30%三唑锡悬浮剂的研制及作用机理分析

[目的]解决30%三唑锡悬浮剂分散稳定性的问题。[方法]为提高30%三唑锡悬浮剂分散稳定性,采用流点法对不同类型的分散剂进行初步筛选并测试表面张力,通过测试SC粒径、Zeta电势、悬浮率、流变性能确定分散剂配比与用量并对分散稳定机理进行分析。[结果]与单一分散剂制备SC相比,聚羧酸盐分散剂SD-816和聚氧乙烯醚磷酸酯分散剂SD-208复配体系制备的SC性能较优,其表观黏度、Zeta电势、粒径和悬浮率分别为386 mPa·s、-37.2 mV、2.58μm及98.4%。并且提出了聚羧酸盐分散剂和聚氧乙烯醚磷酸酯分散剂对农药三唑锡可能的分散机理。[结论]聚羧酸盐SD-816和聚氧乙烯醚磷酸酯SD-208的复配体系可同时提供静电排斥作用和空间位阻,明显改善SC体系的悬浮稳定性。     

Molecular Dynamics Simulations Based on 1-Phenyl-4-Benzoyl-1-Hydro-Triazole ERRα Inverse Agonists

Estrogen-related receptor α (ERRα), which is overexpressed in a variety of cancers has been considered as an effective target for anticancer therapy. ERRα inverse agonists have been proven to effectively inhibit the migration and invasion of cancer cells. As few crystalline complexes have been reported, molecular dynamics (MD) simulations were carried out in this study to deepen the understanding of the interaction mechanism between inverse agonists and ERRα. The binding free energy was analyzed by the MM-GBSA method. The results show that the total binding free energy was positively correlated with the biological activity of an inverse agonist. The interaction of the inverse agonist with the hydrophobic interlayer composed of Phe328 and Phe495 had an important impact on the biological activity of inverse agonists, which was confirmed by the decomposition of energy on residues. As Glu331 flipped and formed a hydrogen bond with Arg372 in the MD simulation process, the formation of hydrogen bond interaction with Glu331 was not a necessary condition for the compound to act as an inverse agonist. These rules provide guidance for the design of new inverse agonists.     

Toward Largely Enhanced Toughness and Balanced Strength in PA1012/EPDM Blends via Synergistic Effect of Sacrificial Bonds and Network Structure

Here, zinc-neutralized ethylene propylene diene monomer (EPDM) ionomers with different neutralization levels are prepared through melt blending, and are then incorporated with polyamide 1012 (PA1012) to fabricate PA1012/EPDM ionomer blends. Interestingly, complex crosslinking networks are formed in the blends due to the construction of sacrificial bonds (Zn²⁺-carboxyl, Zn²⁺-amide). The as-formed network structure and sacrificial bond endow the PA/EPDM blends with largely enhanced toughness (16 times higher than that of neat PA), as well as balanced strength and stiffness. Meanwhile, the rheological behaviors of PA1012/EPDM ionomer blends indicate their relative low melting viscosity, which can avoid the processing shortcomings of plastics toughened with rubber. Moreover, PA1012/EPDM ionomer blends show obvious gelation behavior, and a maximum notched Izod impact strength exhibited at the gel point, in which unique double network structure can be observed obviously, indicating that there is a corresponding correlation between the rheological and mechanical parameters. Furthermore, the supper-toughening mechanism of PA1012/EPDM ionomer blends at gel point is explored, which origins from the large deformation and cavitation of rubber particles and the destruction of special double network morphologies. This study provides a novel and effective strategy to fabricate PA materials with outstanding toughness and excellent strength simultaneously.     

