Comb-shaped sulfonated poly(aryl ether sulfone) proton exchange membrane for fuel cell applications

Structure design is the primary strategy to acquire suitable ionomers for preparing proton exchange membranes (PEMs) with excellent performance. A series of comb-shaped sulfonated fluorinated poly(aryl ether sulfone) (SPFAES) membranes are prepared from sulfonated fluorinated poly(aryl ether sulfone) polymer (SPFAE) and sulfonated poly(aryl ether sulfone) oligomer (SPAES-Oligomer). Chemical structures of the comb-shaped membranes are verified by ¹H nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectra. The comb-shaped SPFAES membranes display more continuous hydrophilic domains for ion transfer, because the abundant cations and flexible side-chains structure possess higher mobility and hydrophilicity, which show significantly improved proton conductivity, physicochemical stability, mechanical property compared to the linear SPFAE membranes. In a H₂/O₂ single-cell test, the SPFAES-1.77 membrane achieves a higher power density of 699.3 mW/cm² in comparison with Nafion® 112 (618.0 mW/cm²) at 80 °C and 100% relative humidity. This work offers a promising example for the synthesis of highly branched polymers with flexible comb-shaped side chains for high-performance PEMs.     

Increased hydroxyl concentration by tungsten oxide modified h-BN promoted catalytic performance in partial oxidation of methane

Hexagonal boron nitride (h-BN) as a layered inorganic nonmetallic material has been widely used. Hydrogen peroxide (H₂O₂) modification can trigger exfoliation and afford abundant B–OH active sites at edge of h-BN, which can enhance methane activation ability. Introducing tungsten oxide (WO₃) to h-BN produces a similar effect, because doping WO₃ into h-BN resulted in electron transfer to N, inducing fracture of B–N bond, resulting in N vacancy (triboron center), exposing more B sites and promoting the generation of B–OH. Significantly, the introduction of WO₃ on the modified h-BN dramatically increased the concentration of B–OH compared with the unmodified h-BN, because H₂O₂ modification weakened B–N bond. By means of XRD, TEM, XPS,EPR, FT-IR, it is proved that the high concentration of B–OH active sites contributed to activating C–H bond, thus methane conversion and CO and H₂ selectivity were significantly improved.     

From modification to mechanism: Supercritical hydrothermal synthesis of nano-zirconia

Nano-zirconia has been widely applied due to its excellent physical and chemical properties (e.g., high strength, corrosion resistance, oxygen ion conductivity). Existing preparation methods of nano-zirconia tend to require long reaction time, and the sizes of final particles are large with uneven distributions. Sub-/supercritical hydrothermal synthesis of nanoparticles is favored by researchers owing to controllable reaction process, uniform particle size distribution, good reproducibility, short reaction time, high conversion rate and harmlessness to environment. In this paper, the characteristics and mechanisms of dissolution, crystallization and growth of nano-zirconia during sub-/supercritical hydrothermal synthesis are systematically reviewed. The influences of process and material parameters on the size and purity of particles are analyzed. Then, the reaction mechanism and product phase transition mechanism during hydrothermal synthesis of zirconia are summarized to provide a theoretical reference for the oriented preparation. Finally, the improvement and commercialization of sub-/supercritical hydrothermal synthesis technology are evaluated, and the future research topics are proposed.     

Synthesis and characterization of a long side-chain double-cation crosslinked anion-exchange membrane based on poly(styrene-b-(ethylene-co-butylene)-b-styrene)

By choosing a triple block polymer, poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS), as the backbone and adopting a long side-chain double-cation crosslinking strategy, a series of SEBS-based anion-exchange membranes (AEMs) was successively synthesized by chloromethylation, quaternization, crosslinking, solution casting, and alkalization. The 70C16-SEBS-TMHDA membrane showed high OH⁻ conductivity (72.13 mS/cm at 80 °C) and excellent alkali stability (only 10.86% degradation in OH⁻ conductivity after soaking in 4-M NaOH for 1700 h at 80 °C). Furthermore, the SR was only 9.3% at 80 °C and the peak power density of the H₂/O₂ single cell was up to 189 mW/cm² at a current density of 350 mA/cm² at 80 °C. By introducing long flexible side chains into a polymer SEBS backbone, the structure of the hydrophilic–hydrophobic microphase separation in the membrane was constructed to improve the ionic conductivity. Additionally, network crosslinked structure improved dimensional stability and mechanical properties.     

Spinal Excitatory Dynorphinergic Interneurons Contribute to Burn Injury-Induced Nociception Mediated by Phosphorylated Histone 3 at Serine 10 in Rodents

The phosphorylation of serine 10 in histone 3 (p-S10H3) has recently been demonstrated to participate in spinal nociceptive processing. However, superficial dorsal horn (SDH) neurons involved in p-S10H3-mediated nociception have not been fully characterized. In the present work, we combined immunohistochemistry, in situ hybridization with the retrograde labeling of projection neurons to reveal the subset of dorsal horn neurons presenting an elevated level of p-S10H3 in response to noxious heat (60 °C), causing burn injury. Projection neurons only represented a small percentage (5%) of p-S10H3-positive cells, while the greater part of them belonged to excitatory SDH interneurons. The combined immunolabeling of p-S10H3 with markers of already established interneuronal classes of the SDH revealed that the largest subset of neurons with burn injury-induced p-S10H3 expression was dynorphin immunopositive in mice. Furthermore, the majority of p-S10H3-expressing dynorphinergic neurons proved to be excitatory, as they lacked Pax-2 and showed Lmx1b-immunopositivity. Thus, we showed that neurochemically heterogeneous SDH neurons exhibit the upregulation of p-S10H3 shortly after noxious heat-induced burn injury and consequential tissue damage, and that a dedicated subset of excitatory dynorphinergic neurons is likely a key player in the development of central sensitization via the p-S10H3 mediated pathway.     

