Molecular Structure and Dynamics of Ionic Liquids in a Rigid-Rod Polyanion-Based Ion Gel

The recent fabrication of liquid crystalline ion gels featuring rigid-rod polyanions aligned within room-temperature ionic liquids (RTILs) opens up exciting new avenues for engineering ion conducting materials. These gels exhibit an unusual combination of properties including high ionic conductivity, distinct transport anisotropy, and widely tunable elastic modulus. Using molecular simulations, we study the structure and dynamics of the ions in an ion gel consisting of rigid-rod polyanions and [C2mim]­[TfO] RTILs. We show that the ion distribution in the interstitial space between polymer rods exhibits the hallmarks of the RTIL structure near charged surfaces; i.e., cations (C2mim+) and anions (TfO–) form alternating layers around the polymer rods and the charge on the rod is overscreened by the ionic layer surrounding it. The distinct ordering of ions suggests the formation of a long-range “electrostatic network” in the ion gel, which may contribute to its mechanical cohesion and high modulus. The dynamics of both C2mim+ and TfO– ions slow down due to the fact that some C2mim+ ions become associated with the sulfonate groups of the polymer rod on nanosecond time scales, which hinders the dynamics of all ions in the gel. C2mim+ and TfO– ion diffusion in the gel are only 2–10 times slower than in bulk RTILs, which is still much faster than, e.g., Li ions in typical ion conducting polymers. This fast ion transport combined with strong mechanical cohesion open up exciting opportunities for application of these gels in electrochemical devices including Li-metal batteries

Table_1_Identification of Bladder Cancer Subtypes Based on Necroptosis-Related Genes, Construction of a Prognostic Model.DOCX

BackgroundNecroptosis is associated with the development of many tumors but in bladder cancer the tumor microenvironment (TME) and prognosis associated with necroptosis is unclear.MethodsWe classified patients into different necroptosis subtypes by the expression level of NRGS (necroptosis-related genes) and analyzed the relationship between necroptosis subtypes of bladder cancer and TME, then extracted differentially expressed genes (DEGS) of necroptosis subtypes, classified patients into different gene subtypes according to DEGS, and performed univariate COX analysis on DEGS to obtain prognosis-related DEGS. All patients included in the analysis were randomized into the Train and Test groups in a 1:1 ratio, and the prognostic model was obtained using the LASSO algorithm and multivariate COX analysis with the Train group as the sample, and external validation of the model was conducted using the GSE32894.ResultsTwo necroptosis subtypes and three gene subtypes were obtained by clustering analysis and the prognosis-related DEGS was subjected to the LASSO algorithm and multivariate COX analysis to determine six predictors to construct the prognostic model using the formula: riskScore = CERCAM × 0.0035 + POLR1H × −0.0294 + KCNJ15 × −0.0172 + GSDMB × −0.0109 + EHBP1 × 0.0295 + TRIM38 × −0.0300. The results of the survival curve, roc curve, and risk curve proved the reliability of the prognostic model by validating the model with the test group and the results of the calibration chart of the Nomogram applicable to the clinic also showed its good accuracy. Necroptosis subtype A with high immune infiltration had a higher risk score than necroptosis subtype B, gene subtype B with low immune infiltration had a lower risk score than gene subtypes A and C, CSC index was negatively correlated with the risk score and drug sensitivity prediction showed that commonly used chemotherapeutic agents were highly sensitive to the high-risk group.ConclusionOur analysis of NRGS in bladder cancer reveals their potential role in TME, immunity, and prognosis. These findings may improve our understanding of necroptosis in bladder cancer and provide some reference for predicting prognosis and developing immunotherapies.</p

Dynamic Charge Storage in Ionic Liquids-Filled Nanopores: Insight from a Computational Cyclic Voltammetry Study

Understanding the dynamic charge storage in nanoporous electrodes with room-temperature ionic liquid electrolytes is essential for optimizing them to achieve supercapacitors with high energy and power densities. Herein, we report coarse-grained molecular dynamics simulations of the cyclic voltammetry of supercapacitors featuring subnanometer pores and model ionic liquids. We show that the cyclic charging and discharging of nanopores are governed by the interplay between the external field-driven ion transport and the sloshing dynamics of ions inside of the pore. The ion occupancy along the pore length depends strongly on the scan rate and varies cyclically during charging/discharging. Unlike that at equilibrium conditions or low scan rates, charge storage at high scan rates is dominated by counterions while the contribution by co-ions is marginal or negative. These observations help explain the perm-selective charge storage observed experimentally. We clarify the mechanisms underlying these dynamic phenomena and quantify their effects on the efficiency of the dynamic charge storage in nanopores

Supplemental Material - Fiber reinforced polypropylene composites interfacial behavior improvement fabricated by cold plasma jet SiO_x nanoparticles deposition

Supplemental Material for Fiber reinforced polypropylene composites interfacial behavior improvement fabricated by cold plasma jet SiOx nanoparticles deposition by Lin Zhang, Zhangchuan Xia, Yadong He, Chunling Xin, Yang Yu, Feng Ren and Ruixue Wang in Journal of Composite Materials</p

Supplemental Material - Fiber reinforced polypropylene composites interfacial behavior improvement fabricated by cold plasma jet SiO_x nanoparticles deposition

Supplemental Material for Fiber reinforced polypropylene composites interfacial behavior improvement fabricated by cold plasma jet SiOx nanoparticles deposition by Lin Zhang, Zhangchuan Xia, Yadong He, Chunling Xin, Yang Yu, Feng Ren and Ruixue Wang in Journal of Composite Materials</p

Simultaneous Enhancements in Toughness and Electrical Conductivity of Polypropylene/Carbon Nanotube Nanocomposites by Incorporation of Electrically Inert Calcium Carbonate Nanoparticles

Although the presence of carbon nanotubes (CNTs) makes polypropylene (PP) electrically conductive, the resulting PP/CNT binary nanocomposites become brittle limiting their practical applications. To toughen PP/CNT nanocomposites, calcium carbonate (CaCO₃) inorganic nanoparticles are melt-compounded with PP and CNTs components to fabricate electrically conductive and tough PP/CNT/CaCO₃ ternary nanocomposites. The PP/CNT nanocomposites have a relatively large percolation threshold of 6.2 wt %, which reduces to 5.6 wt % by the addition of 30 wt % of pristine CaCO₃, and further to 3.6 wt % in the presence of 30 wt % of modified CaCO₃. Simultaneously, the electrically conductive PP/CNT nanocomposites are efficiently toughened by the CaCO₃ nanoparticles, and the notched impact strength increases from 16.0 to 33.1 KJ/m² by compounding 30 wt % of modified CaCO₃ with PP/9 wt % CNT components. The dual roles of CaCO₃ in volume-exclusion and toughening are well demonstrated

Importance of Ion Packing on the Dynamics of Ionic Liquids during Micropore Charging

Molecular simulations of the diffusion of EMIM⁺ and TFSI^– ions in slit-shaped micropores under conditions similar to those during charging show that in pores that accommodate only a single layer of ions, ions diffuse increasingly faster as the pore becomes charged (with diffusion coefficients even reaching ∼5 × 10^–9 m²/s), unless the pore becomes very highly charged. In pores wide enough to fit more than one layer of ions, ion diffusion is slower than in the bulk and changes modestly as the pore becomes charged. Analysis of these results revealed that the fast (or slow) diffusion of ions inside a micropore during charging is correlated most strongly with the dense (or loose) ion packing inside the pore. The molecular details of the ions and the precise width of the pores modify these trends weakly, except when the pore is so narrow that the ion conformation relaxation is strongly constrained by the pore walls