Hygroresponsive Torsional Yarns and Actuators Based on Cascade Amplification of the Deformation

Fiber-based hygroresponsive torsional actuators provide desirable merits, such as light weight and shapeability, for developing smart systems to harvest energy from moisture which is a ubiquitous natural resource. A key challenge in this development is to realize moisture-triggered actuation combining large actuation and rapid responses. Here, a multiscale design strategy is explored to create high-performance hygroresponsive torsional actuators consisting of chitosan and multiwalled carbon nanotubes (MWCNTs). The superior actuation performance arises from the synergism of contributing factors at different scales, including 1) MWNCTs accelerate the water transport in primary twisted fibers (PTFs), fostering the rotation of PTFs upon moisture stimuli; 2) in situ-formed hierarchically-assembled twists realize cascade amplification of moisture-triggered actuation. Specifically, PTFs are self-twisted to generate secondary helical yarns, that are subsequently over-twisted to yield tertiary coiled yarn. The resultant yarn actuator can reach a maximum rotation speed of 11 400 rpm in 5 s, output gravitational potential energy of 2.4 J kg⁻¹ and gravitational potential power of 0.053 W kg⁻¹ during contraction. This work represents the first design of fiber-based actuators by virtue of moisture-triggered in situ formation of yarns. The established principles of multiscale design will enable high-performance fiber-based hygroresponsive actuators toward advanced intelligent textile and soft robotics.     

Importance of Low-Temperature Melt-Mixing on the Construction of Stereocomplex Crystallites with Superior Nucleation Efficiency in Asymmetric Poly(l-lactide)/Poly(d-lactide) Blends

The nucleation efficiency (NE) of stereocomplex crystallites (SCs) formed in asymmetric poly(L-lactide)/poly(D-lactide) (PLLA/PDLA) blends is generally unsatisfactory because the competition between stereocomplexation and chain mixing involved in the melt-mixing process can cause low formation efficiency and even severe aggregation of SCs. Herein, it is attempted to achieve high-efficient formation of finely dispersed SCs particles by designing a unique melt-mixing procedure, where the mixing of PLLA with 0.75 wt% PDLA is first performed at elevated temperatures (far above the melting temperature of SCs) to allow the homogeneous mixing of PLLA/PDLA chains and then at a low temperature (slightly above that of homocrystallites) to permit the full stereocomplexation of the premixed chains. It is found that the SCs formed in the blends exhibit unexpectedly low NEs (e.g., 54.5%), much inferior to that (73.6%) in the counterpart without undergoing premixing. This is because the introduction of premixing leads to a remarkable deterioration in the amount of SCs particles formed, despite decreased particle size, highlighting that the direct mixing at low temperatures of 170–180 °C (about 20–30 °C lower than that used in common melt-processing of PLA) is more effective for the construction of SCs with superior NE. The mechanisms for these striking findings are discussed.     

A Dual Physical Cross-Linking Strategy to Construct Tough Hydrogels with High Strength,Excellent Fatigue Resistance,and Stretching-Induced Strengthening Effect

Hydrogels with excellent stiffness, toughness, anti-fatigue, and self-recovery properties are regarded as promising water-containing materials. In this work, a dual physically cross-linked (DPC) sodium alginate (SA)/poly[acrylamide (AAm)-acrylic acid (AAc)-octadecyl methacrylate (OMA)]-Fe³⁺ hydrogel is reported, which is constructed by hydrophobic association (HA) and ionic coordination (IC). The optimal DPC hydrogel demonstrates excellent mechanical performance: tensile modulus of 0.65 MPa, tensile strength of 3.31 MPa, elongation at break of 1547%, and toughness of 27.8 MJ m^–3. SA/P(AAm-AAc-OMA)-Fe³⁺ DPC hydrogels also exhibit prominent anti-fatigue and self-recovery performance (99.1–109.7% modulus recovery and 90.4–108.9% dissipated energy recovery after resting for 5 min without additional stimuli at ambient temperature) through the reconstruction of reversible physical cross-linking. Some of the SA/P(AAm-AAc-OMA)-Fe³⁺ DPC hydrogels even exhibit a stretching-induced strengthening effect, which is similar to the performance of muscle—“the more training, the more strength.” Hence, the combination of HA and IC will provide an effective approach to design DPC hydrogels with desirable mechanical performances and a longer service life for wider applications of soft materials.     

