides (ArF) were used in polycondensation reactions to form poly(arylene ether sulfone)s (PAES). Interestingly, the kinetics of the ArF reaction fit a third-order rate law, which is attributed to the activation of the carbon–fluorine bond by two potassium cations (at least one bound to phenolate), which form a three-body complex. The ArCl monomer follows a second-order rate law, where a two-body complex forms at the initial state of the aromatic nucleophilic substitution (S N Ar) pathway. These metal cation-activated complexes act as intermediates during the attack by the nucleophile. This finding was reproduced with either the potassium or the sodium counterion (introduced via potassium carbonate or sodium carbonate). Through a combination of experimental analysis of reaction kinetics and computational calculations with density functional theory (DFT) methods, the present work extends the fundamental understanding of polycondensation mechanisms for two aryl halides and highlights the importance of the CX–metal interaction(s) in the S N Ar reaction, which is translational to other ion-activated substitution reactions. 
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  7. Abstract

    A major goal of community ecology is understanding the processes responsible for generating biodiversity patterns along spatial and environmental gradients. In stream ecosystems, system‐specific conceptual frameworks have dominated research describing biodiversity change along longitudinal gradients of river networks. However, support for these conceptual frameworks has been mixed, mainly applicable to specific stream ecosystems and biomes, and these frameworks have placed less emphasis on general mechanisms driving biodiversity patterns. Rethinking biodiversity patterns and processes in stream ecosystems with a focus on the overarching mechanisms common across ecosystems will provide a more holistic understanding of why biodiversity patterns vary along river networks. In this study, we apply the theory of ecological communities (TEC) conceptual framework to stream ecosystems to focus explicitly on the core ecological processes structuring communities: dispersal, speciation, niche selection, and ecological drift. Using a unique case study from high‐elevation networks of connected lakes and streams, we sampled stream invertebrate communities in the Sierra Nevada, California, USA to test established stream ecology frameworks and compared them with the TEC framework. Local diversity increased and β‐diversity decreased moving downstream from the headwaters, consistent with the river continuum concept and the small but mighty framework of mountain stream biodiversity. Local diversity was also structured by distance below upstream lakes, where diversity increased with distance below upstream lakes, in support of the serial discontinuity concept. Despite some support for the biodiversity patterns predicted from the stream ecology frameworks, no single framework was fully supported, suggesting “context dependence.” By framing our results under the TEC, we found that species diversity was structured by niche selection, where local diversity was highest in environmentally favorable sites. Local diversity was also highest in sites with small community sizes, countering the predicted effects of ecological drift. Moreover, higher β‐diversity in the headwaters was influenced by dispersal and niche selection, where environmentally harsh and spatially isolated sites exhibit higher community variation. Taken together our results suggest that combining system‐specific ecological frameworks with the TEC provides a powerful approach for inferring the mechanisms driving biodiversity patterns and provides a path toward generalization of biodiversity research across ecosystems.

     
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