The use of silica‐coated magnetic graphene microspheres as the adsorbent for the extraction of pyrethroid pesticides from orange and lettuce samples followed by GC–MS analysis

Graphene‐grafted ferroferric oxide microspheres were used as the adsorbent to extract some pyrethroid pesticides (bifenthrin, λ‐cyhalothrin, cyfluthrin, cypermethrin, fenvalerate, and deltamethrin) from orange and lettuce samples prior to their determination by GC–MS. The main variables that could affect the extraction, including the amount of the adsorbent, pH of the sample solution, extraction time, concentration of salt, and desorption conditions, were investigated and optimized. Under the optimized conditions, a linear response was obtained in the concentration range of 0.3–100.0 ng/g for the analytes with the coefficients of determination ranging from 0.9877 to 0.9925. The LODs for the pyrethroids ranged from 0.01 to 0.02 ng/g. The method provided a good repeatability with RSDs < 10.6%. The recoveries for the six pyrethroid pesticides were in the range from 90.0 to 103.7%. The method was applied to the determination of the pesticides in orange and lettuce samples with a satisfactory result.     

基于分形理论的飞机雷击初始附着点的数值模拟

飞机雷击附着点的确定能够为飞机防雷设计提供依据,是飞机雷击区域划分和飞机各部件进行雷电试验鉴定的先决条件.本文提出了一种基于分形理论的飞机雷击初始附着点数值模拟的新方法.该方法首先依据标准SAE-ARP5416中有关飞机雷击附着点试验的规定,确定放电间隙、雷电起始坐标、飞机姿态和放电次数等参数,然后根据分形理论,使用电介质击穿模型模拟符合自然界雷电物理机理和几何特征的雷电先导分形发展过程,同时考虑飞机自身触发双向先导的情况,最终得到飞机的雷击附着点分布.通过本文方法仿真模拟得到飞机F-4雷击附着点的分布概率,并分别与该飞机飞行实验和实验室高压放电实验测试得到的真实雷击附着点的概率分布情况比较,结果基本吻合,验证了该方法的有效性.研究结果为飞机雷击附着点仿真模拟提供了一个有潜力的方法,可作为飞机防雷设计和今后开展相关研究工作的基础.     

TFTTP作为阴极缓冲层提高有机薄膜太阳能电池的内建电场和载流子收集效率

采用一种新型的电子传输材料TFTTP作为阴极缓冲层提高基于SubPc/C₆₀异质结的有机薄膜太阳能电池的性能. 通过在有机活性层和金属电极之间加入TFTTP界面层,器件的能量转换效率提高了约30%. 系统研究了器件的二极管特性、光电流特性以及内部的光场分布情况,结果表明,TFTTP阴极缓冲层的引入可以有效地提高器件的内建电场,进而增加电荷转移激子的分离效率. 通过使用TFTTP作为阴极缓冲层,在C₆₀/金属界面形成良好的欧姆接触,降低了界面接触电阻,有利于自由载流子的收集.     

Dynamic property and constitutive model of polyvinyl butaral material at high strain rates

The polyvinyl butaral (PVB) interlayer of automotive windshield plays an important role in the protection of both pedestrian and passenger, the mechanical property of PVB material should be in‐depth studied. In this article, the systematical uniaxial tensile experiments of PVB material under high strain rates are conducted, the strain rates range from 125.6 to 3768 s^?1. The results of experiments show that there exists a phenomenon of stress spurt caused by the stress hardening in the final stage of tension, and the strain rate exerts great influence on mechanical property of PVB material. Further, the data fitting basing on Mooney–Rivlin model is carried out, it is found that the fitting results are consistent with the experiment data, which means that the Mooney–Rivlin constitution model can describe the large deformation behavior of PVB material. At last, the rate‐dependent mechanical behavior of the PVB material is further investigated in this article. On the basis of the experiment results and Johnson–Cook model, a rate‐dependent constitutive model is proposed to describe the tensile mechanical property of PVB material under high strain rates. This work will be beneficial to the simulation and analysis of automotive collision safety and pedestrian safety protection, which are related to damage of automotive windshield. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and crystal structures of two Zinc(II) complexes with 4-hydroxypyridine-2,6-dicarboxylic acid

Two new complexes [Zn(Hpda)(Bth-6)]_2n (I) and [Zn(Hpda)₂] · 2(H-Bpe) (II) (HpdaH₂ = 4-hydroxypyridine-2,6-dicarboxylic acid, Bth-6 = 1,6-bis(1,2,4-triazol-1-yl)hexane, Bpe = 1,2-bi(4-pyridyl)ethene) have been synthesized and characterized structurally. Their X-ray crystal structures show that the two complexes belong to a monoclinic system; space group P2₁/n with a = 11.9328(12), b = 20.975(2), c = 17.1544(17) Å; β = 91.406(2)°, Z = 4 for I; space group P2₁/c with a = 12.7150(19), b = 14.000(2), c = 22.171(3) Å; β = 96.481(2)°, Z = 4 for II. Compound I possesses a one-dimensional (1D) zigzag chain structure, each zinc(II) ion is five-coordinated with a distorted triangle bipyramid geometry. Compound II is discrete mononuclear species, in which the zinc(II) ion is six-coordinated with a distorted octahedral geometry. The [Zn(Hpda)₂]^2? units are connected one-dimensional chain by the intermolecular hydrogen bonds.     