Crystalline phase of TiO2 nanotube arrays on Ti–35Nb–4Zr alloy: Surface roughness,electrochemical behavior and cellular response

An investigation was made into the electrochemical, structural and biological properties of self-organized amorphous and anatase/rutile titanium dioxide (TiO₂) nanotubes deposited on Ti–35Nb–4Zr alloy through anodization-induced surface modification. The surface of as-anodized and heat-treated TiO₂ nanotubes was analyzed by field emission scanning electron microscopy (FE-SEM), revealing morphological parameters such as tube diameter, wall thickness and cross-sectional length. Glancing angle X-ray diffraction (GAXRD) was employed to identify the structural phases of titanium dioxide, while atomic force microscopy (AFM) was used to measure surface roughness associated with cell interaction properties. The electrochemical stability of TiO₂ was examined by electrochemical impedance spectroscopy (EIS) and the results obtained were correlated with the microstructural characterization. The in vitro bioactivity of as-anodized and crystallized TiO₂ nanotubes was also analyzed as a function of the presence of different TiO₂ polymorphic phases. The results indicated that anatase TiO₂ showed higher surface corrosion resistance and greater cell viability than amorphous TiO₂, confirming that TiO₂ nanotube crystallization plays an important role in the material's electrochemical behavior and biocompatibility.     

减水剂类型对赤泥—矿渣基地聚物注浆材料性能的影响及机理研究

针对赤泥等固体废弃物对环境危害性大且利用率低等问题,以碱激发赤泥-矿渣基地聚物注浆材料为 研究对象,研究了不同掺量的聚羧酸(PA)减水剂、醛酮缩合物(AKC)减水剂和萘系(N)减水剂对材料凝结时间、流动 性及强度等的影响,并通过 XRD、傅里叶红外光谱及 SEM 等设备对减水剂的作用机理进行研究。 结果表明:减水剂增 强了材料的流动性但降低了材料的剪切应力;N 和 PA 减水剂能缩短材料的凝结时间,但 AKC 减水剂会延长材料的凝 结时间;N 和 AKC 减水剂能提高材料的强度,但 PA 减水剂会降低材料的强度;N 减水剂对材料的综合性能提升效果 更加明显,其最优掺量为 0. 7%;减水剂对赤泥-矿渣基地聚物性能提升的作用机理主要是促进地聚合物凝胶的形成。 研究成果为拓展赤泥在工程上的使用途径和效率提供了理论指导。     

Photoregulation of Gene Expression with Ligand-Modified Caged siRNAs through Host/Guest Interaction

Small interfering RNA (siRNA) can effectively silence target genes through Argonate 2 (Ago2)-induced RNA interference (RNAi). It is very important to control siRNA activity in both spatial and temporal modes. Among different masking strategies, photocaging can be used to regulate gene expression through light irradiation with spatiotemporal and dose-dependent resolution. Many different caging strategies and caging groups have been reported for light-activated siRNA gene silencing. Herein, we describe a novel caging strategy that increases the blocking effect of RISC complex formation/process through host/guest (including ligand/receptor) interactions, thereby enhancing the inhibition of caged siRNA activity until light activation. This strategy can be used as a general approach to design caged siRNAs for the photomodulation of gene silencing of exogenous and endogenous genes.     

Spatiotemporal Magnetocaloric Microenvironment for Guiding the Fate of Biodegradable Polymer Implants

The degradation behavior of implants is significantly important for bone repair. However, it is still unprocurable to spatiotemporally regulate the degradation of the implants to match bone ingrowth. In this paper, a magneto-controlled biodegradation model is established to explore the degradation behavior of magnetic scaffolds in a magnetothermal microenvironment generated by an alternating magnetic field (AMF). The results demonstrate that the scaffolds can be heated by magnetic nanoparticles (NPs) under AMF, which dramatically accelerated scaffold degradation. Especially, magnetic NPs modified by oleic acid with a better interface compatibility exhibit a greater heating efficiency to further facilitate the degradation. Furthermore, the molecular dynamics simulations reveal that the enhanced motion correlation between magnetic NPs and polymer matrix can accelerate the energy transfer. As a proof-of-concept, the feasibility of magneto-controlled degradation for implants is demonstrated, and an optimizing strategy for better heating efficiency of nanomaterials is provided, which may have great instructive significance for clinical medicine.     

Mechanical Properties of Single-Layer Diamond Reinforced Poly(vinyl alcohol) Nanocomposites through Atomistic Simulation

Low-dimensional carbon nanostructures are ideal nanofillers to reinforce the mechanical performance of polymer nanocomposites due to their excellent mechanical properties. Through molecular dynamics simulations, the mechanical performance of poly(vinyl alchohol) (PVA) nanocomposites reinforced with a single-layer diamond – diamane is investigated. It is found the PVA/diamane exhibits similar interfacial strengths and pull-out characteristics with the PVA/bilayer-graphene counterpart. Specifically, when the nanofiller is fully embedded in the nanocomposite, it is unable to deform simultaneously with the PVA matrix due to the weak interfacial load transfer efficiency, thus the enhancement effect is not significant. In comparison, diamane can effectively promote the tensile properties of the nanocomposite when it has a laminated structure as it deforms simultaneously with the matrix. With this configuration, the interlayer sp³ bonds endows diamane with a much higher resistance under compression and shear tests, thus the nanocomposite can reach very high compressive and shear stress. Overall, enhancement on the mechanical interlocking at the interface as triggered by surface functionalization is only effective for the fully embedded nanofiller. This work provides a fundamental understanding of the mechanical properties of PVA nanocomposites reinforced by diamane, which can shed lights on the design and preparation of next generation high-performance nanocomposites.