Advancing elastomer performance with dynamic bond networks in polymer-grafted single-chain nanoparticles: a molecular dynamics exploration.

This research introduces a method to enhance the mechanical properties of elastomers by grafting polymer chains onto single-chain flexible nanoparticles (SCNPs) and incorporating dynamic functional groups. Drawing on developments in grafting polymers onto hard nanoparticle fillers, this method employs the distinct flexibility of SCNPs to diminish heterogeneity and enhance core size control. We use molecular dynamics (MD) simulations for a mesoscale analysis of structural properties, particularly the effects of dynamic functional group quantities and their distribution. The findings demonstrate that increased quantities of functional groups are correlated with enhanced mechanical strength and toughness, showing improved stress-strain responses and energy dissipation capabilities. Moreover, the uniformity in the distribution of these functional groups is crucial, promoting a more cohesive and stable dynamic bonding network. The insights gained from MD simulations not only advance our understanding of the microstructural control necessary for optimizing macroscopic properties, but also provide valuable guidance for the design and engineering of advanced polymer nanocomposites, thereby enhancing the material performance through strategic molecular design.

Manipulating the Properties of Polymer Vitrimer Nanocomposites by Designing Dual Dynamic Covalent Bonds.

Polymer vitrimer is a novel material that contains dynamic covalent bonds (DCBs) allowing it to combine the desirable characteristics of both thermoplastics and thermosets. Similar to the traditional polymer nanocomposites, introducing nanoparticles into polymer vitrimer is also an effective strategy to further enhance its properties. However, a comprehensive understanding of matrix and interfacial bond exchange reactions (BERs) to tailor the properties of polymer vitrimer nanocomposites (PVNs) is still lacking. Herein, we utilized coarse-grained molecular dynamics simulations to investigate model PVNs in which there are two different kinds of DCBs in the vitrimer matrix and at the interface. Our results show that the normalized bond autocorrelation function (Csw) confirms the independence of BERs in the vitrimer matrix and in the interface. By varying the bond swap energy barrier (ΔEsw) in the matrix ΔEswmat or in the interface ΔEswint, or in both ΔEswall, a maximum mechanical property is observed at the moderate value of ΔEswmat, ΔEswint, orΔEswall. Meanwhile, the effect of ΔEsw on the stress relaxation and the bond orientation as a function of the time under a fixed strain is well probed, which both decay more slowly at greater ΔEsw. We simulated the tension-recovery curve to examine the effect of ΔEsw on the hysteresis loss and permanent deformation of PVNs, finding an optimal value to achieve its minimum energy dissipation and maximum recovery ratio. Lastly, we investigated the efficiency of self-healing by building and removing walls from the system. Interestingly, a maximum self-healing efficiency of the stress-strain behavior is observed at moderate ΔEsw. Overall, this study provides valuable insights into the relationship between the structure and properties of PVNs, offering implications for the manipulation of their mechanical properties and enhancement of their self-healing capabilities.

Integrating transcriptome and physiological analyses to elucidate the molecular responses of sorghum to fluxofenim and metolachlor herbicide.

The extensive use of herbicides has raised concerns about crop damage, necessitating the development of effective herbicide safeners. Fluxofenim has emerged as a promising herbicide safener; however, it's underlying mechanism remains unclear. Here, we screened two inbred lines 407B and HYZ to investigate the detoxication of fluxofenim in mitigating metolachlor damage in sorghum. Metolachlor inhibited seedling growth in both 407B and HYZ, while, fluxofenim could significantly restore the growth of 407B, but not effectively complement the growth of HYZ. Fluxofenim significantly increased the activities of glutathione-S-transferase (GST) to decrease metolachlor residue in 407B, but not in HYZ. This implys that fluxofenim may reduce metolachlor toxicity by regulating its metabolism. Furthermore, metolachlor suppressed AUX-related and JA-related genes expression, while up-regulated the expression of SA-related genes. Fluxofenim also restored the expression of AUX-related and JA-related genes inhibited by metolachlor and further increased expression of SA-related genes. Moreover, we noted a significant increase in the content of trans-zeatin O-glucoside (tZOG) and Gibberellin1 (GA1) after the fluxofenim treatment. In conclusion, fluxofenim may reduce the injury of herbicide by affecting herbicide metabolism and regulating hormone signaling pathway.

Conformation and Dynamics along the Chain Contours of Polymer-Grafted Nanoparticles.

Densely grafted polymer chains onto spherical nanoparticles produce a diverse range of conformations. At high grafting densities, the corona region near the nanoparticle surface undergoes intense confinement due to a high concentration of chains in the concentrated polymer brush (CPB) region, which results in strong stretching for portions of the chains located within. In contrast, a semi-dilute polymer brush (SDPB) forms farther away from the core and offers reduced confinement for the polymer and more ideal conformations. However, conventional experimental methods are limited in their ability to provide detailed information on individual segments of grafted polymers in these regions; hence, molecular dynamics (MD) simulations are essential for gaining comprehensive insights into the behavior of the grafted chains. This study aims to explore the variations in polymer structure and dynamics that occur along the contour of the grafted chains as influenced by spatial confinement. We focus on the motions and relative positions of each bead along grafted polymers. Our results show that only the initial few grafted beads near the nanoparticle surface exhibit the strong stretching attributed segments in the CPB region of the brush. Increased grafting density or decreased chain flexibility leads to more stretched grafted chains and more aligned bond vectors. As a result, the relaxation dynamics of local regions of the polymer are also strongly influenced by these parameters. Although the grafted beads in the interior of the CPB region are highly sensitive to these parameters, those farther from the nanoparticle core experience significantly diminished effects. In comparison to the Daoud-Cotton (DC) model's predictions of CPB size, beads near the nanoparticle surface show slower dynamic decay, especially in high grafting densities, aligning with the DC model's estimates. Finally, we compare our simulations to previous works for additional insight into polymer-grafted nanoparticles.

Molecular dynamics simulation of the impact of the surface topology of carbon black on the mechanical properties of elastomer nanocomposites.

Carbon black has always played a pivotal role in reinforcing elastomers because it remarkably improves the mechanical properties. The reinforcing effect of carbon black is influenced by its grades, which mainly depend on the difference in the structure of the carbon black particles. Despite many traditional experiments on the performance of carbon black composites, there has been less emphasis on reinforcement mechanisms due to the challenges associated with unraveling the intermolecular interactions. In this paper, a coarse grained molecular dynamics simulation was employed to examine the relationship between the morphology of the carbon black particles and the mechanical properties of the elastomer nanocomposites. Specifically, three different morphological carbon black nanoparticle models, including the smooth particle model, rough particle model, and the rough ellipsoid model, were constructed first. We then focused on investigating the changes of the mechanical properties by systematically varying the filling fraction of the carbon black particles, and the strength of the interfacial interaction between the filler and the rubber. The results indicated that the surface roughness and the filler's shape had a significant impact on the mechanical properties of the filled rubber models. The mechanical enhancement effect of the rough ellipsoidal carbon black is around 50-400% higher than that of the smooth carbon black, and the stronger the interfacial interactions, the more pronounced the enhancement. In addition, the rough ellipsoid filled system has low hysteresis, low permanent deformation, and high fatigue resistance. In general, this work explores the strengthening mechanism of carbon black on the elastomer at the molecular level and generates new insight into the design and fabrication of novel reinforcing fillers.