Polyoxometalate‐Based Entangled Coordination Networks Induced by an Extended Bis(triazole) Ligand

The introduction of an extended bridging bis(triazole) ligand, that is, 4,4′‐bis(1,2,4‐triazol‐1‐ ylmethyl)biphenyl (BBPTZ), into the hydrothermal reaction system containing transition metal ions and Keggin‐type polyoxometalates (POMs) led to the isolation of three new organic–inorganic hybrid entangled coordination networks, [Cu^I₂Cu^II(BBPTZ)₆][SiW₁₂O₄₀]?12 H₂O ( 1 ), [Ni(BBPTZ)₂(H₂O)][H₂SiW₁₂O₄₀]?11 H₂O ( 2 ), and [Ni₂(BBPTZ)₄(H₂O)₂][SiW₁₂O₄₀]?3 H₂O ( 3 ). All three compounds were characterized by elemental analysis, IR spectroscopy, TG analysis, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. Compound 1 contains a 2‐D POM‐based metal–organic layer entangled with 1‐D ladder‐like metal–organic chains. The adjacent 2‐D networks are parallel to each other, further stacking into a 3‐D supramolecular framework with 1‐D channels. Compound 2 exhibits a 1‐D cantilever‐type loop‐containing chain. The Keggin‐type POMs act as the cantilever groups, leading to the adjacent catilever‐type chains interwaving together to form a 3‐D supramolecular open framework with two types of channels. Compound 3 possesses a 3‐D open framework based on 2‐D metal–organic undulated layer and Keggin‐type POM clusters. Three sets of such frameworks further interpenetrate with each other to form an interesting three‐fold interpenetrating framework. The photocatalytic activities of compounds 1–3 for the decomposition of methylene blue (MB) under UV light have been investigated.     

A Multifunctional 3D Chiral Porous Ferroelectric Metal–Organic Framework for Sensing Small Organic Molecules and Dye Uptake

A flexible aromatic multicarboxylate ligand and Cd^II ions assemble into a chiral multihelical porous metal–organic framework with second‐order nonlinear optical and ferroelectric properties. The obtained guest‐free form highly selectively senses small organic molecules and adsorbs large dye molecules.     

Constructing Oxygen Vacancies via Engineering Heterostructured Fe3C/Fe3O4 Catalysts for Electrochemical Ammonia Synthesis

Electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions provides an intriguing pathway to convert N₂ into NH₃. However, significant kinetic barriers of the NRR at low temperatures in desirable aqueous electrolytes remain a grand challenge due to the inert N≡N bond of the N₂ molecule. Herein, we propose a unique strategy for in situ oxygen vacancy construction to address the significant trade-off between N₂ adsorption and NH₃ desorption by building a hollow shell structured Fe₃C/Fe₃O₄ heterojunction coated with carbon frameworks (Fe₃C/Fe₃O₄@C). In the heterostructure, the Fe₃C triggers the oxygen vacancies of the Fe₃O₄ component, which are likely active sites for the NRR. The design could optimize the adsorption strength of the N₂ and N_xH_y intermediates, thus boosting the catalytic activity for the NRR. This work highlights the significance of the interaction between defect and interface engineering for regulating electrocatalytic properties of heterostructured catalysts for the challenging NRR. It could motivate an in-depth exploration to advance N₂ reduction to ammonia.     

Substituent Effect to Fine-Tune Energy Levels of Atom-Precise [MoOS3]2− Modified Copper(I) Thiolate Clusters Boosting Recyclable Photocatalysis

The propulsion of photocatalytic hydrogen (H₂) production is limited by the rational design and regulation of catalysts with precise structures and excellent activities. In this work, the [MoOS₃]²⁻ unit is introduced into the Cu^I clusters to form a series of atomically-precise Mo^VI−Cu^I bimetallic clusters of [Cu₆(MoOS₃)₂(C₆H₅(CH₂)S)₂(P(C₆H₄−R)₃)₄] ⋅ xCH₃CN (R=H, CH₃, or F), which show high photocatalytic H₂ evolution activities and excellent stability. By electron push-pull effects of the surface ligand, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels of these Mo^VI−Cu^I clusters can be finely tuned, promoting the resultant visible-light-driven H₂ evolution performance. Furthermore, Mo^VI−Cu^I clusters loaded onto the surface of magnetic Fe₃O₄ carriers significantly reduced the loss of catalysts in the collection process, efficiently addressing the recycling issues of such small cluster-based catalyst. This work not only highlights a competitively universal approach on the design of high-efficiency cluster photocatalysts for energy conversion, but also makes it feasible to manipulate the catalytic performance of clusters through a rational substituent strategy.     

Tunable Chirality of Self-Assembled Dipeptides Mediated by Bipyridine Derivative

Supramolecular peptide assemblies have been widely used for the development of biomedical, catalytical, and optical materials with chiral nanostructures in view of the intrinsic chirality of peptides. However, the assembly pathway and chiral transformation behavior of various peptides remain largely elusive especially for the transient assemblies under out-of-equilibrium conditions. Herein, the N-fluorenylmethoxycarbonyl-protected phenylalanine-tyrosine dipeptide (Fmoc-FY) was used as a peptide assembly platform, which showed that the assembly proceeds multistep evolution. The original spheres caused by liquid-liquid phase separation (LLPS) can nucleate and elongate into the formation of right-handed helices which were metastable and easily converted into microribbons. Interestingly, a bipyridine derivative can be introduced to effectively control the assembly pathway and induce the formation of thermodynamically stable right-handed or left-handed helices at different stoichiometric ratios. In addition, the chiral assembly can also be regulated by ultrasound or enzyme catalysis. This minimalistic system not only broadens the nucleation-elongation mechanisms of protein aggregates but also promotes the controllable design and development of chiral biomaterials.