Preparation of Iron Filler-Based Photocomposites and Application in 3D Printing

The introduction of metallic fillers to polymers via the photopolymerization approach can endow the composite materials with some unique properties, but the relevant research is still scarce due to the issue of light penetration and inner filter effect. Herein, for the first time the fabrication of photocomposites based on fine iron powder (i.e., a typical kind of metallic filler) is reported in this work. The free radical polymerization of two different acrylate monomers, poly(ethylene glycol) diacrylate and trimethylolpropane triacrylate, is performed in the presence of iron filler under mild conditions (i.e., light emitting diode (LED)@405 nm irradiation at room temperature under air). And the real-time Fourier transform infrared spectroscopy reveals remarkable photopolymerization kinetics of acrylates with high final conversions and fast polymerization rates despite the increasing contents of iron filler in the composites. Interestingly, the 3D printing technique is applied to the iron filler-based composites to produce tridimensional patterns with excellent spatial resolution. This work not only paves the way for the investigation of photocomposites based on metallic fillers through photochemical methods, but also broadens the potential application prospects.     

Dissipative Particle Dynamics Simulation: A Review on Investigating Mesoscale Properties of Polymer Systems

Polymer systems have typical multiscale characteristics, both in space and time. The mesoscopic properties of polymers are difficult to describe through traditional experimental approaches. Dissipative particle dynamics (DPD) is a simulation method used for solving mesoscale problems of complex fluids and soft matter. The mesoscopic properties of polymer systems, such as conformation, dynamics, and transport properties, have been studied extensively using DPD. This paper briefly summarizes the application of DPD to research involving microchannel flow, electrospinning, free-radical polymerization, polymer self-assembly processes, polymer electrolyte fuel cells, and biomedical materials. The main features and possible development avenues of DPD are described as well.     

Synergistic Flame Retardant Effects of Carbon Nanotube-Based Multilayer Nanocoatings

In an effort to develop highly functionalized flame retardant materials, hybrid nanocoatings are prepared by alternately depositing a positively charged polyaniline (PANi) and negatively charged montmorillonite (MMT) using the layer-by-layer (LbL) assembly technique. Carbon nanotubes (CNTs) are employed in polymer nanocomposites as effective reinforcement, where nanotubes are stabilized in MMT aqueous solution. The 3D structure and high density of CNTs deposited in the PANi/CNTs-MMT multilayers produce thicker and heavier coatings in comparison to the LbL assemblies without CNTs. Vertical and horizontal flame testing show that the incorporation of CNTs improves fire resistance. Additionally, cone calorimetry reveals that stacking two nanomaterials (MMT and CNTs) in a single coating shows a significant reduction in peak heat release rate (up to 51%), total smoke release (up to 47%), and total heat release (up to 37%) for the polyurethane foam. The enhancement of flame retardancy is attributed to a synergistic effect; MMT serves as a physical barrier that retards the diffusion of heat and gas. The addition of CNTs strengthens the thermal stability and high char yield. These results, coupled with the simplicity with which the LbL deposition is applied, present a viable alternative to halogen-free flame retardant nanocoatings to natural and synthetic fibers.     

Perm-Inspired High-Performance Soy Protein Isolate and Chicken Feather Keratin-Based Wood Adhesive without External Crosslinker

Crosslinking modification can effectively improve the water resistance of soy protein isolate (SPI) adhesive, but it often depends on petroleum-based reagents, violating the concept of green environmental protection. Here, inspired by the breaking and recombination of the disulfide bond in the perm process, a high-performance wood adhesive is prepared by incorporation of SPI (modified by sodium sulfite to cleave the disulfide bonds of protein chains) and feather keratin (FK, extracted from waste chicken feathers by breaking the disulfide bond) without using any other crosslinkers. The crosslinking reaction occurs by disulfide bonds derived from the sulfhydryl group of FK and SPI. Thus the wet shear strength of the SPI/FK-20 adhesive is improved from 0.57 to 1.18 MPa, an increment of 107%. This study provides a green strategy to prepare high-performance protein-based adhesive from the waste products-chicken feathers, which will contribute to the development of the environmentally friendly wood adhesive industry.